Process for producing an oil and water absorbent polymer capable of entrapping solid particles and liquids and the product thereof

Abstract: The present invention is directed to a porous polymer microparticle, in the form of broken spheres, open to a porous oleophilic interior surface area, having a high oil and water absorbency and an apparent bulk density of about 0.008 to about 0.1 grams/cc. The preferred method of the present invention comprises the steps of: dissolving at least one, and preferably at least two, polyunsaturated monomers along with an effective amount of an organic polymerization initiator in a water-immiscible organic solvent to provide a monomer mixture; adding the monomer mixture to an aqueous solution, preferably having an effective amount of a suspension stabilizer dissolved therein, to form an organic/aqueous biphasic liquid system; vigorously agitating the biphasic liquid system at a rate sufficient to cause the water-immiscible organic phase to be suspended as microdroplets in the aqueous phase; continuing vigorous agitating during polymerization of the monomers in the suspended microdroplets to produce a microporous polymer microparticle; and separating the microporous polymer microparticle from the organic solvent to produce a microporous and oil sorbent polymer microparticle having a mean unit diameter of less than about 50 microns and a total sorptive capacity for mineral oil that is at least about 72% by weight, preferably at least about 90% by weight dry polymer basis.

Description: BACKGROUND OF THE INVENTION A. Field Of The Invention The present invention relates to a process for producing an oil and water adsorbent polymer in broken microparticle form capable of entrapping any desired solid and/or liquid oleophilic and/or hydrophilic compound and composition (organic and/or aqueous) for delivery. More particularly, the present invention relates to a process for producing a highly porous and highly crosslinked hydrophilic/oleophilic polymer in the form of open (broken) spheres and sphere sections characterized by a mean unit particle size of about 0.5 to about 3000 microns, preferably about 1 to about 300 microns, more preferably about 0.5 to about 100 microns, and most preferably, for cosmetic uses, about 0.5 to about 80 microns. The microparticles have an oil sorbency of at least about 72% by weight, preferably at least about 80% by weight (calculated as weight of material sorbed divided by total weight of material sorbed plus dry weight of polymer sorbent). The present invention is also directed to the oil and water adsorbent microparticles produced by the process having an extremely low bulk density in the range of about 0.008 gm/cc to about 0.1 gm/cc, preferably about 0.009 gm/cc to about 0.07 gm/cc, more preferably about 0.0095 gm/cc to about 0.04-0.05 gm/cc. The microparticles produced by the process of the present invention are capable of holding and releasing oleophilic oils, creams, cleaners, medicaments, and other organic active compounds and compositions, as well as hydrophilic active compounds and aqueous compositions, individually, or both oleophilic and hydrophilic materials simultaneously, for use in the cosmetic, cleaning, chemical process, and pharmaceutical industries. B. Background Early disclosures of polymer particles appear in U.S. Patents 3,493,500 and 3,658,772. These patents disclose the production of aqueous suspensions of polymer particles from acrylic acid monomer and/or acrylamide monomer in an aqueous reaction medium at pH 1-4. Both patents teach that the result in polymer suspensions, which were not characterized as to particle size or structure, were suitable for use as flocculating agents for sewage treatment. It was subsequently discovered that polymers could be made in a porous particulate form by a variety of techniques. The art has stated that "the type of polymerization technique used is an important factor in the determination of the resulting product." See U.S. Patent No. 4,962,170 at column 2, line. 4. As stated in U.S. Patent No. 4,962,170 at column 2, lines 7-11, "within each type of polymerization, there are procedural alternatives which can have significant impact on the resulting product" "[t]he differences in the polymerization techniques are enough that a procedure used in one type of polymerization technique that will not necessarily have the same effect if used in another polymerization technique." Thus, there is a significant degree of unpredictability in the art. Porous polymeric particles are capable of being prepared by one of two processes, i.e., precipitation polymerization in a single solvent system, or suspension polymerization in a two phase liquid system. The precipitation polymerization technique is disclosed in U.S. Patent Nos. 4,962,170 and 4,962,133. U.S. Patent No. 4,962,170 discloses a precipitation polymerization process wherein the disclosed monomers are soluble in the single solvent system, and the resulting polymer, which is insoluble, precipitates out of solution once a critical size is obtained. In the disclosed process, the solution of monomer consists exclusively of one or more types of polyunsaturated monomer. Because each monomer is polyunsaturated, each monomer also functions as a crosslinker, resulting in a highly crosslinked polymer particle. U.S. Patent No. 4,962,133 also utilizes the precipitation polymerization process for producing a porous polymeric particle. However, unlike the above-described process, wherein the monomer solution consists exclusively of polyunsaturated monomers, the process of U.S. Patent No. 4,962,133 discloses that the monomer solution can include one monosaturated monomer in combination with one polyunsaturated monomer, wherein the polyunsaturated monomer can comprise up to 90% by weight of the total weight of monomers. Because the precipitation polymerization technique relies upon the formation of polymer aggregates of precipitated polymer particles, the monomer solution is not vigorously agitated during polymerization in order to avoid separation of the aggregated polymer particles. U.S. Patent No. 5,316,774 is directed to a suspension polymerization process, again limited to a maximum of 90% by weight polyunsaturated monomers, based on the total weight of monomers. Accordingly, it is an object of the present invention to provide a process for making sorbent microparticles from a monomer solution that contains more than 90%, preferably about 92% to 100%, by weight, polyunsaturated monomers, based on the total weight of monomers in the monomer solution. The process of U.S. Patent No. 4,962,133 is limited to a solvent system that is an aqueous/organic azeotrope. Because the organic solvent cannot be separated from the water in an azeotrope, azeotropic solutions present special waste disposal problems. Accordingly, it is an object of the present invention to provide a process for making oil and water adsorbent microparticles that do not require an azeotropic solution. Further, the particles produced by the process of U.S. Patent No. 4,962,133 range extensively in size from less than about 1 micron in average diameter for unit particles to about twelve hundred microns in average diameter for clusters of fused aggregates. The large variability in size limits the utility and properties of the polymeric particles. Accordingly, it is also an object of the present invention to provide a process for making polymeric microparticles of a less diverse size distribution. Another process disclosed in the art for producing microscopic polymeric particles is in situ suspension polymerization wherein an active ingredient included within the monomer mixture is retained in the formed polymer upon completion of polymerization. Examples of in situ suspension polymerization include U.S. Patent No. 4,724,240, wherein polymerization of a monounsaturated monomer and a polyunsaturated monomer in an aqueous/polyvinylpyrrolidone system containing an emollient, as the active agent, produced relatively large microparticles, having a mean diameter "between 0.25 to 0.5 mm" (i.e., 250 to 500 microns), that contain the emollient therein upon completion of polymerization. A problem with a particle having a mean diameter of 250-500 microns is that the particle is capable of being sensed by touch. This is an undesirable property if the particle is to be used in a lotion, cream, or other cosmetic formulations. Accordingly, it is also an object of the present invention to provide a process that is capable of manufacturing polymeric particles having a smaller mean diameter, e.g., about 0.5 µm to about 120 µ m, preferably about 1 µm to about 100 µm, for a smoother skin feel. A second problem with the process of U.S. Patent No. 4,724,240 is that it is limited to those active ingredients that are capable of dissolving in the organic solvent. Further, the active ingredient(s), which may be proprietary, are provided in bulk to the polymer manufacturer so that they can become trapped in the particles during the polymerization process. To overcome these problems, it is a further object of the present invention to provide polymeric microparticles having evacuated internal pores, within broken (open) microparticle spheres and sphere portions that are capable of adsorbing both oleophilic and hydrophilic solids and liquids in higher amounts than prior art microparticles. It is theorized that the oleophilic solids and liquids are adsorbed within the interior porous surface area of each open sphere or sphere portion, in large amounts, so that they may be loaded within the interior of the spheres with adsorbed active oleophilic organic ingredient(s) in solid or solvent-dissolved form, and it is theorized that the exterior porous surface area of the broken spheres adsorb both hydrophilic and oleophilic solids and liquids via capillary adsorption in the porous outer surface (oleophilic materials) or by surface attraction of hydrophilic materials. The polymeric microparticles of the present invention are capable of adsorbing both (a) organic compounds and organic compositions containing oleophilic compounds dissolved in an organic solvent, as well as solid organic compounds entrapped within an interior of the open (broken) microparticle sphere pores; and (b) liquid hydrophilic compounds and hydrophilic aqueous compositions containing watersoluble compounds dissolved in water, as well as solid hydrophilic solid compounds that are adsorbed on an exterior, porous surface area of the broken spheres. A third problem with the process of U.S. Patent No. 4,724,240 is that it is not suited for use when the active ingredient is a mixture of components that differ significantly from one another as to oleophilicity. In such a situation, the more oleophilic of the active ingredients would be selectively isolated in the pores of the polymer made by the process of U.S. Patent No. 4,724,240. To overcome this problem, the process of U.S. Patent No. 4,724,240 would have to be separately applied to each of the active ingredients, and thereafter, the resulting products would be mixed. Such additional processing and mixing is costly. Accordingly, it is a further object of the present invention to provide a process for producing a microparticle wherein the microparticle is capable of receiving a plurality of oleophilic active ingredients and/or a plurality of hydrophilic active ingredients. WO 96/40809 describes the production of a terpolymer from butyl methacrylate, allyl methacrylate and an ethylene glycol dimethacrylate in a mole ratio of about 1:3 to 5:5 to 7. There is, however, no disclosure or suggestion of eliminating the monounsaturated monomer from the reaction mix. SUMMARY OF THE INVENTION It was unexpectedly discovered that the process of the present invention is capable of producing microparticles in a more uniform and more narrow particle size distribution that have not only a high oil adsorbency, but that also exhibit a high adsorbency for water, hydrophilic compounds, and aqueous compositions. The oleophilic materials and hydrophilic materials can be adsorbed alone or together to deliver materials separately or simultaneously. Both materials can be held simultaneously in the microparticles of the present invention. Prior art materials, such as Dow DC-5640, can hold oleophilic or hydrophilic materials, but not both simultaneously. According to one aspect of the present invention there is provided a process for producing a microporous oil and water sorbent polymer comprising the steps of: dissolving at least one polyunsaturated monomer in a substantially water- immiscible organic solvent to provide a monomer mixture containing more than 60% by weight polyunsaturated monomers, based on a weight of the monomers; said monomer mixture containing no monounsaturated monomer combining the monomer mixture with an aqueous solution to form a biphasic liquid system; shearing the biphasic liquid system in an amount sufficient to suspend the water-immiscible organic phase, containing the dissolved monomers, as microdroplets in the aqueous phase; polymerizing the monomers in the suspended microdroplets during shearing to produce a microporous, copolymer microparticle therein; and separating the microporous polymer microparticle from the substantially water-immiscible organic solvent to produce a microporous oil and water adsorbent polymer microparticle, in the form of broken spheres, having a mean unit diameter of less than about 50 microns, and having a bulk density of about 0.008 to about 0.1 gm/cc. Preferably the biphasic liquid composition is vigorously agitated at a rate sufficient to cause the water-immiscible organic phase to be suspended as microdroplets in the aqueous phase, and the vigorous agitation is continued during polymerization of the monomers in the suspended microdroplets to produce microporous polymer microparticles in the form of broken (i.e., open) spheres. Preferably the microparticle produced has a mean unit diameter of less than about 25 microns, more preferably less than about 20 microns. The microparticle has a new and unexpected adsorptive capacity for both hydrophobic and hydrophilic compounds, in both solid and liquid (organic solvent and aqueous) forms. According to a second aspect of the invention there is provided a microsporous oil and water sorbent microparticle comprising a copolymer of a first diunsaturated monomer and a second diunsaturated monomer, in a mole ratio of about 1:1 to about 1:2, wherein the microparticle has a mean unit diameter of less than about 50 microns, a bulk density of about 0.008 to about 0.1 gm/cc, and a total sorption capacity for mineral oil that is 72% by weight or greater, said copolymer being free from monounsaturated monomer. According to a third aspect of the invention there is provided a microporous oil and water sorbent microparticle comprising a terpolymer of butyl methacrylate, allyl methacrylate, and an ethylene glycol dimethacylate, in a mole ratio of about 1:3 to 5:5 to 4, respectively, said microparticle having a mean unit diameter of less than about 50 microns, a bulk density of about 0.008 to about 0.1 gm/cc, and a total sorption capacity for mineral oil that is 72% by weight or greater, said terpolymer being free from monounsaturated monomer. According to a fourth aspect of the invention there is provided a microporous oil and water sorbent microparticle comprising a polymer of at least one polyunsaturated monomer, wherein the microparticle has a mean unit diameter of less than about 50 microns and a bulk density of about 0.008 to about 0.1 gm/cc, said polymer being free from monounsaturated monomer. The present invention is further directed to microporous oil- and water-adsorbent microparticles comprising a polymer that includes at least two polyunsaturated monomers, the microparticle characterized by being open to its interior, by virtue of particle fracture upon removal of the porogen after polymerization, or by virtue of subsequent milling, and having a mean unit diameter of less than about 50 microns, preferably less than about 25 microns, having a total adsorption capacity for organic liquids, e.g., mineral oil, within the pores of the interior, porous surface area of the particles, that is at least about 72% by weight, preferably at least about 80% by weight, and an adsorption capacity for hydrophilic compounds and aqueous solutions of about 70% to about 93% by weight, preferably about 75% to about 93% by weight. In a preferred embodiment, the broken sphere microparticles of the present invention are characterized by a mean unit diameter from about 1 to about 50 microns, more preferably from about 1 to about 25 microns, most preferably, from about 1 to about 20 microns. BRIEF DESCRIPTION OF THE FIGURES FIGS. 1 and 2 are graphs showing the time release of silicone fluid (DC 244) and vitamin E acetate, respectively, from the PolyPore E of Example 1, (tested under 10 liter/min air velocity), compared to vaporization of these materials from a nonsorbent open dish (blank); FIGS. 3-5 are photographs of the microparticles of Example 1 magnified 100, 1500 and 10000 times, respectively; FIGS. 6 and 7 are graphs showing oil adsorbance vs. bulk density and oil adsorbance vs. monomer concentration, respectively; and FIG. 8 is a graph showing bulk density vs. monomer concentration. DETAILED DESCRIPTION OF THE INVENTION The present invention has two aspects. In its first aspect, it is directed to a process for making a polymer in a porous microparticle form that is capable of sorbing high volumes of one or both of oleophilic (hydrophobic) and hydrophilic compounds in solid and/or liquid forms. Oleophilic compounds are adsorbed within the interior of the broken spheres, and adsorbed by capillary adsorption within pores in the outer surface area, and hydrophilic compounds are adsorbed on the exterior surfaces of the spheres, theoretically by electrostatic attraction with the exterior surfaces of the spheres by virtue of the surrounding water molecules present during the polymerization process. The preferred process of the present invention comprises the steps of: dissolving at least one, and preferably at least two, polyunsaturated monomers, along with an effective amount of an organic polymerization initiator, in a water-immiscible organic solvent to provide a monomer mixture; adding the monomer mixture to an aqueous solution, preferably having an effective amount of a suspension stabilizer dissolved therein, to form an organic/aqueous biphasic liquid system including an organic phase and an aqueous phase; vigorously agitating or otherwise shearing the biphasic liquid system at a rate sufficient to cause the water-immiscible organic phase to be suspended as microdroplets in the aqueous phase, e.g., by rotating a stirring paddle at a tip speed of about 1 to about 15 meters per second, preferably at least about 5 meters per second, most preferably about 8 meters per second. continuing said vigorous agitation or other shear means during polymerization of the monomers in the suspended microdroplets to produce a microporous polymer microparticle; and separating the microporous polymer microparticle from the organic solvent to produce microporous, oil and water adsorbent polymer microparticles in the form of broken spheres having a mean unit diameter of less than about 50 microns and a new and unexpected adsorptive capacity for both oleophilic and hydrophilic compounds, in both solid and liquid (organic solvent and aqueous) forms. The term "sorptive" (or "sorption") is used herein to refer to the capability or capacity of the microparticles of the present invention to both adsorb and absorb lipophilic and hydrophilic materials. However, the amount of liquid that is absorbed is negligible in comparison to the amount of oleophilic and hydrophilic solids and/or liquids that are adsorbed on both the interior and exterior, respectively, of the broken spheres. In discussing microparticles, the art loosely uses the term "adsorptive," such as in "total adsorptive capacity" or in "free flowing adsorptive capacity." However, it is understood that references in the art to "total adsorptive capacity" inherently include the total absorptive capacity of a particle as well as its adsorptive capacity, unless otherwise defined. Likewise, references in the art to "free flowing adsorptive capacity" also inherently include both the absorptive and adsorptive capacities. The process of the present invention preferably copolymerizes at least two polyunsaturated (polyethylenically unsaturated) monomers, preferably allyl methacrylate and an ethylene glycol dimethacrylate. Both the allyl methacrylate and the ethylene glycol dimethacrylate are diunsaturated monomers. The diunsaturated monomers also function as crosslinking agents. The water immiscible organic solvent preferably comprises an aliphatic hydrocarbon selected from the group consisting of a C 5 to C 12 alkane, a C 5 to C 8 cycloalkane, a volatile hydrocarbon having the structure wherein n is 2 to 5. The aliphatic hydrocarbon preferably comprises a heptane, a cyclo-hexane, or a mixture thereof. The aromatic hydrocarbon preferably comprises benzene, toluene, xylene, and mixtures thereof. Preferably the process further comprises adding a suspension stabilizer to the monomer mixture, wherein the suspension stabilizer is selected from the group consisting of starch, gum arabic, polyvinyl alcohol, sodium polymethacrylate, magnesium silicate, sodium bentonite, magnesium hydroxide, methylcellulose, polyvinylpyrrolidone, calcium phosphate, magnesium phosphate, lignite, and mixtures thereof. A preferred suspension stabilizer is methylcellulose. The invention also includes the microparticles produced by the procedures of the invention. The highly crosslinked polymeric microparticles of this invention are prepared by polymerizing at least one, and preferably at least two, monomers having at least two unsaturated bonds (hereinafter referred to as "polyunsaturated" monomers), said monomers being polymerized including no more than about 40%, preferably less than about 9%, by weight, by total monomer weight of monounsaturated comonomers. Examples of polyunsaturated monomers can be polyacrylates ("poly" meaning two or more), -methacrylates, or -itaconates of: ethylene glycol, propylene glycol; di-, tri-, tetra-, or polyethylene glycol and propylene glycol; trimethylol propane, glycerine, erythritol, xylitol, pentaerythritol, dipentaerythrieol, sorbitol, mannitol, glucose, sucrose, cellulose, hydroxyl cellulose, methylcellulose, 1,2- or 1,3-propanediol, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanediol, or cyclohexanetriol. Similarly, bis(acrylamido or methacrylamido) compounds can be used. These compounds are, for example, methylene bis(acryl or methacryl)amide, 1,2-dihydroxy ethylene bis(acryl or methacryl)amide, hexamethylene bis(acryl or methacryl)amide. Another group of useful monomers could be represented by di or polyvinyl esters, such as divinyl propylene urea, divinyl-oxalate, -malonate, -succinate, -glutamate, -adipate, -sebacate, -maleate, - fumerate, -citraconate, and -mesaconate. Other suitable polyunsaturated monomers include divinyl benzene, divinyl toluene, diallyl tartrate, allyl pyruvate, allyl maleate, divinyl tartrate, triallyl melamine, N,N'-methylene bis acrylamide, glycerine dimethacrylate, glycerine trimethacrylate, diallyl maleate, divinyl ether, diallyl monoethylene glycol citrate, ethylene glycol vinyl allyl citrate, allyl vinyl maleate, diallyl itaconate, ethylene glycol diester of itaconic acid, divinyl sulfone, hexahydro-1,3,5-triacryltriazine, triallyl phosphite, diallyl ether of benzene phosphonic acid, maleic anhydride triethylene glycol polyester, polyallyl sucrose, polyallyl glucose, sucrose diacrylate, glucose dimethacrylate, pentaerythritol di-, tri- and tetra- acrylate or methacrylate, trimethylolpropane di- and triacrylate or methacrylate, sorbitol dimethacrylate, 2-(1-aziridinyl)-ethyl methacrylate, triethanolamine diacrylate or dimethacrylate, triethanolamine triacrylate or trimethacrylate, tartaric acid dimethacrylate, triethylene glycol dimethacrylate, the dimethacrylate of bis-hydroxy ethylacetamide and the like. Other suitable polyethylenically unsaturated crosslinking monomers include ethylene glycol diacrylate, diallyl phthalate, trimethylolpropane trimethacrylate, polyvinyl and polyallyl ethers of ethylene glycol, of glycerol, of pentaerythritol, of diethylene glycol, of monothio- and dithio-derivatives of glycols, and of resorcinol; divinylketone, divinylsulfide, allyl acrylate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallyl aconitrate, triallyl citrate, triallyl phosphate, divinyl naphthalene, divinylbenzene, trivinylbenzene; alkyldivinylbenzenes having from 1 to 4 alkyl groups of 1 to 2 carbon atoms substituted on the benzene nucleus; alkyltrivinylbenzenes having 1 to 3 alkyl groups of 1 to 2 carbon atoms substituted on the benzene nucleus; trivinylnaphthalenes, and polyvinylanthracenes. In addition, acryl or methacryl-encapped siloxanes and polysiloxanes, methacryloyl end-capped urethanes, urethane acrylates of polysiloxane alcohols and bisphenol A bis methacrylate and ethoxylated bisphenol A bis methacrylate also are suitable as polyunsaturated monomers. Still another group of monomers is represented by di or polyvinyl ethers of ethylene, propylene, butylene, and the like, glycols, glycerine, penta erythritol, sorbitol, di or poly allyl compounds such as those based on glycols, glycerine, and the like, or combinations of vinyl allyl or vinyl acryloyl compounds such as vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, methallyl methacrylate, or methallyl acrylate. In addition, aromatic, cycloaliphatic and heterocyclic compounds are suitable for this invention. These compounds include divinylbenzene, divinyltoluene, divinyldiphenyl, divinylcyclohexane, trivinylbenzene, divinylpyridine, and divinylpiperidine. Furthermore, divinylethylene or divinylpropylene urea and similar compounds may be used, e.g., as described in U.S. Patent Nos. 3,759,880, 3,992,562, and 4,013,825, hereby incorporated by reference. Acryloyl- or methacryloyl end-capped siloxane and polysiloxanes such as those described in U.S. Patent Nos. 4,276,402, 4,341,889, French Patent No. 2,465,236, and German Publication No. DE 30 34 505, hereby incorporated by reference, are suitable for this invention. Methacryloyl end-capped urethanes, such as those described in U.S. Patent Nos. 4,224,427, 4,250,322, and 4,423,099, German Publication Nos. DE 23 65 631 and DE 25 42 314, Japanese Patent Application Nos. 60-233,110, 61-09,424, and 61-30,566, and British Patent No. 1,443,715, are suitable for this invention. Urethane acrylates of polysiloxane alcohols, as described in U.S. Patent Nos. 4,543,398 and 4,136,250, and bisphenol A, bismethacrylate, and ethoxylated bisphenol A bismethacrylate are also suitable monomers for this invention. Monoethylenically unsaturated monomers suitable, in an amount up to about 40%, and preferably less than about 9% by weight, based on the total weight of monomers, for preparing polymer microparticles include ethylene, propylene, isobutylene, disobutylene, styrene, vinylpyridine, ethylvinylbenzene, vinyltoluene, and dicyclopentadiene; esters of acrylic and methacrylic acid, including the methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, hexyl, octyl, ethylhexyl, decyl, dodecyl, cyclohexyl, isobornyl, phenyl, benzyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxyproyl, propoxymethyl, propoxyethyl, propoxypropyl, ethoxyphenyl, ethoxybenzyl, and ethoxycyclohexyl esters; vinyl esters, including vinyl acetate, vinyl propionate, vinyl butyrate and vinyl laurate, vinyl ketones, including vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropyl ketone, and methyl isopropenyl ketone, vinyl ethers, including vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl isobutyl ether; and the like. Other monounsaturated monomer materials which can be utilized in accordance with the present invention, in an amount up to about 40%, and preferably less than about 9% by weight, based on the total weight of monomers in the monomer solution, include hydroxy alkyl esters of alpha, beta-unsaturated carboxylic acids, such as 2-hydroxy ethylacrylate or methacrylate, hydroxypropylacrylate or methacrylate and the like. Many derivatives of acrylic or methacrylic acid other than the esters mentioned are also suitable as starting monounsaturated monomer materials for use in forming the unsaturated polymer microparticles of the present invention. These include, but are not limited to, the following monomers: methacrylylglycolic acid, the monomethacrylates of glycol, glycerol, and of other polyhydric alcohols, the monomethacrylates of dialkylene glycols and polyalkylene glycols, and the like. The corresponding acrylates in each instance may be substituted for the methacrylates. Examples include the following: 2-hydroxyethyl acrylate or methacrylate, diethylene glycol acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, tetraethylene glycol acrylate or methacrylate, pentaethylene glycol acrylate or methacrylate, dipropylene glycol acrylate or methacrylate, acrylamide, methacrylamide, diacetone acrylamide methylolacrylamide or methylolmethacrylamide, any acrylate or methacrylate having one or more straight or branched chain alkyl groups of 1 to 30 carbon atoms, preferably 5 to 18 carbon atoms, and the like. Other suitable examples include isobornyl methacrylate, phenoxyethyl methacrylate, isodecyl methacrylate, stearyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, 2-acrylamido propane sulfonic acid, 2-ethylexyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, and methoxyethyl methacrylate. Examples of monounsaturated monomers containing carboxylic acid groups as functional groups and suitable for use as starting materials in accordance with the invention include the following: acrylic acid, methacrylic acid, itaconic acid, aconitic acid, cinnamic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid and the like. Partial esters of the above acids are also suitable as monosaturated monomers for use in accordance with the invention. Instances of such esters include the following: mono-2-hydroxypropyl aconitate, mono-2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monoethyl itaconate, monomethyl cellosolve ester of itaconic acid, monomethyl cellosolve ester of maleic acid, and the like. Instances of suitable monounsaturated monomers containing amino groups as functional groups include the following: diethylaminoethyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate, monoethylaminoethyl acrylate or methacrylate, tert. butylaminoethyl methacrylate, para-amino styrene, ortho-amino styrene, 2-amino-4-vinyl toluene, piperidinoethyl methacrylate, morpholinoethyl methacrylate, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-ethyl-5-vinylpyridine, dimethylaminopropyl acrylate and methacrylate, dimethylaminoethyl vinylether, dimethylaminoethyl vinylsulfide, diethylaminoethyl vinyl ether, aminoethyl vinyl ether, 2-pyrrolidinoethyl methacrylate, 3-dimethylaminoethyl-2-hydroxy-propyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, isopropyl methacrylamide, N-methyl acrylamide or methacrylamide, 2-hydroxyethyl acrylamide or methacrylamide, 1-methacryloyl-2-hydroxy-3-trimethyl ammonium chloride or sulfomethylate, 2-(1-aziridinyl)-ethyl methacrylate, and the like. Polyethylenically unsaturated monomers which ordinarily act as though they have only one unsaturated group, such as isopropene, butadiene and chloroprene, should not be calculated as part of the polyunsaturated monomer content, but as part of the monoethylenically unsaturated monomer content. The process of the present invention preferably utilizes an effective amount of an organic polymerization initiator to cause polymerization to occur in the organic phase solvent. However, other methods of initiating polymerization can be used instead, such as UV light, actinic radiation, or the like. By way of example, suitable organic initiators include the organic peroxide initiators, such as dibenzoyl peroxide or t-butyl peroctoate, or the azo initiators. Preferred initiators are the azo initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylpentanenitrile). An especially preferred azo initiator is 2,2'-azobis(2,4-dimethylpentanenitrile) , which is commercially available under the tradename VAZO 52 from DuPont, Wilmington, Delaware. A typical effective amount of organic initiator relative to dry monomer was found to be about 0.5 to about 2% by weight, preferably about 1 to about 1.2% by weight. Examples of redox systems include secondary or tertiary amines and, most preferably amine (preferably tertiary) and peroxide combinations. The ratio between the peroxide and the amine may vary from 0.1 to 5 moles of amine per mole of peroxide. It is useful to first dissolve the peroxide in a part of the solvent, and separately dissolve the amine in the other part of the solvent, then mix the peroxide part with the monomer solution at room temperature and, subsequently, add the amine part. The charging of the peroxide and amine part can be done at the beginning of the reaction or in portions throughout the reaction period. These amines are generally of the formula R 2 NH or R 3 N, wherein R is an alkyl or substituted alkyl, cycloalkyl, or aryl group. Preferably the amine is a tertiary amine. Illustrative reducing agents of this invention are methylbutyl amine, bis(2-hydroxyethyl)butyl amine, butyldimethyl amine, dimethyl amine, dibenzylethyl amine, diethylmethyl amine, dimethylpentyl amine, diethyl amine, 2,2',2"-trihydroxy dipropyl ethyl amine, di-n-propylene amine, 2,2',2"-trimethyl tributyl amine, triethyl amine, dimethyl aminoacetal, pentylhexyl amine, triethanolamine, trihexyl amine, trimethyl amine, trioctadecyl amine, tripropyl amine, trisopropyl amine, tetramethylene diamine, and esters of para-amino benzoic acid, e.g., p-dimethyl amino-2-ethylhexyl-benzoate, dimethyl aminoethyl acetate, 2-(n-butoxy)ethyl 4-dimethylaminobenzoate, 2-(dimethylamino) ethyl benzoate, ethyl-4-dimethylaminobenzoate, methyldiethanolamine, dibutyl amine, N,N-dimethylbenzylamine, methylethyl amine, dipentyl amine, and peroxide Fe 2+ . Other preferred initiators are selected from inorganic initiators such as sodium, potassium, and/or ammonium persulfates, and hydrogen peroxide. In the preferred process of the present invention, the monomers and the organic initiator are dissolved in a substantially water-immiscible organic solvent porogen to produce the organic phase. Suitable substantially water-immiscible organic porogens include a wide range of substances, notably inert, nonpolar organic solvents, like hydrocarbons, silicones, fluorosilicones, and chlorinated hydrocarbons. Some of the most convenient examples are alkanes, cycloalkanes, and aromatic hydrocarbons. Specific examples of such solvents are alkanes having 5 to 12 carbon atoms, straight or branched chain cycloalkanes having 5 to 8 carbon atoms, benzene, and alkyl-substituted benzenes. Typical of these solvents are toluene, the xylenes, cyclohexane, chlorinated solvents, such as trichloroethylene, tetrachlormethane, dichlormethane, and the like, and one or more of the heptanes, alone or in combination. Based upon considerations of boiling point, volatility, toxicity, and solubility, a heptane is a preferred solvent; most preferably, n-heptane. A silicone porogen can be, for example, a polyalkyl siloxane, a polyalkylmethyl siloxane, a polyaryl siloxane, a polyalkylaryl siloxane, or a fluorosilicone. Mixtures of these silicones also are useful. Preferred silicones include linear and branched polydimethylsiloxanes of the following general formula: (CH 3 ) 3 SiO-[Si(CH 3 ) 2 O] n -Si(CH 3 ) 3 , and having a viscosity up to about 1,000 centistokes. Diphenyl dimethyl siloxanes, phenylmethyl siloxanes, and polyfluoroalkylmethylsiloxanes also are useful porogens. Silicones useful in compositions of the present invention are available from a variety of commercial sources, including, for example, General Electric Company, Waterford, New York and Dow Corning Corp., Midland, Michigan. Preferred silicone porogens are linear or cyclic, low molecular weight, volatile polydimethylsiloxane compounds, for example, hexamethyldisiloxane and cyclomethicone. Hexamethyldisiloxane has a viscosity of 0.65 cs (centistokes) and is available commercially under the tradename DOW CORNING 200 FLUID, from Dow Corning Corp., Midland, Michigan. Other linear polydimethylsiloxanes, such as decamethyltetrasiloxane, having a boiling point of about 172°C, and a viscosity of 2.5 centistokes, octamethyltrisiloxane, and dodecamethylpentasiloxane, also are useful in the composition of the present invention. The cyclomethicones are low molecular weight, water-insoluble cyclic compounds having an average of about 3 to about 6 -[O-Si(CH 3 ) 2 ]- repeating group units per molecular and boil at atmospheric pressure in a range of from about 150°C to about 250°C. Suitable cyclomethicones are available commercially under the tradenames SILICONE SF-1173 (octamethylcyclopentasiloxane) and SILICONE SF-1202 (decamethylcyclopentasiloxane) from General Electric, Waterford, New York, and SILICONE 334 FLUID and SILICONE 345 FLUID from Dow Corning Corporation, Midland, Michigan, the tetramer being listed first in each instance. The cyclic volatile silicones can be used as the porogen in combination with a linear volatile silicone, and a volatile silicone can be used in conjunction with a nonvolatile silicone. In another embodiment, the porogen is a volatile hydrocarbon having about 12 to about 24 carbon atoms, and a boiling point of about 100°C to about 300°C. Exemplary volatile hydrocarbons are depicted in the following general structural formula wherein n ranges from 2 to 5, Examples of such volatile hydrocarbon solvents are the Examples of such volatile hydrocarbon solvents are the commercially available compounds PERMETHYL 99A and PERMETHYL 101A, corresponding to compounds of the above general structural formula wherein n is 2 and 3, respectively, from Permethyl Corporation, Frazer, Pennsylvania. Other porogens include C 4 -C 20 alcohols, perfluoro polyethers, and silicone compounds, like amodimethicone, trimethylsilylamodimethicone, polysiloxanepolyalkyl copolymers (such as stearyl dimethicone and cetyl dimethicone), dialkoxydimethylpolysiloxanes (such as stearoxy dimethicone), dimethicone copolyol, and cetyl dimethicone copolyol. Preferably, the porogen is relatively volatile, having a boiling point of less than about 200°C, more preferably less than about 180°C, at one atmosphere and is water-immiscible. The removal of the porogen can be accomplished by extraction, filtration, or evaporation, e.g., by heat and/or vacuum, or the porogen can be left adsorbed by the polymeric spheres, on the interior of the spheres if lipophilic, or on the outer surfaces of the spheres if hydrophilic. The polymer can be washed with a suitable solvent, e.g., isopropyl alcohol, acetone, silicone fluids, and mixtures thereof, before it is dried. Polymerization is accomplished by dissolving the monomers or their mixtures in an inert porogen which does not react with the monomers or the resulting polymer. Based on the parts by weight of the monomer and the solvent totalling 100 parts by weight, the monomers are used from 0.1 to less than about 40 parts by weight, preferably, from about 2 to less than about 40 parts by weight, and, more preferably, from about 5 to about 25 parts by weight. Correspondingly, the solvent porogen is present from greater than about 60 parts by weight, preferably greater than about 70 parts by weight, more preferably greater than about 75-80 parts by weight to 99.9 parts by weight, preferably, from greater than about 75 parts by weight to about 98 parts by weight, and, most preferably, from about 80 parts by weight to about 95 parts by weight. No surfactant or dispersing aid is required. The process of the present invention also utilizes an aqueous phase. The aqueous phase comprises an aqueous solution, preferably having an effective amount of a suspension stabilizer dissolved therein. Suspension stabilizers are well known in the art. Suitable suspension stabilizers include starch, gum arabic, sodium polymethacrylate, magnesium silicate, sodium bentonite clay, methylcellulose, magnesium hydroxide (Mg(OH) 2 ), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVOH), calcium phosphate, magnesium phosphate, and lignites. A preferred suspension stabilizer is methylcellulose, such as is commercially available from Dow Chemical Company, Midland, MI., under the tradename METHOCEL A4C Premium. In performing the process of the present invention, the organic phase is combined under an inert (e.g., argon or nitrogen) atmosphere with the aqueous phase. The combination is typically performed at about room temperature (e.g., about 23°C) and at a ratio of organic phase to water phase of 10% to 90% by weight organic phase with 90% to 10% by weight water phase. Preferably about 50% to about 90% by weight water phase is included to assure that each suspended organic phase droplet is completely surrounded by water during polymerization of the monomer(s) in the organic phase. The combined phases should be vigorously stirred, or otherwise subjected to sufficient shear to separate the organic phase into microdroplets (i.e., having a diameter of about 1 µm to 120 µ m) surrounded by the aqueous phase. The stirring or shearing can commence during or after the combination of the two phases. Preferably, the vigorous stirring is employed during the combination of the two phases. More preferably, the organic phase is added slowly with vigorous stirring or vigorous agitation to the aqueous phase. By the phrase "vigorous agitation" as used herein is meant that the stirring paddle or impeller is rotated at a tip speed of about 1 meter per second to about 15 meters per second, preferably at least about 5 meters per second, more preferably about 5-10 meters per second, most preferably about 8 meters per second. For example a paddle stirrer is rotated at a speed between about 800-2000 revolutions per minute ("rpm"), preferably at about 1400-1600 rpm. The function of the vigorous agitation is to facilitate separation of the organic phase into microdroplets that become isolated from one another as discrete minireaction vessels that are surrounded by water. In the process of the present invention, the water functions not only to separate the microdroplets but also as a heat transfer vehicle for the transfer of heat to microdroplets of monomers to initiate the exothermic polymerization reactions occurring in each microdroplet, and to render the outer surfaces of the microparticles hydrophilic for adsorption of hydrophilic compounds and aqueous compositions. The polymerization reaction is allowed to proceed in the vigorously agitated reaction mixture by raising the reaction temperature. As disclosed in Example 1, at about 46°C, some polymerization was observed in the stirred reaction mixture. At about 53°C, massive polymerization was observed. The mixture then is preferably heated to about 60°C to about 65°C to drive the polymerization reaction to completion. Once the monomers have been polymerized through gelation and crosslinking, vigorous agitation can be stopped while maintaining slow agitation for heat transfer and homogeneity during subsequent polymer curing; or vigorous agitation can be continued. Once polymerization is completed, the resulting microporous polymer microparticles are separated from the reaction mixture, such as by filtering or by screening. At this point, however, the separated particles are filled with the water-immiscible porogen of the reaction mixture. By selecting a porogen that is also volatile, the porogen can be removed readily from the internal pores of the polymer particles, preferably by steam distillation. Most of the microparticle spheres are fractured via escape of porogen from an interior of the microparticle spheres at this point in the process. If the porogen is left in place as an active ingredient of the polymer product, the spheres can be broken by milling. Once the microporous polymer microparticles have been separated from the water-immiscible organic solvent, such that the oleophilic interior surfaces of the broken spheres are now evacuated, they become the preferred embodiment of the microporous, oil and water adsorbent polymer microparticles of the present invention. Theoretically, the interior of the spheres adsorb oleophilic compounds and the exterior of the spheres adsorb both oleophilic and hydrophilic compounds. Alternatively, the porogen(s) can remain in place as an active material ( in situ suspension polymerization). Thus, the present invention is also directed to a composition of matter, i.e., a microporous and oil and water adsorbent microparticle in the form of broken spheres comprising a polymer formed by polymerizing at least one, and preferably at least two, polyunsaturated monomers (each containing at least two carbon to carbon double bonds) optionally including one or more monounsaturated monomers, in an amount up to about 40% by weight, preferably no more than about 9% by weight, and most preferably 0 to about 5% monounsaturated monomers, based on the total weight of monomers. It has been found that adsorptive capacity increases dramatically as the percentage of monounsaturated monomers approaches zero. The resulting microparticles, in the form of broken hollow spheres having nonsmooth, irregular porous interior surfaces that provide more surface area than the outer surface of the spheres, having a mean unit diameter of less than about 50 microns, preferably less than about 25 microns, have total adsorption capacity for mineral oil that is 72% by weight or greater, based upon the total weight of the polymer plus adsorbed oil, preferably at least about an 80%, most preferably about 80% to about 93%, by weight adsorptive capacity for oleophilic compounds and compositions, e.g., organics, such as mineral oil, and an adsorption capacity for hydrophilic compounds and aqueous solutions thereof of at least about 70% by weight, and preferably about 75% to about 90% by weight, adsorption capacity for aqueous solutions/dispersions and hydrophilic solids, based on the total weight of polymer plus adsorbed aqueous/hydrophilic material. The phrase "mean unit diameter" refers to mean diameter of the individual particle and not to the diameter of agglomerates which may form from time to time due to static charge or otherwise. The mean unit diameter of the microparticle is more preferably from about 1 to about 25 microns; most preferably, from about 1 to about 20 microns. Particles can be manufactured having particle sizes up to about 3000 µm, particularly about 1000 µm to about 2000 µm. A preferred particle size distribution spans about 1-100 microns, more preferably about 1 to about 80 microns, with particles generally not less than about 0.5 micron in size, with most particles being about 1 micron or larger. Preferably, the microparticles of the present invention have a total adsorption capacity for mineral oil of about 74% by weight or greater; more preferably, about 76% by weight or greater; most preferably about 78-80% by weight or greater. The most preferred particles have an adsorption capacity for mineral oil of at least about 90% by weight, based on the total weight of particles plus adsorbed oil. It is not expected that the sorption capacity of the polymers of the present invention for light mineral oil would exceed about 95% by weight, based on the total weight of polymer plus adsorbed mineral oil. The microparticles of the present invention appear as a white powder and constitute free flowing discrete solid particles even when loaded with a hydrophilic and/or oleophilic material to their "free flowing" sorption capacity, e.g., about 85% by weight for the particles of Example 1 (POLY PORE™ E 200) when loaded with mineral oil. In a preferred microporous, oil and water adsorbent microparticle of the present invention, two diunsaturated monomers are copolymerized--one of the polyunsaturated monomers being an ethylene glycol dimethacrylate, preferably monoethylene glycol dimethacrylate. The preparation of such a microparticle is described in Example 1 herein, wherein the other diunsaturaced monomer is allyl methacrylate and the mole ratio of allyl methacrylate: monoethylene glycol dimethacrylate was within a preferred molar ratio of allyl methacrylate:ethylene glycol dimethacrylate of 1:1 to 1:2, specifically 1:1.22. The polymers of the present invention, containing at least one and preferably at least two polyunsaturated monomers, have a superior total adsorption capacity for mineral oil over the (BMA/-EGDM) copolymers and a commercially available copolymer (MMA/EGDM). In particular, the polymer of Example 1 exhibited a total sorption capacity for mineral oil of 91.7% by weight, compared to 72.2% by weight for the best reported BMA/EGDM copolymer of the prior art and 64% by weight for the commercially available product (Dow Corning Product No. 5640). The abbreviations used herein are identified as follows: BMA butyl methacrylate EGDMA monoethylene glycol dimethacrylate AMA allyl methacrylate MMA methyl methacrylate EXAMPLE 1 (2 diunsaturated monomers Poly Pore™ E 200) METHOCEL A4C Premium (5.25 grams) was dissolved in 573.3 grams of water in a 2000 ml three-necked resin equipped with a stirrer, thermometer, condenser, and argon purge. A solution of 40.92 grams of allyl methacrylate, 76.48 grams of ethylene glycol dimethacrylate, 765.20 grams of n-heptane and 2.33 grams of VAZO 52 was bubbled with argon for 10 minutes. The resulting mixture was slowly added to the 1,500 rpm stirred aqueous solution of the METHOCEL at 23°C under argon. The temperature was raised to 46°C with constant agitation when precipitation started. Massive polymerization was observed at 53°C. The reaction mixture then was heated to 60°C to 65°C, and that temperature was held for an additional six hours. Thereafter, the reaction mixture was subjected to steam distillation to remove the heptane and residual monomers. The copolymer was separated from the reaction mixture by filtration. The separated copolymer was washed with deionized water and dried in an oven at 80°C. The dried polymer was an odorless, white, soft powder having a total adsorption capacity for light mineral oil of 11.1 grams/1 gram, and apparent density of 0.032 g/cc, a mole ratio of allyl methacrylate:ethylene glycol dimethacrylate 1:1.22, and a corresponding ratio mole percent 46:54. The particle size distribution was analyzed and was as follows: High Size Under % High Size Under % High Size Under % High Size Under % High Size Under % High Size Under % 80.0 100 24.9 67.5 7.75 11.0 2.41 2.2 0.75 0.3 0.23 0.0 71.9 99.8 22.4 58.6 6.97 9.5 2.17 1.9 0.68 0.2 0.21 0.0 64.7 99.5 20.1 49.7 6.27 8.2 1.95 1.7 0.61 0.2 0.19 0.0 58.2 99.0 18.1 41.4 5.64 7.1 1.75 1.5 0.55 0.1 0.17 0.0 52.3 98.2 16.3 34.3 5.07 6.1 1.58 1.3 0.49 0.1 0.15 0.0 47.1 97.1 14.6 28.6 4.56 5.3 1.42 1.1 0.44 0.1 0.14 0.0 42.3 95.1 13.2 23.9 4.10 4.5 1.28 1.0 0.40 0.0 0.12 0.0 38.1 92.0 11.8 20.1 3.69 3 9 1.15 0.9 0.36 0.0 0.11 0.0 34.2 88.2 10.7 17.1 3.32 3.4 1.03 0.7 0.32 0.0 0.10 0.0 30.8 82.8 9.58 14.8 2.98 2.9 0.93 0.6 0.29 0.0 27.7 75.7 8.62 12.7 2.68 2.5 0.83 0.4 0.26 0.0 EXAMPLE 2 The copolymer powder of Example 1 was mixed with zinc pyrithione (solids having a particle size of 3 to 5 microns slurried in water) to a content of 12 grams of slurry per one gram of the polymer and dried in an oven at 80°C to evaporate water. The dry polymeric powder was a white, fine powder with 85% entrapped zinc pyrithione, i.e., 5.76 grams per gram. Zinc pyrithione is supplied by Ruetger Nease Company as mixture of 48% of zinc pyrithione, 51% water and 1% zinc chloride and is used as antidandruff component in hair care products, e.g., antidandruff shampoos. EXAMPLE 3 The copolymer of Example 1 was loaded with methanol/salicylic acid solution to a content of 12 grams per gram, and dried in an oven at 80°C to evaporate methanol. The dry polymeric powder was a white, fine powder, with 74% entrapped salicylic acid, i.e, 2.8 grams per gram. Entrapped salicylic acid is not light sensitive, nor explosive. Salicylic acid is an antiseptic and antifungal agent. EXAMPLE 4 A solution was made by dissolving 1 gram of dibenzoyl peroxide in 8 grams of chloroform. The solution was adsorbed in 1 gram of polymer of Example 1, thereafter chloroform was evacuated, and the entrapped dibenzoyl peroxide polymer system was pulverized to very fine white powder. Usually dibenzoyl peroxide is shock sensitive and has tendency to explode at contact with metals. The entrapped dibenzoyl peroxide polymer system was inactive to friction, to shock, and to contact with metals. The loading capacity of dibenzoyl peroxide was 50%, i.e., 1 gram per gram. EXAMPLE 5 Retinol was dissolved in same amount of ether. The solution (5.5 grams) was adsorbed in 1 gram of the polymer powder of Example 1. Thereafter, ether was evacuated by vacuum and a free-flowing light yellow powder was obtained. The retinol capacity was 2.5 grams per gram, i.e., 71%. Usually retinol is in the form of sticky crystals, is light sensitive, and is skin irritant. Retinol is used in cosmetic formulations and as a vitamin. EXAMPLE 6 The procedure for preparation of the polymer in Example 1 was repeated except that 46 mole percent allyl methacrylate monomer (crosslinker #1) was copolymerized with 54 mole percent ethylene glycol dimethacrylate (crosslinker #2), mole ratio 1:1.22. Porogen (n-heptane) content was 69% by weight to monomers weight. Total adsorption capacity for light mineral oil of the resultant polymer was 81%, i.e., 4.3 grams of mineral oil per one gram of the polymer. EXAMPLES 7-11 The same monomers with same mole ratio were employed as in Example 6, however porogen (n-heptane) concentration was increased in each series of syntheses. Due to the augmented porogen concentration, the adsorption capacities were enhanced and the apparent densities were decreased. In each instance submicron size copolymeric powders, in the form of broken microspheres, were produced. Adsorption capacities of the various copolymeric powders for light mineral oil were determined and are shown in Table 1. Example No. Porogen % Adsorption Capacity g/1g Apparent Density g/cc25 7 69 4.3 0.084 8 80 5.9 0.069 9 82.5 6.5 0.049 10 86 9.7 0.036 11 87.7 11.1 0.032 Therefore, in accordance with another important feature of the present invention, the microparticles have a bulk density of about 0.008 to about 0.1 gm/cc, and preferably about 0.009 gm/cc to about 0.07 gm/cc. To achieve the full advantage of the present invention, the microparticles have a bulk density of about 0.0095 gm/cc to about 0.05 gm/cc. As described in Examples 7-11, a low bulk density is preferred because oil absorbency increases as bulk density decreases. The following Table 2 illustrates that as the monomer concentration in the porogen is decreased, the bulk density of the microparticles decreases and oil absorbency increases. In each of Samples 1-4 of Table 2, the monomer ratio of ethylene glycol dimethacrylate to allyl methacrylate was 1.87:1.00. Sample Monomer Conc. Bulk Density Oil Adsorbancy g/g Heptane (gm/ml) Sample 1 0.1533 0.03 10.5 Sample 2 0.0713 0.0154 17 Sample 3 0.0344 0.0148 21 Sample 4 0.0169 0.0095 23 The results summarized in Table 2 are set forth in Figs. 6-8, which show that oil absorbance increases with decreasing bulk density (Fig. 6) and with decreasing monomer concentration (Fig. 7), and that bulk density increases with monomer concentration (Fig. 8). EXAMPLES 12-14 Adsorptive polymers were obtained following the procedure of Examples 7-11, except that various monomer combinations were employed, all with 87.7% of n-heptane as a porogen. Adsorption capacities of the various polymeric powders were determined and are shown in Table 3. Example No. Porogen % Adsorption Capacity g/g Min. Oil Apparent Bulk Density g/cc 12 85 9.1 0.038 DMAEMA/EGDM 13 85 8.7 0.049 VAC/ST/EGDM 14 85 10 0.036 1,4-BDDMA The abbreviations used in Table 2: DMAEMA : Dimethylaminoethyl Methacrylate EGDM Ethylene Glycol Dimethacrylate VAC Vinyl Acetate ST Styrene 1,4-BDDMA 1,4-Butanediol Dimethacrylate The microparticles of Example 1 (POLYPORE™ E 200) were tested for adsorption of various solid and liquid hydrophilic and oleophilic materials for adsorption and free-flowing capacities with the results shown in Table 4: Total (g/g) Free-Flowing (g/g) Water 7.8 6.0 Mineral Oil 10.4 8.1 Artificial Sebum 10.8 8.1 Glycerin 8.0 6.0 Cyclomethicone (DC 244) 12.0 9.6 Isopropyl Myristate 10.7 8.0 Vitamin E Acetate 7.2 5.6 Benzophenone-3 12.3 9.2 PEG 200 11.2 8.8 Benzyl Acetate 12.3 10.2 Fragrance/Floral Lavender (Q-12512) 11.1 8.1 Dimethicone (DCC 10) 10.6 8.5 Dimethicone (DCC 200) 10.2 7.1 Dimethicone (DCC 350) 10.0 6.9 Dimethicone (DCC 1000) 10.0 6.9 Motor Oil (10 W 40) 10.1 Heptane 8.0 Toluene 10.0 Xylene 9.6 Methylene Chloride 18.8 Irgasan DP 300 5-chloro-2-(2, 4 dichloro-phenoxy)phenol 10.0

Claims: A process for producing a microporous oil and water sorbent polymer comprising the steps of: dissolving at least one polyunsaturated monomer in a substantially water-immiscible organic solvent to provide a monomer mixture containing more than 60% by weight polyunsaturated monomers, based on a weight of the monomers; said monomer mixture containing no monounsaturated monomer combining the monomer mixture with an aqueous solution to form a biphasic liquid system; shearing the biphasic liquid system in an amount sufficient to suspend the water-immiscible organic phase, containing the dissolved monomers, as microdroplets in the aqueous phase; polymerizing the monomers in the suspended microdroplets during shearing to produce a microporous, copolymer microparticle therein; and separating the microporous polymer microparticle from the substantially water-immiscible organic solvent to produce a microporous oil and water adsorbent polymer microparticle, in the form of broken spheres, having a mean unit diameter of less than about 50 microns, and having a bulk density of about 0.008 to about 0.1 gm/cc. A process as claimed in claim 1, wherein the polyunsaturated monomer mixture comprises an ethylene glycol dimethacrylate selected from the group consisting of monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and mixtures thereof. A process as claimed in claim 2, wherein said dimethyacrylate is monoethylene glycol dimethacrylate. A process as claimed in any one of the preceding claims, wherein two polyunsaturated monomers are dissolved in the water-immiscible organic solvent. A process as claimed in claim 4, wherein one polyunsaturated monomer is an ethylene glycol dimethacrylate and the second monomer is allyl methacrylate in a mole ratio of allyl methacrylate:ethylene glycol dimethacrylate of 4:6. A process as claimed in any one of the preceding claims, wherein the weight ratio of monomers to organic solvent is about 40:60 to about 0.1:99.9. A process as claimed in any one of the preceding claims, wherein the weight ratio of monomers to organic solvent is about 20:80 to about 0.1:99.9. A process as claimed in any one of the preceding claims, wherein the substantially water-immiscible solvent comprises an aromatic hydrocarbon, an aliphatic hydrocarbon, a chlorinated hydrocarbon, a silicone, or mixtures thereof. A process as claimed in claim 8, wherein the substantially water-immiscible organic solvent comprises an aliphatic hydrocarbon selected from the group consisting of a C 5 to C 12 alkane, a C 5 to C 8 cycloalkane, a volatile hydrocarbon having the structure wherein n is 2 to 5. A process as claimed in claim 8, wherein the silicone is selected from the group consisting of a polydimethylsiloxane having a viscosity up to 1,000 centistokes, a dimethicone, a cyclomethicone, a polyaryl siloxane, a polyarylalkylsiloxane, a polyalkyl siloxane, a polyalkylmethyl siloxane, a fluorosilicone, a diphenyl dimethyl siloxane, a phenylmethyl siloxane, a perfluoroalkylmethyl siloxane, and mixtures thereof. A process as claimed in any one of the preceding claims, further including adding a polymerization initiator to the monomer mixture. A process as claimed in claim 11 wherein the polymerization initiator comprises an azo nitrile type initiator. A process as claimed in any one of the preceding claims, wherein the mean unit particle diameter is about 1 to about 25 microns. A process as claimed in claim 13, wherein the means unit particle diameter is about 1 to about 20 microns. A process as claimed in any one of the preceding claims, wherein the microparticles have a particle size distribution wherein a majority of the microparticles have a particle size between about 6.2 and about 32.7 microns. A process as claimed in any one of the preceding claims, wherein the microparticles have a bulk density of about 0.009 to about 0.07 gm/cc. A process as claimed in claim 16, wherein the microparticles have a bulk density of about 0.0095 to about 0.05 gm/cc. A microsporous oil and water sorbent microparticle comprising a copolymer of a first diunsaturated monomer and a second diunsaturated monomer, in a mole ratio of about 1:1 to about 1:2, wherein the microparticle has a mean unit diameter of less than about 50 microns, a bulk density of about 0.008 to about 0.1 gm/cc, and a total sorption capacity for mineral oil that is 72% by weight or greater, said copolymer being free from monounsaturated monomer. A microparticle as claimed in claim 18, wherein the first diunsaturated monomer is allyl methacrylate. A microparticle as claimed in claim 18 or 19, wherein the second diunsaturated monomer comprises an ethylene glycol dimethacrylate. A microparticle as claimed in claim 20, wherein the ethylene glycol dimethacrylate is selected from the group consisting of monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and mixtures thereof. A microparticle as claimed in claim 21, wherein the ethylene glycol dimethyacrylate is monoethylene glycol dimethacrylate. A microparticle as claimed in any one of claims 18 to 22, wherein the total adsorption capacity for mineral oil is 74% by weight or greater. A microparticle as claimed in any one of claims 18 to 23, wherein the total adsorption capacity for mineral oil is 80% by weight or greater. A microparticle as claimed in any one of claims 18 to 24, having a total adsorption capacity for hydrophilic compounds and aqueous solutions of about 70% to about 93%, by weight. A microparticle as claimed in any one of claims 18 to 25, capable of adsorbing oil and water simultaneously. A microparticle as claimed in any one of claims 18 to 26, wherein the mean unit diameter is at least 1 micron. A microparticle as claimed in any one of claims 18 to 27, wherein the mole ratio of first diunsaturated monomer:second diunsaturated monomer is about 1:1.87. A microparticle as claimed in any one of claims 18 to 28, wherein the first diunsaturated monomer is allyl methacrylate and the second diunsaturated monomer is an ethylene glycol dimethacryalte, in a mole ratio of first to second diunsaturated monomer of about 1:1.2 to about 1:1.25. A microparticle as claimed in any one of claims 18 to 29, wherein the mean unit particle diameter is from about 1 to about 25 microns. A microparticle as claimed in any one of claims 18 to 30 having a particle size distribution that is within about 120 microns. A microparticle as claimed in any one of claims 18 to 31, having a bulk density of about 0.009 to about 0.07 gm/cc. A microporous oil and water sorbent microparticle comprising a terpolymer of butyl methacrylate, allyl methacrylate, and an ethylene glycol dimethacylate, in a mole ratio of about 1:3 to 5:5 to 4, respectively, said microparticle having a mean unit diameter of less than about 50 microns, a bulk density of about 0.008 to about 0.1 gm/cc, and a total sorption capacity for mineral oil that is 72% by weight or greater, said terpolymer being free from monounsaturated monomer. A microsporous oil and water sorbent microparticle comprising a polymer of at least one polyunsaturated monomer, wherein the microparticle has a mean unit diameter of less than about 50 microns and a bulk density of about 0.008 to about 0.1 gm/cc, said polymer being free from monounsaturated monomer.

Inventors: SOJKA MILAN F, SOJKA, MILAN F.
Applicants: AMCOL INTERNATIONAL CORP, AMCOL INTERNATIONAL CORPORATION
Application year: 1998
Main classification: C08F2
IPC codes: C09K3, C08F20, C08F222, B01J20, C08F2