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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.
1. A microporous 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.
2. The microparticle of claim 1 wherein the first diunsaturated monomer is allyl methacrylate.
3. The microparticle of claim 1 wherein the second diunsaturated monomer comprises an ethylene glycol dimethacrylate.
4. The microparticle of claim 3 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.
5. The microparticle of claim 2 wherein the ethylene glycol dimethacrylate is monoethylene glycol dimethacrylate.
6. The microparticle of claim 1 wherein the total adsorption capacity for mineral oil is 74% by weight or greater.
7. The microparticle of claim 1 wherein the total adsorption capacity for mineral oil is 80% by weight or greater.
8. The microparticle of claim 1 having a total adsorption capacity for hydrophilic compounds and aqueous solutions of about 70% to about 93%, by weight.
9. The microparticle of claim 1 capable of adsorbing oil and water simultaneously.
10. The microparticle of claim 1 wherein the mean unit diameter is at least 1 micron.
11. The microparticle of claim 1 wherein the mole ratio of first diunsaturated monomer:second diunsaturated monomer is about 1:1.87.
12. The microparticle of claim 1 wherein the first diunsaturated monomer is allyl methacrylate and the second diunsaturated monomer is an ethylene glycol dimethacrylate, in a mole ratio of first to second diunsaturated monomer of about 1:1.2 to about 1:1.25.
13. The microparticle of claim 1 wherein the mean unit particle diameter is from about 1 to about 25 microns.
14. The microparticle of claim 1 having a particle size distribution that is within about 120 microns.
15. The microparticle of claim 1 having a bulk density of about 0.009 to about 0.07 gm/cc.
16. The microparticle of claim 1 wherein the copolymer is free of a monounsaturated monomer.
17. The microparticle of claim 1 wherein the copolymer further comprises a C1 to C4 ester of acrylic acid, a C1 to C4 ester of methacrylic acid, or a mixture thereof, in an amount up to about 40% by weight, based on the total weight of the monomers.
18. The microparticle of claim 1 wherein the copolymer further comprises a C1 to C4 ester of acrylic acid, a C1 to C4 ester of methacrylic acid, or a mixture thereof, in an amount up to about 9% by weight, based on the total weight of the monomers.
This application is a continuation-in-part application of Ser. No. 08/810,268, filed Mar. 3, 1997, now U.S. Pat. No. 5,830,967, which is a continuation-in-part of application Ser. No. 08/486,107, filed Jun. 7, 1995, now U.S. Pat. No. 5,677,407, and application Ser. No. 08/486,455, filed Jun. 7, 1995, now U.S. Pat. No. 5,618,877, which is a continuation-in-part of application Ser. No. 08/327,580, filed Oct. 24, 1994, abandoned.
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. Pat. Nos. 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. Pat. No. 4,962,170 at column 2, line. 4. As stated in U.S. Pat. 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. Pat. Nos. 4,962,170 and 4,962,133. U.S. Pat. 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. Pat. 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. Pat. 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. Pat. 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. Pat. 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. Pat. 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. Pat. 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 μm, preferably about 1 μm to about 100 μm, for a smoother skin feel.
A second problem with the process of U.S. Pat. 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 water-soluble 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. Pat. 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. Pat. No. 4,724,240. To overcome this problem, the process of U.S. Pat. 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.
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.
The present invention is directed to a process for making a porous polymer of microparticulate size that exhibits a high oil and water adsorbency. The 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 porogen that is inert (i.e., not reactive) with respect to the monomers and resulting polymer 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 composition including an organic phase and an aqueous phase;
vigorously agitating the biphasic liquid composition at a rate sufficient to cause the water-immiscible organic phase to be suspended as microdroplets in the aqueous phase;
continuing vigorous agitation during polymerization of the monomers in the suspended microdroplets to produce microporous polymer microparticles in the form of broken (i.e., open) spheres; and
separating the microporous polymer microparticles from the organic solvent to produce a microporous, oil and water adsorbent polymer microparticle having a mean unit diameter of less than about 50 microns, preferably less than about 25 microns, more preferably less than about 20 microns, and a new and unexpected adsorptive capacity for both hydrophobic and hydrophilic compounds, in both solid and liquid (organic solvent and aqueous) forms.
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.
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.
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 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, dipentaerythritol, 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. Pat. Nos. 3,759,880, 3,992,562, and 4,013,825, hereby incorporated by reference. Acryloyl- or methacryloyl endcapped siloxane and polysiloxanes such as those described in U.S. Pat. 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 endcapped urethanes, such as those described in U.S. Pat. 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. Pat. 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, Del. 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 R2 NH or R3 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 Fe2+.
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:
(CH3)3 SiO--[Si(CH3)2 O]n --Si(CH3)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, N.Y. and Dow Corning Corp., Midland, Mich.
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, Mich. 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(CH3)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, N.Y., and SILICONE 334 FLUID and SILICONE 345 FLUID from Dow Corning Corporation, Midland, Mich., 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, ##STR1## 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, Pa.
Other porogens include C4 -C20 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, Mich., 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 μm) 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 monoun-saturated 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 diunsaturated 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
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 Under High Under High Under High Under High Under High UnderSize % Size % Size % Size % Size % Size %__________________________________________________________________________80.0 100 24.9 67.5 7.75 11.0 2.41 2.2 0.75 0.3 0.23 0.071.9 99.8 22.4 58.6 6.97 9.5 2.17 1.9 0.68 0.2 0.21 0.064.7 99.5 20.1 49.7 6.27 8.2 1.95 1.7 0.61 0.2 0.19 0.058.2 99.0 18.1 41.4 5.64 7.1 1.75 1.5 0.55 0.1 0.17 0.052.3 98.2 16.3 34.3 5.07 6.1 1.58 1.3 0.49 0.1 0.15 0.047.1 97.1 14.6 28.6 4.56 5.3 1.42 1.1 0.44 0.1 0.14 0.042.3 95.1 13.2 23.9 4.10 4.5 1.28 1.0 0.40 0.0 0.12 0.038.1 92.0 11.8 20.1 3.69 3.9 1.15 0.9 0.36 0.0 0.11 0.034.2 88.2 10.7 17.1 3.32 3.4 1.03 0.7 0.32 0.0 0.10 0.030.8 82.8 9.58 14.8 2.98 2.9 0.93 0.6 0.29 0.027.7 75.7 8.62 12.7 2.68 2.5 0.83 0.4 0.26 0.0__________________________________________________________________________
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.
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.
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.
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.
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.
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.
TABLE 1______________________________________ Adsorption ApparentExample Porogen Capacity DensityNo. % g/1 g g/cc 25______________________________________7 69 4.3 0.0848 80 5.9 0.0699 82.5 6.5 0.04910 86 9.7 0.93611 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.
TABLE 2______________________________________ Monomer Conc. Bulk Density OilSample g/g Heptane2) (gm/ml) Adsorbancy3)______________________________________Sample 11) 0.1533 0.03 10.5Sample 2 0.0713 0.0154 17Sample 3 0.0344 0.0148 21Sample 4 0.0169 0.0095 23______________________________________ 1) microparticles of Example 1; 2) grams of monomer per gram of hexane; and 3) grams of oil adsorbed per gram of microparticles.
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).
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.
TABLE 3______________________________________ AdsorptionExample Porogen Capacity Apparent BulkNo. % g/g Min. Oil Density g/cc______________________________________12 85 9.1 0.038 DMAEMA/EGDM13 85 8.7 0.049 VAC/ST/EGDM14 85 10 0.036 1,4-BDDMA______________________________________The abbreviations used in Table 2:DMAEMA Dimethylaminoethyl MethacrylateEGDM Ethylene Glycol DimethacrylateVAC Vinyl AcetateST Styrene1,4-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:
TABLE 4______________________________________ Total Free-Flowing (g/g) (g/g)______________________________________Water 7.8 6.0Mineral Oil 10.4 8.1Artificial Sebum 10.8 8.1Glycerin 8.0 6.0Cyclomethicone (DC 244) 12.0 9.6Isopropyl Myristate 10.7 8.0Vitamin E Acetate 7.2 5.6Benzophenone-3 12.3 9.2PEG 200 11.2 8.8Benzyl Acetate 12.3 10.2Fragrance/Floral Lavender 11.1 8.1(Q-12512)Dimethicone (DCC 10) 10.6 8.5Dimethicone (DCC 200) 10.2 7.1Dimethicone (DCC 350) 10.0 6.9Dimethicone (DCC 1000) 10.0 6.9Motor Oil (10 W 40) 10.1Heptane 8.0Toluene 10.0Xylene 9.6Methylene Chloride 18.8Irgasan DP 300 10.05-chloro-2-(2,4 di-chloro-phenoxy)phenol______________________________________
Patent Citations
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A tractor-trailer overturned at about 11:35 a.m. Thursday at the intersection of Startown Road and West Maiden Road in Maiden.
A driver for Queen Transportation said he was making a right turn onto West Maiden Road on Thursday when his tractor-trailer overturned on its right side on a grass embankment.
The driver said he did not know what happened. Maiden Police Officer Chad Long said the driver was not speeding. The tractor-trailer was delivering paper to the VonDrehle Corporation.
With one week of filing remaining for some area municipalities, 17 candidates officially declared for the 2011 Catawba County municipal elections.
Two non-incumbent candidates filed for Newton's mayoral race, which is the only election that currently has multiple people filed for one position. Newton Mayor pro Tem Anne Stedman, along with the Newton Merchant Group's President Wes Weaver, officially filed for the mayoral election that will take place later this year. Newton's current mayor Robert Mullinax said, earlier this year, he will not seek re-election.
The area American Red Cross chapter urges people to donate blood during a time when supplies are traditionally low.

The Catawba Valley Chapter of the American Red Cross will team with the Texas Roadhouse in Hickory on Monday to hold a blood drive from 4-8 p.m. Monday's blood drive comes during a season when Red Cross officials say blood supplies are dangerously low.

Suzan Anderson, executive director for the Catawba Valley's Red Cross chapter, said blood donations and supplies are typically lower in the summer months.
Twenty-fifth Prosecutorial District Attorney Jay Gaither reinstated Eric Bellas to active status in his role as chief assistant district attorney this week, but that doesn't necessarily mean Bellas will be handling prosecution of Elisa Baker if and when her case goes to trial.
In an emailed response to inquiries by the (Lenoir) News-Topic, Gaither indicated that he is taking the lead in the case against Elisa Baker, who was charged in February with second-degree murder in the death and dismemberment of her 10-year-old stepdaughter Zahra Baker.

subset: commoncrawl


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Terrorism Financing
Witnesses testified about efforts to combat the financing of global terrorism. Following Mr. Conrad testimony about a case… read more
Witnesses testified about efforts to combat the financing of global terrorism. Following Mr. Conrad testimony about a case involving cigarette smuggling to fund Hamas operatives, other panels talked about strategies to block accounts and activities of groups linked to terrorism and criminal liability in cases linked to the deaths of Americans. close
People in this video
- Salam al-Marayati Director Muslim Public Affairs Council
- David D. Aufhauser Chairman Interagency Task Force on Terrorism
- Robert Conrad U.S. Attorney Department of Justice->Western District of North Carolina
- Allan Gerson Professor (Former) George Mason University->International Law
- Jimmy Gurule Undersecretary Department of the Treasury->Enforcement
- Nathan Lewin Attorney
- Jonathon Winer Member Council on Foreign Relations->Terrorism Financing Task Force
- Arlen Specter U.S. Senator [R] Pennsylvania
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Elinor Tatum
Elinor Ruth Tatum is the Publisher and Editor in Chief of the New York Amsterdam News,[1] the oldest and largest black newspaper in the City of New York, and one of the oldest ethnic papers in the Country.[2]
Ms. Tatum was appointed to her position by her father Wilbert Tatum in 1997, and became one of the youngest publishers in the history of the Afro-American Press. As editor and publisher Ms. Tatum oversees a staff of twenty-five full-time employees. Under her watch, the newspaper was modernized, and changes have included: a new layout for the paper, and refocusing content to emphasize more current issues facing Harlem and the wider African American community in New York and the Nation. Under her leadership, The Amsterdam News has also gone online and is seen nationally as part of the Black Press USA Network.
Elinor Tatum also produces and co-hosts a weekly segment of Al Sharpton's Weekly Radio Show "Keep'in It Real"-- inviting members of the Black Press to discuss national issues facing the African American community.[3] She has guest hosted the WWRL Radio morning and afternoon drive programs. Ms. Tatum has appeared on The O'Reilly Factor, 20/20, New York 1, CUNY TV, The Today Show, and NBC Nightly News.
Ms. Tatum born and raised in New York City. She studied Government at St. Lawrence University in Canton, New York where she graduated in 1993.[4] She continued her education at Stockholm University in Stockholm, Sweden. While abroad, she studied International relations and the Swedish model of government.
In 1994, Ms. Tatum returned to New York to join her father at the New York Amsterdam News. She accepted a position as Assistant to the Publisher, her work included reporting for the paper. While reporting, she filed stories on topics ranging from the Million Man March, to Boxing, to a student strike at the City University of New York.
In 1996, Ms. Tatum was promoted to Associate Publisher and Chief Operating Officer of the newspaper. That fall, she entered New York University working toward her Master's Degree in Journalism and Mass Communication, while continuing to work full-time at the Amsterdam News. In December 1997, she completed the course work for her Master's Degree and was promoted to Publisher and Editor-in-Chief.
In addition to her career in journalism, Ms. Tatum is also an active member of the greater New York community. She is currently, a member of the Board of Trustees of her college alma mater, St. Lawrence University. In addition she sits on the Board of the New York Urban League, The Neighborhood Defender Service of Harlem, And The Creative Vision Foundation. She also sits on Community Board 3 in Manhattan.
Ms. Tatum has been received numerous honors for her work including: inclusion in Who's Who of American Women (the Millennium Edition and subsequent editions), a Doctor Of Humane Letters Honorus Causae from Metropolitan College (New York City), Manhattan Borough Presidents' Women's History Month Award, Public Advocates Award, Women Who Make A Difference, Outstanding Business Empowerment from the New York Chapter of Black Business and Professional Women, Award, Standing On their Shoulders Award from the National Action Network, and the Good Scout Award.
Ms. Tatum has one daughter, Willa.
- ^ http://www.nytimes.com/1997/12/10/nyregion/metro-business-editor-for-amsterdam-news.html
- ^ http://www.nytimes.com/1997/12/21/nyregion/neighborhood-report-harlem-new-editor-new-ideas-same-name.html
- ^ http://www.hadassahmagazine.org/site/apps/nlnet/content2.aspx?c=twI6LmN7IzF&b=5764469&ct=7873025
- ^ "Jet". google.com.


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The V-Neck detail on this Tea Rose One-Piece gives you the perfect swimsuit for lounging in the sun or playing in the water.
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The most famous Israeli swimwear company worldwide, Gottex has been manufacturing eye-catching suits since 1949. Celebrated for its use of bold, vivid colors, Gottex also takes the time and care to create suits that specifically follow a woman's curves and flatter her body. Through technical innovation and the use of cultural influences, Gottex has taken swimwear from a functional product into a fashion icon.


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ANAHEIM – Mark Trumbo's name was on the invitation list for this year's All-Star Game and Home Run Derby.
But it also popped up frequently on another mid-summer list – players deemed by stat-immersed observers most likely to regress in the second half and not match their first-half performances.
"I'll tell you one thing – I don't play the game to please people who sit behind computers and crunch numbers even though there appears to be a market for that sort of thing," said Trumbo who was a whipping boy for those numbers crunchers after finishing his rookie season with a .254 batting average and .291 on-base percentage (numbers that probably cost him the American League Rookie of the Year award even though he led the Angels with 29 home runs and 87 RBI).
In this case, though, the prophecy seems to be coming true.
Trumbo reached the All-Star break with a .306 batting average, .358 on-base percentage and .608 slugging percentage – all drastic jumps from his 2011 stat line, buoyed (some would say) by a BABIP (batting average on balls in play) and uncharacteristic plate discipline that were not sustainable.
A six-week slump that began shortly after the break, however, has steadily dragged those numbers down. He started the night Wednesday batting .279 with a .331 on-base percentage and .529 slugging percentage.
Trumbo's second-half struggles could be equal parts slump – and course correction, the inexorable pull of reality bringing his stat line back where it should be.
"I don't really know what I am yet," Trumbo said to that. "Two things I know I can do – I hit home runs and I drive the ball. Those are things I try to focus on. I haven't done the best job over the past month, month and a half. But I fully anticipate having a strong finish over this final month.
"In an ideal world, there wouldn't be any down times. But our season is basically six months long. That's what makes what Mike (Trout) is doing even more remarkable. His longest slump has been, what, two games?"
Trumbo heard the criticism of his low OBP and lack of selectivity at the plate as a rookie and took pains to address it this spring. That improved discipline was a big part of his first-half success – and he admits it has slipped during his second-half regression.
"I know I've chased more recently," he said. "That's always going to happen when you're not going well. You're going to expand a little bit because you feel you have to."
You're also going to get advice from all corners on how to turn things around. Trumbo considered the source and heeded some of that advice over the weekend, modifying the 'toe-tap' timing mechanism he used to start his swing in favor of a leg kick that he used in the past.
The advice came from teammate Albert Pujols. Pujols offered his observations after watching the Angels' weekend series in Detroit from the bench with a calf injury.
"My stride had gotten real inconsistent," Trumbo said. "When he wasn't playing in Detroit, he just offered it as, 'This is what I see. This is what has changed.'"


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Though it feels like only yesterday since I started the BA Top Up Degree, we have now finished our first term! It's crazy how quickly time flies when you are having fun! When Logan was first born and I started my last your of my HND in September 2013 there were a few months that were incredibly rough. Learning to be a mum for the first time, dealing with a child with Colic (I think thats how the doctors spell it!) and then also, getting used to being a student again after nearly 2 years off! Back then I remember thinking, 'oh next year will be easier' but oh my goodness, I thought wrong!
Logan is now 15 months old I think, (I lost count after 12!) and he is turning into such a character. There are days he has me in absolute stitches so on one hand it's a nice break from the stresses of coursework, on the other hand, he can be the cutest distraction!
He is so very close to walking now...when I say close...I mean he can walk but he is too lazy and would prefer to have is zimmer frame aka baby walker. Honest to god some days I think he is a miniature grandad! I love his laugh and the way he smiles when he is sleeping, which I take as a good sign that I'm not doing too bad as I'm not giving him nightmares...though I do wish he would sleep more...I feel tired constantly!
So it is Christmas in 11 days (Holy Cow I Didn't Realise Until I Checked!) I have done approximately zero wrapping but atleast all the presents are brought...which might explain the appalling state of my bank account. It was like this on Logan's birthday. I think, subconsciously, I feel quilty for leaving him as often as I do so I tend to over compensate my boy with gifts in hope that he won't hate me when he is older. Only time will tell if that was a mistake or not!
Over my holiday's I will be focusing as much of my attention as possible, on my dissertation. It's not until you have to write in 'proper english' that you realise how appalling your writing as got! Hashtag THANK GOD FOR SPELL CHECK! Hopefully I do alright, I think I am suffering from writers block at the moment which is why I am probably doing this post which is completely irrelevant too my dissertation topic! I know what will happen...my fiance will ask me what time I went to sleep. My response will be, 3/4am (pretty standard for me) His next question will be...did you get a lot done...and that is probably the only times in our relationship where I just have to say a white lie. In my defense, its only to avoid the, why don't you sleep argument!
Anyways, probably should be getting on with it now.
Merry Christmas All and To All Goodnight.


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Event Name- OR - Select an option below
Frog's legs and Vin du Pays, frites and aioli, escargot and pot de crème--this duskily lit Provencal cavern of a restaurant serves everything you love from the garlic-and-passion tradition of French life, and does it under-budget, cheerfully, and well. Escargot are plump as grapes and bathed in such a garlic cream sauce that you know this is what they serve James Beard in heaven. Frog's legs are served golden and crisp, with plenty of garlic butter to dredge your good bread through, and so what if the entrees are hit and miss? It's more passionate to share thousands of appetizers with your loved ones, no? Anyhoo, since the wine list here features plenty of country bottles, you can schedule date night without endangering the Christmas trip to Paris.


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Bob Howry Rumors
Twitter Rumors: Lyon, Holliday, Counsell
Looking for more rumblings and analysis? These tidbits are all 140 characters or less…
- The Rangers are talking to Jason Kendall, according to Ed Price of AOL FanHouse. The Royals have made the veteran backstop a two-year offer.
- Ken Rosenthal of FOX Sports says Brandon Lyon is asking for $9MM over two years. Speaking of Lyon, Jayson Stark of ESPN.com says the Phillies are pursuing him and Fernando Rodney with equal interest.
- MLB.com's Bill Ladson reports that the Blue Jays expressed interest in Craig Stammen. However, the Nats aren't likely to trade him.
- Yahoo's Steve Henson hears that the Yankees will be strong players for Matt Holliday.
- The Brewers still have interest in Craig Counsell, according to MLB.com's Adam McCalvy. Tom Haudricourt of the Milwaukee Journal-Sentinel says the two sides met and continue to talk. He expects them to reach a deal.
- The Indians have no money to spend, according to ESPN.com's Jerry Crasnick.
- Ruddy Lugo signed a minor league deal with the Tigers, according to Jorge Arangure Jr. of ESPN.com.
- Arangure's colleague, Jayson Stark, has a similar update. The Dodgers could soon sign Jay Gibbons to a minor league deal.
- Yankees GM Brian Cashman doesn't consider Aroldis Chapman an option for the team's rotation next year, according to Newsday's Ken Davidoff. They'll still watch him throw in Houston, according to MLB.com's Bryan Hoch.
- The Red Sox will be there too, according to Gordon Edes of ESPN.
- MLB.com's Corey Brock reports that the Padres are considering some options in the Rule 5 draft.
- ESPN.com's Jayson Stark says the Royals inquired on Brett Gardner after the Yankees acquired Curtis Granderson.
- The Phillies asked Cliff Lee's agent to fly to Indianapolis this week to discuss an extension, according to Scott Lauber of the Journal News.
- You can expect the D'Backs to pursue Bob Howry, according to Steve Gilbert of MLB.com.
Full Story | Comments | Categories: Arizona Diamondbacks | Aroldis Chapman | Bob Howry | Boston Red Sox | Brandon Lyon | Brett Gardner | Cleveland Indians | Cliff Lee | Craig Counsell | Craig Stammen | Detroit Tigers | Fernando Rodney | Kansas City Royals | Los Angeles Dodgers | Matt Holliday | Milwaukee Brewers | New York Yankees | Philadelphia Phillies | San Diego Padres | Toronto Blue Jays | Washington Nationals
Giants' Talk: Catchers, Rotation, Howry
Andrew Baggarly of The Mercury News and John Shea of The SF Chronicle have some notes on the Giants' for us…
- GM Brian Sabean said "nobody thinks [Buster Posey] is ready to catch 100-plus games in the big leagues," however they haven't made any "money offers" to any free agent catchers. He acknowledged that a multi-year deal for a backstop "wouldn't be wise."
- As for why they didn't offer Type-A free agent Bengie Molina arbitration, Sabean said the team didn't "need another arbitration case," and that they "have multiple needs and we want to spread the money throughout the roster."
- Sabean indicated that the team isn't comfortable paying Brad Penny or Juan Uribe what they want, and neither is likely to return. Both players declined one year deals last week.
- Shea says that if Penny leaves, the team probably won't move Jonathan Sanchez in a trade, while Baggarly says there is "less resistance to the idea of Madison Bumgarner beginning the season in the rotation."
- The team has informed reliever Bob Howry that they would like to bring him back, but they have not yet talked about money.
- The Giants will not forfeit a draft pick to sign a player, which rules out the Type-A's. They hold the 24th overall pick in next year's draft. However, Sabean said that Type-A's who weren't offered arbitration were "more sensible targets."
Full Story | Comments | Categories: Bengie Molina | Bob Howry | Brad Penny | Buster Posey | Jonathan Sanchez | Juan Uribe | Madison Bumgarner | San Francisco Giants
Giants Do Not Offer Arb To Any Free Agents
The Giants did not offer arbitration to any of their free agents – Type A catcher Bengie Molina and Type Bs Bob Howry, Randy Johnson, and Randy Winn. It's a mixed result for Molina – he's more attractive to other teams (the Mets, for example) now that he will not cost a draft pick, but if he'd been offered and accepted arbitration he probably would've maximized his 2010 salary.
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Full Story | Comments | Categories: Bengie Molina | Bob Howry | Randy Johnson | Randy Winn | San Francisco Giants | Transactions
Odds & Ends: Gordon, Uribe, D'backs, Igawa
Links for a busy Wednesday, as writers, agents, and GMs catch their flights out of O'Hare…
- Welcome to Twitter: ESPN's Buster Olney.
- ESPN's Keith Law assesses the Mark Teahen, J.J. Hardy, Jeremy Hermida, and Akinori Iwamura trades.
- The Royals are committed to Alex Gordon as their third baseman despite acquiring Josh Fields, according to Ken Rosenthal and Jon Paul Morosi of FOX Sports. Fields instead could play left field in the event David DeJesus is traded. DeJesus' name popped up in our left field trade market post.
- Rosenthal and Morosi also note that the Giants are talking with Juan Uribe about a new contract. Uribe was one of the year's best minor league deals. He's represented by Barry Praver.
- Rosenthal reported yesterday that the Nationals hired Bryan Minnitti from the Pirates to be their new assistant GM. Jake from New Bucs interviewed the young exec last year.
- Nick Piecoro of the Arizona Republic names four relievers who might be of interest to the Diamondbacks: Rafael Betancourt, Mike Gonzalez, LaTroy Hawkins, and Bob Howry.
- Joe Pawlikowski of River Ave. Blues has a reality check for fans as we head toward the offseason insanity.
- Victor Martinez's agent Alan Nero told WEEI's Rob Bradford there's been "little or no dialogue" in terms of the Red Sox extending his client.
- Joel Sherman of the New York Post wonders if the Yankees' championship might enable them to take things more slowly this winter.
- Sherman tweets that there is interest in Japan from Kei Igawa, but he doesn't want to go. Igawa posted a 4.15 ERA in 145.3 Triple A innings this year, and still has $8MM remaining on his contract.
- Baseball America's Matt Eddy has your minor league transactions. Wilson Valdez and Mike Gosling are among those joining the free agent ranks.
- New Blue Jays GM Alex Anthopoulos seems passionate, talking to Bob Elliott of the Toronto Sun. Anthopoulos even gives props to the fine Jays blogs out there.
- Padres pitcher Chris Young told Bill Center of the San Diego Union-Tribune that he understands the business aspect of baseball. With a healthy first half, Young could be a trade candidate.
- Grant at McCovey Chronicles says AT&T Park isn't a pitcher's park anymore, and agents know that.
Full Story | Comments | Categories: Alex Anthopoulos | Alex Gordon | Arizona Diamondbacks | Bob Howry | Boston Red Sox | Chris Young | David DeJesus | Josh Fields | Juan Uribe | Kansas City Royals | Kei Igawa | LaTroy Hawkins | Mike Gonzalez | New York Yankees | Rafael Betancourt | San Diego Padres | San Francisco Giants | Toronto Blue Jays | Victor Martinez | Washington Nationals
Giants Rumors: Molina, Pudge, Bay, Holliday
Andrew Baggarly of the San Jose Mercury News reports that the Giants are open to bringing Bengie Molina back, but prepared in case the catcher signs elsewhere. Here are the details:
- The Giants won't likely offer Molina much more than the $6MM he made this year.
- Molina wants a two-year deal, so Baggarly says the 35-year-old is unlikely to re-sign with the Giants.
- The Mets could have interest, and Baggarly says an unnamed AL team expects to get involved, too.
- Baggarly expects the Giants to offer Molina arbitration, but would be surprised to see the team extend similar offers to Bob Howry, Randy Johnson or Randy Winn.
- The Giants have tried to acquire Ivan Rodriguez before, so they could bring him in to mentor Buster Posey and provide the club with insurance in case the top prospect struggles.
- The Giants believe Matt Holliday's defense regressed a shocking amount last year.
- Jason Bay seems like a better fit for the Giants.
Full Story | Comments | Categories: Bengie Molina | Bob Howry | Buster Posey | Ivan Rodriguez | Jason Bay | Matt Holliday | Randy Johnson | Randy Winn | San Francisco Giants
Diamondbacks Seeking Veteran Reliever
The Diamondbacks could have two potential holes to fill in their rotation depending on what happens with Doug Davis and Brandon Webb after the season, but GM Josh Byrnes also wants to add a veteran reliever according to Nick Piecoro of The Arizona Republic.
"We've had our share of adversity this year, and in the bullpen it's not going to be a smooth ride for six months," Byrnes said. "We'd like to have people who can sort of understand that a bad game is going to happen but not let it happen too often and set an example that way."
Arizona's pen was supposed to be anchored by Chad Qualls, Scott Schoeneweis, Tony Pena and Jon Rauch, but Rauch and Pena were traded, Qualls battled injury, and Schoeneweis dealt with the unfortunate passing of his wife. The foursome combined for a 4.46 ERA in 163.1 IP for the D-Backs this season.
Looking the list of available free agents this offseason, could Bobby Howry or Octavio Dotel make sense? Maybe a Brandon Lyon reunion?
Full Story | Comments | Categories: Arizona Diamondbacks | Bob Howry | Brandon Lyon | Brandon Webb | Chad Qualls | Doug Davis | Jon Rauch | Octavio Dotel | Scott Schoeneweis | Tony Pena
Reds Sign Mike Lincoln, Still Like Weathers
10:43pm: Reds GM Walt Jocketty says that even with the Lincoln signing he still hopes to sign David Weathers. Four or five other teams are said to be in the mix for Stormy. We'll know by midnight Sunday whether Weathers will accept the Reds' offer of arbitration.
3:49pm: La Velle E. Neal III of the Minneapolis Star-Tribune says the Twins were "hot after" Lincoln and were "barely outbid" by the Reds. The Twins weren't in on Bob Howry though.
12:43pm: According to Troy E. Renck of the Denver Post, the Reds re-signed reliever Mike Lincoln to a two-year deal worth $4MM plus incentives. Lincoln, 34 in April, posted a 4.48 ERA in 70.1 innings this year. His command was respectable, though he was prone to the longball. It was an impressive comeback from two Tommy John surgeries.
Full Story | Comments | Categories: Bob Howry | Cincinnati Reds | David Weathers | Mike Lincoln | Minnesota Twins
Giants Sign Bob Howry
4:03pm: According to the AP, Howry gets a reasonable base salary of $2.75MM. He can earn an additional $500K based on games and another $1MM based on games finished. Dave Cameron calls it a bargain.
2:45pm: According to Henry Schulman of the San Francisco Chronicle, the Giants signed Bob Howry to a one-year deal. They moved quickly after the Cubs decided not to offer arbitration to the Type A free agent. If Howry bounces back (the Giants think Lou Piniella overworked him this year), he'll be a nice complement to Jeremy Affeldt and Brian Wilson in the late innings.
Howry came up through the Giants' system before being traded to the Sox in the White Flag deal of '97.
Full Story | Comments | Categories: Bob Howry | San Francisco Giants
Giants Rumors: Renteria, Howry
8:02pm: MLB.com's Chris Haft says the Giants accelerated their pursuit of Bob Howry now that the Cubs chose not to offer him arbitration.
6:55pm: The AP has an update on the Giants' pursuit of free agent shortstop Edgar Renteria, though there's not much new info. The Giants and Renteria are discussing the parameters of a deal and he is their top option at short. It makes sense that things will get moving now that Renteria failed to receive an offer of arbitration from the Tigers.
Full Story | Comments | Categories: Bob Howry | Rafael Furcal | San Francisco Giants
Reds Unlikely To Sign Wood
TUESDAY: Baker might make a call, but Reds GM Walt Jocketty admits that Wood is likely to find offers to close elsewhere.
MONDAY, 11:03pm: Dusty Baker plans to give Wood a call and see if he might be interested in setting up Francisco Cordero in Cincinnati.
7:55pm: According to MLB.com's Carrie Muskat, the Cubs declined to offer arbitration to Type A free agents Kerry Wood and Bob Howry. The Cubs decided they could not take on the financial risk of Wood accepting, as they're tight on payroll. Trading him might've been difficult, as he would've been a 10-and-5 player. It seems that payroll forced the Cubs to make the questionable baseball decision to pass on a one-year deal for Wood.
Wood now has an advantage on the market over Francisco Rodriguez and Brian Fuentes – he won't cost a draft pick to sign.
Full Story | Comments | Categories: Bob Howry | Brian Fuentes | Chicago Cubs | Cincinnati Reds | Francisco Rodriguez | Kerry Wood


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SAN ANTONIO -- A 19-year-old man was rushed to the hospital on Thursday morning after he was shot multiple times, police say.
The man pulled up to the Gibbs Mart at the intersection of Gibbs Sprawl and Walzem Road around 8:45 a.m. and told the store clerk he had been shot, San Antonio police said.
The victim was later identified as Nicholas Ornelas.
Police Sgt. Ramiro Juarez said officers found drugs inside the Honda Accord that Ornelas was driving.
He's not saying where it happened, how it happened, Ramiro said. Based off some of the evidence we've recovered, we're thinking it might have something to do with a possible drug deal gone bad.
Ornelas was rushed to San Antonio Military Medical Center in critical condition.


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La Cantina de Daniel
Sahagun house
5 BR / 4 BA / Sleeps 10 | Quick view
It´s a terraced house. It´s in old building which was renovated last year. It has two floors. The ground floor has high wooden ceilings, a big bedroom with a vintage bed a bathroom a warm kitchen and a huge living room. Obiusly, the garden is 150square meter large, where you can see many different kind of flowers. …
- Internet Access
- Washing Machine
- Clothes Dryer
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- Balcony or terrace
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ACE Fit Share
Add some variety to your fitness routine with these upper and lower leg exercises from The American Council on Exercise. We have a large selection of leg exercises that will will help you strengthen and build muscle throughout your legs including your hamstrings, thighs, shin and calf muscles. Start taking advantage of this free information today! If you are looking for full workout routines that incorporate these leg exercises, check out our Workouts section.
Fit Life Articles
Harsh winter weather can make it a challenge to stick with a running program, especially if treadmill running just isn't your thing. But with the arrival of spring, you might be itching to get back on the road. Here are five tips that will help you avoid injury and get your...
No equipment? No excuses. This fun and effective equipment-free workout combines six creative exercises into one complete total-body workout that will improve your fitness using nothing more than your own bodyweight.
When was the last time you tried jumping rope? This schoolyard favorite offers huge health benefits, including improved cardio endurance and greater bone density. Check out this fun and effective cardio-blasting jump rope workout, which can be performed almost anywhere and...
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Publisher's Description+
From Rubicon Mobile, Ltd: Great Big War Game for Windows 8 features 50 Mission single player campaign, online asynchronous multiplayer, pass and play and Skirmish vs AI, achievements to unlock, stunning visuals, simple, and intuitive control method. You've plenty of units to play with, covering land, sea and airborne combat.
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100,000 - 500,000 downloadsAdd this app to your lists
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Email your newest creations or upload it to Twitter and Facebook and share it with your friends. Embarrass and amuse your friends and family as you choose from over 60 overlays to add to their face or pets and let the good times roll. Even your kids will laugh as you add facial hair and put them on the cover a magazine. Picturizr is a fun image editor suitable for all ages.
Also, check out the Picturizr Download area to get more fun overlays and frames.
We've had a lot of great feedback on our app and want you to know we really appreciate it! If you come across any problems with the app on your Android device, please let us know what Android device you are using and what version of the Android OS you have. We want to make the Picturizr app the best it can be and hearing your issues will go a long way. Please e-mail us at email@example.com. Help support the FREE Picturizr app by writing us a good review. Thanks!
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Now you can redeem Picturizr Promo Codes to download paid overlays and theme packs for free! Find out how by e-mailing email@example.com and ask us.
We've added Theme Packs, Overlays, and Frames to the Picturizr Store where you'll find many free and paid downloads!
Thanks everyone for sharing with us your Picturizr experiences on Android! If you have suggestions, we'd love to hear! Email us at email@example.com, with the phone model and Android OS version you are running. Thanks!
(16 stars)
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This is a very funny app. But why I made it 4 stars instead of five is because it doesn't have a lot of picture eddidting
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Recommend getting this app its addictive and enjoyable.
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Good aap
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(16 stars)
Its so much fun showing mu friends how funny they can look...


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Someone left a bright nightlight on in the universe. One of NASA's spacecrafts located the shiniest galaxy ever discovered.
The most adorable galaxies in the universe may be a series of far-away space blobs with a lot of room, but very few stars.
The opah fish is able to keep its body warmer than its surroundings, which grants it some special powers over its cold-blooded compadres.
Britain's deadliest secret agent needs suitably lethal wheels. We take a look at the best of 007's cars, boats, and helicopters...oh, and a jet pack.
Honoured at the famous Abbey Road Studios, Alan Dower Blumlein pioneered all kinds of technologies before his untimely death during a top-secret wartime mission.
While Google bus protests continue, the Web giant tests another ferry service to bring employees from the East Bay to its Silicon Valley campus.
Internet connections up to 10x faster have been given the green light to get online when you're on a boat, train or plane.
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Learn how to quickly create and share professional diagrams with Microsoft Visio 2013.
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Let me start by saying WOW!!! This is my 2nd enclosure ive ever had in my life and I am blown away. I did have a problem after I connected these the first night and tested them with my previous piece of crap Visonik amp. I smelled burning wires, and nothing was coming from the subs. A few days later I got a new amp (Hifonics Hif1000) and rewired all the wiring inside the Polk box. After that I had the amp all tuned up and let me tell you I was skeptical at first but this thing slams! My 1000W RMS amp powers these things so good.
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Disney Theme Park Toys
Edit Page Last Edit: 1 year 7 months ago
This is a guide to Disney Theme Park Toys that can be found in or added to Disney Infinity.
- Castle Set
- Cinderella's Castle
- Happiest Place - Downloadable Toy Box World
- Haunted Mansion
- Monstro the Whale
- The Matterhorn
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