|Número de publicación||US5102662 A|
|Tipo de publicación||Concesión|
|Número de solicitud||US 07/463,000|
|Fecha de publicación||7 Abr 1992|
|Fecha de presentación||8 Dic 1989|
|Fecha de prioridad||8 Dic 1989|
|También publicado como||CA2030829A1, CA2030829C|
|Número de publicación||07463000, 463000, US 5102662 A, US 5102662A, US-A-5102662, US5102662 A, US5102662A|
|Inventores||Margarethe J. Gallagher|
|Cesionario original||Dow Corning Corporation|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (28), Citada por (59), Clasificaciones (12), Eventos legales (7)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
This invention relates to a plastic composition containing a macroporous cross-linked copolymer. More particularly, the invention includes the concept of entrapping an insect repellent in the copolymer, and incorporating the copolymer into a plastic.
The concept of producing spheres or beads by means of suspension polymerization techniques is well known in the prior art. An exemplary one of such processes is disclosed in U.S. Pat. No. 2,809,943, issued Oct. 15, 1957. However, it was found that when a material was added which is a solvent for the monomers, but acts as a precipitant for the resulting polymer, a novel form of bead was provided containing a network of microscopic channels. This discovery is set forth in U.S. Pat. No. 4,224,415, filed July 18, 1958, issuing some twenty-two years later on Sept. 23, 1980. In this patent, beads are produced ranging in size from about 350 to about 1200 microns. Typical monomers include divinyl toluene, diallyl maleate, and triallyl phosphate. The precipitant employed is an alkane, acid ester, or alcohol.
This technology was expanded and the precipitant was variously described in the patent literature as a diluent, porogen, active ingredient, solvent, functional material, and volatile agent. For example, in U.S. Pat. No. Re. 27,026, issued Jan. 12, 1971, porous beads of a diameter less than ten microns are disclosed. Among the monomers used to produce the beads are ethyl methacrylate, divinyl benzene, and ethylene glycol dimethacrylate. In U.S. Pat. No. 3,418,262, issued Dec. 24, 1968, there is described a bead characterized as having a rigid sponge structure, and wherein the porogenic agent employed is an acid such as stearic acid. Intermediates in bead form were produced in U.S. Pat. No. 3,509,078, issued Apr. 28, 1970, using polymeric materials such as polyethylene glycols as the precipitant material during the in situ suspension polymerization process. The macroporous character of such bead construction is graphically portrayed and illustrated in FIG. 1 of U.S. Pat. No. 3,627,708, issued Dec. 14, 1971. Beads termed "pearls" are produced, and containing active ingredients therein such as water or various alcohol ethers. The pearls are crosslinked to the extent of about twenty percent. In U.S. Pat. No. 3,637,535, issued Jan. 25, 1972, beads with a sponge structure are said to be capable of being compressed to an imperceptible powder. These beads are capable of being loaded with as much as 200-300% of active ingredients such as white spirit, and benzin. A rigid porous bead of a trifunctional methacrylate is taught in U.S. Pat. No. 3,767,600, issued Oct. 23, 1973. Such beads have a size of 10-900 microns, and various other monomers which can be employed include diacetone acrylamide, and ethylhexyl, hydroxyethyl, and hydroxypropyl methacrylates. Paraffin wax in an amount of 5-100% is used to form the microscopic network of channels in U.S. Pat. No. 3,989,649, issued Nov. 2, 1976. The wax may be removed from the bead structure by solvent extraction.
While many of the foregoing U.S. patents relate to ion exchange technology, a bead similar to those previously described is employed as a carrier for enzymes in U.S. Pat. No. 4,208,309, issued June 17, 1980. Such beads are of the size of about 0.1 mm. U.S. Pat. No. 4,661,327, issued Apr. 28, 1987, describes a macroreticular bead containing a magnetic core. The use of hard crosslinked porous polymeric beads in cosmetics as carriers is taught in U.S. Pat. No. 4,724,240, issued Feb. 9, 1988, wherein various emollients and moisturizers are entrapped therein. These beads are said to be capable of entrapping materials such as 2-ethylhexyl oxystearate, arachidyl propionate, petroleum jelly, mineral oil, lanolin, and various siloxanes. The size of the beads ranges from 1-3,000 microns. Typical monomers include ethylene glycol dimethacrylate, lauryl methacrylate, trimethylol propane trimethacrylate, and dipentaerythritol dimethacrylate. "In situ" hydrophobic powders and "in situ" beads may be produced in accordance with the teaching of this patent. Beads having a rigid sponge structure are also described in U.S. Pat. No. 4,690,825, issued Sept. 1, 1987, and wherein the beads function as a delivery vehicle for a host of materials including pigments, vitamins, fragrances, drugs, repellants, detergents, and sunscreens. The beads have a size of 10-100 microns and are preferably of a monomer system of styrene-divinyl benzene. Crosslinking is said to range from 10-40 percent. U.S. Pat. No. 4,806,360, issued Feb. 21, 1989, describes a post adsorbent bead which contains a melanin pigment for use as a sunscreen.
The foreign patent literature includes West German Offenlegungsschrift No. P-2608533.6, published Sept. 30, 1976, and wherein porous polymeric beads produced by "in situ" suspension polymerization are provided, and which are adapted to release perfumes. A controlled release of the fragrance is disclosed, providing utility for such beads in the home, automobiles, airplanes, railway cars, hospitals, classrooms, conference centers, and gymnasiums. Canadian Patent No. 1,168,157, issued May 29, 1984, describes hard, discrete, free flowing, bead constructions in which the beads entrap a series of functional materials which can be incorporated into toilet soap, body powder, and antiperspirant sticks. The Canadian Patent, it is noted, is the equivalent of European Patent No. 61,701, issued on July 16, 1986, both of which are foreign equivalents of the parent case of the '240 patent. In European International Publication No. 0252463A2, published Jan. 13, 1988, there is disclosed a bead having a hydrophobic polymer lattice, and which entraps numerous non-cosmetic materials such as pesticides, pharmaceuticals, pheromones, and various categories of chemicals. Steroids are entrapped, for example, in the porous beads of PCT International Publication No. WO-88/01164, published on Feb. 25, 1988. The steroids are adrenocortical steroids or various anti-inflammatory type steroids. It should therefore be apparent that what began as a simple ion exchange bead concept has rapidly grown into a technology of widely varied application.
In accordance with the present invention, copolymer powders are employed in novel processes not believed to be taught in the prior art, as exemplified by the foregoing patents. Those patents, in general, relate to suspension polymerization processes for the production of porous polymeric and copolymeric spheres and beads in which the precipitant is present during polymerization. These are defined as an "in situ" process.
Thus, according to the prior art, crosslinked porous copolymers in particle form can be produced by at least three distinct processes. One process produces beads by "in situ" suspension polymerization. Another process produces beads by suspension polymerization but the beads are "post adsorbed" with an active ingredient after the volatile porogen is removed. In a third process, powders are produced by "in situ" precipitation polymerization.
What has been accomplished in accordance with the present invention, however, is a unique concept differing from all of the foregoing methods, and wherein post adsorbent powders and beads are produced and used in a novel fashion.
This invention relates to a composition which is an unexpanded plastic resinous material having uniformly dispersed and incorporated therein discrete particles of a highly cross-linked macroporous hydrophobic polymer. The polymer has entrapped therein a chemical which is a repellent for insects. The chemical is compatible with the unexpanded plastic resinous material.
The unexpanded plastic resinous material is a thermoplastic resin, or the unexpanded plastic resinous material can be thermosetting resin. The chemical insect repellent is a compound which repels insects such as mosquitos, ticks, chiggers, and cockroaches. In the most preferred embodiment of the present invention, the insect repellent is N,N-diethyl-m-toluamide. The repellent constitutes from about twenty-five to about ninety percent by weight based on the weight of the repellent and the polymer. More specifically, the repellent constitutes about eighty percent by weight based on the weight of the repellent and the polymer. The repellent and the polymer constitute from about one-half of one percent to about fifty percent by weight based on the weight of the composition.
The invention is also directed to an article manufactured from the above composition, and in which the article is an outdoor accessory such as an item of lawn furniture. However, any article of manufacture which is desired to release a repellent for the purpose of inhibiting or eradicating the collection and swarming of insects would be appropriate in accordance with the concepts of the present invention, whether such articles are intended for indoor or outdoor use. Exemplary articles of manufacture would include trash disposal containers, lawn and garden equipment and tools, structural materials for building and residential dwelling houses.
In certain of the more specific embodiments of the present invention, one monomer of the copolymer is a monounsaturated monomer and the monounsaturated monomer is lauryl methacrylate. One monomer of the copolymer can also be a polyunsaturated monomer and the polyunsaturated monomer is selected from the group consisting of ethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. The polymer can also be formed using only polyunsaturated monomers.
The copolymer is in the form of a powder and the powder is a combined system of particles, the system of particles including unit particles of less than about one micron in average diameter, agglomerates of fused unit particles of sizes in the range of about twenty to eighty microns in average diameter, and aggregates of clusters of fused agglomerates of sizes in the range of about two-hundred to about twelve-hundred microns in average diameter. A bead form of the copolymer can also be employed.
A precipitation polymerization process is used for producing the macroporous cross-linked copolymer. In the process, there is copolymerized at least one monounsaturated monomer and at least one polyunsaturated monomer in the presence of an organic liquid which is a solvent for and dissolves the monomers but not the copolymer. The copolymerization of the monomers is initiated by means of a free radical generating catalytic compound, precipitating a copolymer in the solvent in the form of a powder. A dry powder is formed by removing the solvent from the precipitated copolymeric powder.
The solvent is preferably isopropyl alcohol, although ethanol, toluene, heptane, xylene, hexane, ethyl alcohol, and cyclohexane, may also be employed. The monounsaturated monomer and the polyunsaturated monomer can be present in mol ratios of, for example, 20:80, 30:70, 40:60, or 50:50. The process includes the step of stirring the monomers, solvent, and the free radical generating catalytic compound, during copolymerization. Preferably, the dry powder is formed by filtering excess solvent from the precipitated powder, and the filtered powder is vacuum dried. The powder may then be "post adsorbed" with the functional material.
The powders of the present invention may also be used as carriers or adsorbents for various materials such as water, aqueous systems, emollients, moisturizers, fragrances, dyes, pigments, flavors, drugs such as ibuprofen, phosphoric acid, all categories of insect repellents, vitamins, sunscreens, detergents, cosmetics, pesticides, pheromones, herbicides, steroids, sweeteners, pharmaceuticals, and antimicrobial agents. Finely divided solids such as analgesic materials can be adsorbed by dissolving the finely divided analgesic in a solvent, mixing the analgesic and solvent with the powder, and removing the solvent. Other post adsorbable materials include alkanes, alcohols, acid esters, silicones, glycols, organic acids, waxes, and alcohol ethers.
These and other objects, features, and advantages, of the present invention will become apparent when considered in light of the following detailed description, including the accompanying drawings.
FIG. 1 is a photomicrograph of the various components of the complex structure of the powder produced in Example I, and including unit particles, agglomeratures, and aggregates.
FIGS. 2 and 3 are photomicrographs of the agglomerates and aggregates of FIG. 1, respectively, shown on a larger scale.
FIG. 4 is a photomicrograph of a polymer bead produced by suspension polymerization.
FIG. 5 is a photomicrograph of the bead of FIG. 4 with a portion of the shell removed to reveal the interior structure of the bead.
FIG. 6 is a photomicrograph of a copolymeric powder material. The powder is shown in magnification as it appears when the agitation rate employed in the process for producing the powder is zero rpm.
FIGS. 7-10 are additional photomicrographs of copolymeric powder materials. The powder is shown in magnification as it appears when the agitation rate employed in the process for producing the powder varies from seventy-five rpm up to eight hundred rpm.
In the above figures in the drawing, the magnification is indicated in each instance. For example, the magnification in FIGS. 6-9 is 1000 X, and 2000 X in FIG. 10. FIGS. 6-10 also include an insert identifying a length approximating ten microns for comparative purposes.
It should be pointed out, that in viewing the various figures, one will note that as the rate of stirring is increased from zero rpm up to eight hundred rpm, that the size of the unit particles increase. This is in direct opposition to what has been traditionally observed in suspension polymerization systems, wherein increases in stirring rates decrease particle size. Because of the increased size of the unit particles shown in FIG. 10 and the resulting decrease in surface area, the adsorptive capacity of these large particles is less than the adsorptive capacity of the smaller sized particles shown in FIGS. 6-9.
The most effective unit particles can be produced if the rate of stirring is maintained below about three hundred rpm, although particles produced at rates beyond three hundred rpm are useful and adsorptive, but to a lesser extent.
The material of the present invention, can be broadly and generally described as a crosslinked copolymer capable of entrapping solids, liquids, and gases. The copolymer is in particulate form and constitutes free flowing discrete solid particles even when loaded with an active material. When loaded, it may contain a predetermined quantity of the active material. One copolymer of the invention has the structural formula: ##STR1## where the ratio of x to y is 80:20, R' is --CH2 CH2 --, and R" is --(CH2)11 CH3.
The copolymer is highly crosslinked as evidenced by the foregoing structural formula, and is more particularly a polymethacrylate. This material is manufactured by the Dow Corning Corporation, Midland, Mich., U.S.A., and sold under the trademark POLYTRAP®. It is a low density, highly porous, free-flowing white particulate, and the particles are capable of adsorbing high levels of lipophilic liquids and some hydrophilic liquids, while at the same time maintaining a free-flowing particulate character.
In the powder form, the structure of the particulate is complex, and consists of unit particles less than one micron in average diameter. The unit particles are fused into agglomerates of twenty to eight microns in average diameter. These agglomerates are loosely clustered into macro-particles termed aggregates of about 200 to about 1200 microns in average diameter.
Adsorption of actives to form post adsorbent powder, can be accomplished using a stainless steel mixing bowl and a spoon, wherein the active ingredient is added to the empty dry powder, and the spoon is used to gently fold the active into the powder. Low viscosity fluids may be adsorbed by addition of the fluids to a sealable vessel containing the powder and tumbling the materials until a consistency is achieved. More eleborate blending equipment such as ribbon or twin cone blenders can also be employed.
The following example illustrates a method for making a post adsorbent powder, of the type illustrated in FIGS. 1-3 and 6-10.
A hydrophobic porous copolymer was produced by the precipitation polymerization technique by mixing in a five hundred milliliter polymerization reactor equipped with a paddle type stirrer, 13.63 grams of ethylene glycol dimethacrylate monomer, or eighty mole percent, and 4.37 grams of lauryl methacrylate monomer, or twenty mole percent. Isopropyl alcohol was added to the reactor as the solvent in the amount of 282 grams. The monomers were soluble in the solvent, but not the precipitated copolymer. The process can be conducted with only polyunsaturated monomers if desired. The mixture including monomers, solvent, and 0.36 grams of catalytic initiator benzoyl peroxide, was purged with nitrogen. The system was heated by a water bath to about sixty degrees Centigrade until copolymerization was initiated, at which time, the temperature was increased to about 70-75 degrees Centigrade for six hours, in order to complete the copolymerization. During this time, the copolymer precipitated from the solution. The copolymerization produced unit particles of a diameter less than about one micron. Some of the unit particles adhered together providing agglomerates of the order of magnitude of about twenty to eighty microns in diameter. Some of the agglomerates adhered further and were fused and welded one to another, forming aggregates of loosely held assemblies of agglomerates of the order of magnitude of about two to eight hundred microns in diameter. The mixture was filtered to remove excess solvent, and a wet powder cake was tray dried in a vacuum oven. A dry hydrophobic copolymeric powder consisting of unit particles, agglomerates, and aggregates was isolated.
The adsorptive capacity of the hydrophobic particulates produced in Example I, as a function of the stirring rate, was determined. The stirring rate during the reaction in Example I significantly influenced the adsorption properties of the particulate materials. The adsorptivity of the particulate materials decreases with an increase in stirring rate, and the density of the particulates increases. These results are set forth in Tables I-III.
TABLE I______________________________________Agita- Bulk Average Average Averagetion Density Aggregate Agglom- UnitRate Size Size erate Particle Adsorption(RPM) (g/cc) (μ) Size (μ) Size (μ) Capacity*______________________________________ 0 0.067 182.5 33.9 1.0 83.0 75 0.077 140.6 36.6 0.5 84.8150 0.071 149.8 39.8 0.8 83.0300 0.293 47.0 34.0 1.5-2.0 58.3800 0.440 -- 10.0 3.0-5.0 37.7______________________________________ *Percent Silicone Oil
TABLE II______________________________________Stirring Adsorption Capacity %Speed Mineral OrganicRPM Water Oil Glycerine Ester*______________________________________ 0 0 80 75 80 75 0 83.9 75 81.5150 0 80 75 80300 0 54.5 58.3 54.5______________________________________ *2-ethylhexyl-oxystearate
TABLE III______________________________________Adsorption Capacity %Mineral 2-ethylhexyl Silicone Density (g/cm3)RPM Oil oxystearate Oil Bulk Tapped______________________________________ 0 82.5 82.5 86.5 0.0368 0.0580 75 82.3 82.2 86.5 0.0462 0.0667150 82.3 82.3 86.3 0.0527 0.0737200 81.5 81.5 85.7 0.0554 0.0752250 79.2 80.0 84.8 0.0636 0.0859300 68.8 68.8 75.0 0.1300 0.1768450 58.3 58.3 61.5 0.1736 0.2392600 54.5 54.5 60 0.1933 0.2792700 42.2 42.5 45.7 0.2778 0.4142800 33.3 28.6 33.3 0.3862 0.53221000 32.8 28.5 32.9 0.3808 0.5261______________________________________
In the foregoing tables, it can be seen that adsorption and density, as a function of stirring rate, was determined for several fluids including a silicone oil, water, mineral oil, glycerine, and an organic ester. From zero rpm up to about 250 rpm, the adsorptivity of the porous copolymeric powder particulates of Example I remained essentially consistent. However, at about three hundred rpm, there was a substantial decrease in adsorptivity, which decrease became more apparent as the stirring rate was increased up to about one thousand rpm. A similar pattern is evidenced by the data which are reflective of the density.
This phenomenon is more apparent in the photomicrographic figures of the drawing. Thus, it can be seen from FIG. 6, that the particle size of the unit particles increases as the stirring rate is increased, as evidenced by FIG. 10. A progression in this phenomenon can be observed in FIGS. 7-9.
While the procedure of Example I is a precipitation polymerization process and not a suspension polymerization system, the prior art dealing with suspension polymerization processes, teaches that an increase in stirring rate causes a decrease in particle size. This is documented, for example, in U.S. Pat. No. 4,224,415, issued Sept. 23, 1980, and in the PCT International Publication. The PCT International Publication employs stirring rates upwards of nine hundred to twelve hundred rpm. In Example I of the present invention, however, increases in stirring rates not only did not decrease the particle size, but in fact had exactly the opposite effect, causing the unit particle size to increase. As the rate of stirring increased from zero rpm up to one thousand, the density of the particles increased and the adsorptive capacity decreased.
In accordance with the above, it is possible to tailor porous adsorbent powders of a particular particle size and adsorptivity by means of stirring rate. Thus, with large unit particles in FIG. 10, the adsorptive capacity is less than the adsorptive capacity of smaller sized unit particles in FIGS. 6-9. While the most effective particles are produced when the rate of stirring is maintained below about three hundred rpm, particles produced at rates beyond three hundred rpm are useful.
It is important to understand that the method of Example I for the production of porous copolymer particulate powder materials is characterized as a precipitation polymerization technique. In accordance with the technique, monomers are dissolved in a compatible volatile solvent in which both monomers are soluble. Polymer in the form of a powder is precipitated and the polymer is insoluble in the solvent. No surfactant or dispersing aid is required. The materials produced are powders and not spheres or beads. The powder particulates include unit particles, agglomerates, and aggregates. The volatile solvent is subsequently removed resulting in a dry powder, which can be post adsorbed with a variety of functional active ingredients. The suspension polymerization process on the other hand, provides that polymerization be carried out in water, and in some cases chloroform or chlorinated solvents. The monomers, the active, and the catalyst, form beads or droplets in water, and polymerization occurs within each bead. A surfactant or stabilizer, such as polyvinyl pyrrolidone, is required in order to prevent the individually formed beads and droplets from coalescing. The resulting beads, with the active material entrapped therein, include a substantially spherical outer crust or shell, the interior of which contains a macroporous structure of fused unit particles, agglomerates, and aggregates. The bead is about ten microns in average diameter to about one hundred-fifty microns, depending upon the rate of agitation employed during the process. Such beads are shown in FIGS. 4 and 5, and the process is set forth in Example III.
Some unique features of the powders of Example I and FIGS. 1-3 and 6-10 are their ability to adsorb from sixty to eighty percent of a liquid and yet remain free flowing. The materials provide a regulated release of volatile ingredients such as cyclomethicone entrapped therein, and have the capability of functioning as carriers for other non-volatile oils. Loaded powders disappear when rubbed upon a surface. This phenomenon is believed due to the fact that large aggregates of the material scatter light rendering the appearance of a white particulate, however, upon rubbing, these large aggregates decrease in size approaching the range of visible light and hence seem to disappear. The materials find applications in diverse areas such as cosmetics and toiletries, household and industrial products, pesticides, pheromone carriers, and pharmaceuticals. The materials do not swell in common solvents and are capable of physically adsorbing active ingredients by the filling of interstitial voids by capillary action. The active ingredients are subsequently released by capillary action or wicking from the voids within the particulates.
The following example illustrates a precipitation polymerization process in which an organic ester is entrapped "in situ" in the polymer powder.
7 grams of 2-ethylhexyl oxystearate was mixed with 1.5 grams of ethylene glycol dimethacrylate and 1.5 grams of lauryl methacrylate in a glass test tube. The solution was deaerated for five (5) minutes and 0.1 ml of t-butyl peroctoate was added and mixed while heating to 80 degrees Centigrade in an oil bath. After 20 minutes, the contents solidified; and the mixture was maintained at about 80 degrees Centigrade for an additional hour to assure full polymerization. A semi-soft, heterogeneous white opaque polymer mass resulted containing the entrapped ester.
The powder of Example II differs from the powder of Example I in that the solvent in Example I is removed resulting in a dry empty powder which is post adsorbed with other functional materials. The powder of Example II is otherwise similar to the material shown in FIGS. 1--3.
Example III illustrates a process for the production of beads as shown in FIGS. 4 and 5. The process is suspension polymerization and an organic ester is entrapped "in situ".
1.20 grams of polyvinyl pyrrolidone was dissolved in 1500 ml of water in a 2000 ml three necked resin flask equipped with a stirrer, thermometer and nitrogen purge. A solution of 335 grams of 2-ethylhexyl oxystearate, 132 grams ethylene glycol dimethacrylate, 33 grams 2-ethylhexyl methacrylate, and 5 ml t-butyl peroctoate, was bubbled with nitrogen for 5 minutes. The resultant mix was slowly added to the stirred aqueous solution of polyvinyl pyrrolidone at 22 degrees Centigrade under nitrogen. The temperature was raised to 80 degrees Centigrade with constant agitation and held until polymerization started in approximately 15 minutes, and maintained at 80 degrees Centigrade for an additional 2 hours to complete the reaction. Semi-soft, white opaque beads were collected by filtering off the supernatant liquid and dried to remove any excess water. The beads weighed 450 g for a yield of 90%, and were 0.25 to 0.5 mm in diameter. Other protective colloids such as starch, polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, or inorganic systems such as divalent alkali metal hydroxides, for example MgOH, may be used in place of the polyvinyl pyrrolidone suspending medium.
In Example III macroporous polymers submicron in size are produced with two or more monomers, at least one monomer of which contains more than a single double bond. The polymerization is conducted in the presence of an active ingredient which does not dissolve or swell the resulting polymer. The monomers and the active ingredient are mutually soluble, but are insoluble in the aqueous suspending medium in which droplets are formed. Polymerization occurs within suspended droplets, and beads or spheres are produced. The active ingredient which is polymerized "in situ" is entrapped and contained within the beads, but the active ingredient is capable of being released. It is also possible to use a volatile liquid during polymerization, and to subsequently thermally drive off the volatile liquid, leaving behind a porous polymer bead product into which a variety of active materials can be subsequently adsorbed.
Examples of polyunsaturated monomers suitable for use in accordance with the present invention are ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol propane ethoxylated triacrylate, ditrimethylol propane dimethacrylate; propylene, dipropylene and higher propylene glycols, 1,3 butylene glycol dimethacrylate, 1,4 butanediol dimethacrylate, 1,6 hexanediol dimethacrylate, neopentyl glycol dimethacrylate, pentaerythritol dimethacrylate, dipentaerythritol dimethacrylate, bisphenol A dimethacrylate, divinyl and trivinyl benzene, divinyl and trivinyl toluene triallyl maleate, triallyl phosphate, diallyl maleate, diallyl itaconate, and allyl methacrylate. The monounsaturated monomers include allyl methacrylates and acrylates having straight or branched chain alkyl groups with 1 to 30 carbon atoms, preferably 5 to 18 carbon atoms. Preferred monomers include lauryl methacrylate, 2-ethylhexyl methacrylate, isodecylmethacrylate, stearyl methacrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, diacetone acrylamide, phenoxy ethyl methacrylate, tetrahydrofurfuryl methacrylate and methoxy ethyl methacrylate.
As noted previously, the copolymer can be formed by copolymerizing one monounsaturated monomer with one polyunsaturated monomer, or with only polyunsaturated monomers.
Example I was repeated for each of a series of monomer systems shown in Tables IV-XVII. In each instance, submicron sized copolymeric powders were produced employing a stirring speed of about seventy-five RPM. The catalyst was benzoyl peroxide. Adsorption capacities of the various copolymeric powders for fluids were determined and are shown in the Tables, along with the mole ratios of monomers and the solvent. The abbreviations used in Tables IV-XVII are identified as follows:
EGDM--Ethylene gylcol dimethacrylate
TEGDM--Tetraethylene glycol dimethacrylate
TBAEMA--t-butyl aminoethyl methacrylate
AMPS--2-acrylamido propane sulfonic acid
TABLE IV______________________________________ Adsorption Capacity % Mole Sol- Glyc-Monomers Ratio vent EHO erine GG Water______________________________________DAA/EGDM 20/80 Xylene 75 82 83 78DAA/EGDM 30/70 Xylene 77 80 83 78DAA/EGDM 40/60 Xylene 75 75 83 77DAA/EGDM 50/50 Xylene 50 57 67 0DAA/EGDM 60/40 Xylene 40 40 50 0DAA/TEGDM 20/80 Xylene 40 50 62 58DAA/TEGDM 30/70 Xylene 29 40 50 55DAA/TEGDM 40/60 Xylene 25 28 40 43DAA/TEGDM 50/50 Xylene 25 30 40 43DAA/TEGDM 60/40 Xylene 22 29 40 40______________________________________
TABLE V______________________________________ Adsorption Capacity % Mole Glyc-Monomers Ratio Solvent EHO erine PEG Water______________________________________ST/TEGDM 20/80 IPA 58 69 69 67ST/TEGDM 30/70 IPA 58 64 67 69ST/TEGDM 40/60 IPA 62 71 71 61ST/TEGDM 50/50 IPA 67 62 54 58ST/TEGDM 60/40 IPA 50 58 58 54ST/TEGDM 70/30 IPA 50 58 50 54ST/TEGDM 80/20 IPA 44 54 50 50ST/DVB 20/80 IPA 80 75 75 0ST/DVB 30/70 IPA 75 67 75 0ST/DVB 40/60 IPA 69 67 67 0ST/DVB 50/50 IPA 64 72 67 0ST/DVB 60/40 IPA 67 71 71 0ST/DVB 70/30 IPA 71 75 76 0ST/DVB 80/20 IPA 50 50 50 0______________________________________
TABLE VI______________________________________ Adsorption Capacity % Mole Glyc-Monomers Ratio Solvent EHO erine GG Water______________________________________VP/EGDM 20/80 Xylene 77 80 74 73.6VP/EGDM 30/70 Xylene 76 79 78.3 70VP/EGDM 40/60 Xylene 70 67 75.6 75VP/EGDM 50/50 Xylene 72 76 80 76VP/EGDM 60/40 Xylene 74 80 76 77VP/EGDM 70/30 IPA 71 78 74 75VP/EGDM 80/20 IPA 67 75 73 74VP/TEGDM 20/80 Xylene 58 68.8 61.5 67.7VP/TEGDM 30/70 Xylene 70 67 54.5 68.8VP/TEGDM 40/60 Xylene 54.5 61.5 52.4 64.3VP/TEGDM 50/50 Xylene 44.4 47.4 52.4 52.4VP/TEGDM 60/40 Xylene 50 44.4 50 54.4VP/TEGDM 70/30 Xylene 50 47.4 44.4 50VP/TEGDM 80/20 Xylene 54.5 52.4 60 58______________________________________
TABLE VII__________________________________________________________________________ Adsorption Capacity %Monomers Mole Ratio Solvent EHO Glycerine GG Water__________________________________________________________________________IBOMA/EGDM 20/80 IPA 62.9 9.1 71.4 0IBOMA/EGDM 30/70 IPA 64.3 16.6 67.7 0IBOMA/EGDM 40/60 IPA 68.7 28.6 61.5 0IBOMA/EGDM 50/50 IPA 67.7 16.7 58.3 0IBOMA/EGDM 60/40 IPA 50 23.1 50 0IBOMA/EGDM 70/30 IPA 50 9.1 47.3 0IBOMA/EGDM 80/20 IPA 52.3 16.6 44.4 0IBOMA/TEGDM 20/80 IPA 66.6 62.9 61.5 0IBOMA/TEGDM 30/70 IPA 61.5 61.5 70.6 0IBOMA/TEGDM 40/60 IPA 64.3 64.3 71.4 0IBOMA/TEGDM 50/50 IPA 61.5 66.6 67.7 0IBOMA/TEGDM 60/40 IPA 58.3 54.5 54.5 0IBOMA/TEGDM 70/30 IPA 47.3 50 41.1 0IBOMA/TEGDM 80/20 IPA 37.5 41.1 33.3 0__________________________________________________________________________
TABLE VIII______________________________________ Adsorption Capacity % Mole Sol- Glyc- Wa-Monomers Ratio vent EHO erine GG ter______________________________________PEMA/EGDM 20/80 IPA 64.3 68.7 66.6 61.5PEMA/EGDM 30/70 IPA 54.5 50 54.5 44.0PEMA/EGDM 40/60 IPA 52.3 47.3 72.2 9PEMA/EGDM 50/50 IPA 54.5 33.3 62.9 0PEMA/EGDM 60/40 IPA 67.7 28.5 70.5 0PEMA/EGDM 70/30 IPA 69.7 44.4 60.7 0PEMA/EGDM 80/20 IPA 66.6 68.7 66.6 0PEMA/TEGDM 20/80 IPA 58.3 56.5 66.6 58.3PEMA/TEGDM 30/70 IPA 64.2 70.5 67.7 62.9PEMA/TEGDM 40/60 IPA 66.6 67.7 71.4 69.7PEMA/TEGDM 50/50 IPA 66.6 70.5 73.6 72.2PEMA/TEGDM 60/40 IPA 58.3 62.9 52.3 61.5PEMA/TEGDM 70/30 IPA 50 58.3 52.3 54.5PEMA/TEGDM 80/20 IPA 67.7 73.6 76.1 47.3______________________________________
TABLE IX______________________________________ Adsorption Capacity % Mole Sol- Gylc- Wa-Monomers Ratio vent EHO erine PEG ter______________________________________IDMA/EGDM 20/80 IPA 55 64 70 0IDMA/EGDM 30/70 IPA 38 50 44 0IDMA/EGDM 40/60 IPA 50 67 69 0IDMA/EGDM 50/50 IPA 58 64 67 0IDMA/EGDM 60/40 IPA 58 69 69 0IDMA/TEGDM 20/80 IPA 62 70 70 0IDMA/TEGDM 30/70 IPA 50 62 62 0IDMA/TEGDM 40/60 IPA 62 67 67 0IDMA/TEGDM 50/50 IPA 38 44 50 0IDMA/TEGDM 60/40 IPA 38 55 50 0______________________________________
TABLE X______________________________________ Adsorption Capacity % Mole Sol- Glyc- Wa-Monomers Ratio vent EHO erine PEG ter______________________________________STMA/EGDM 10/90 IPA 66 64.3 66.7 0STMA/EGDM 20/80 IPA 69 63 65.5 0STMA/EGDM 30/70 IPA 73-75 58.3 61.5 0STMA/EGDM 40/60 IPA 69-71 54.5 58.3 0STMA/EGDM 50/50 IPA 60-63 52.4 52.4 0STMA/TEGDM 20/80 IPA 50 47.4 52.4 0STMA/TEGDM 30/70 IPA 50 64.3 50 0STMA/TEGDM 40/60 IPA 52.4 61.5 58.3 0STMA/TEGDM 50/50 IPA 47.4 52.4 56.5 0______________________________________
TABLE XI______________________________________ Adsorption Capacity % Mole Sol- Glyc- Wa-Monomers Ratio vent EHO erine PEG ter______________________________________HPMA/EGDM 20/80 Xylene 64.3 61.5 61.5 9HPMA/EGDM 30/70 Xylene 54.5 16.7 58.3 0HPMA/EGDM 40/60 Xylene 54.5 9 58.3 0HPMA/EGDM 50/50 Xylene 37.5 58.3 50 0HPMA/EGDM 60/40 Xylene 44.4 61.5 58.3 0HPMA/EGDM 70/30 Xylene 50 44.4 37.5 0HPMA/EGDM 80/20 Xylene 61.5 16.7 58.3 0HPMA/TEGDM 20/80 Xylene 50 58.3 54.5 61.5HPMA/TEGDM 30/70 Xylene 56.5 54.5 50 60HPMA/TEGDM 40/60 Xylene 50 58.3 52.4 54.5HPMA/TEGDM 50/50 Xylene 52.4 61.5 54.5 56.5HPMA/TEGDM 60/40 Xylene 33.3 47.4 44.4 54.5HPMA/TEGDM 70/30 Xylene 54.5 44.4 54.5 50HPMA/TEGDM 80/20 Xylene 50 47.4 41.2 37.5______________________________________
TABLE XII______________________________________ Adsorption Capacity % Mole Sol- Glyc- Wa-Monomers Ratio vent EHO erine PEG ter______________________________________CYMA/EGDM 80/20 IPA 61.5 71.4 66.6 0CYMA/EGDM 70/30 IPA 60 66 64.2 0CYMA/EGDM 60/40 IPA 61.5 66 66.6 0CYMA/EGDM 50/50 IPA 64.2 66 68.7 0CYMA/EGDM 40/60 IPA 64.2 66 68.7 0CYMA/EGDM 30/70 IPA 61.5 66 66.6 0CYMA/EGDM 20/80 IPA 66.6 71.4 75 61.5CYMA/TEGDM 80/20 IPA 68.7 0 68.7 0CYMA/TEGDM 70/30 IPA 71.4 0 69.7 0CYMA/TEGDM 60/40 IPA 66.6 0 62.9 0CYMA/TEGDM 50/50 IPA 0 0CYMA/TEGDM 40/60 IPA 60 0 72.9 0CYMA/TEGDM 30/70 IPA 64.2 0 72.2 0CYMA/TEGDM 20/80 IPA 61.5 0 66.6 0______________________________________
TABLE XIII__________________________________________________________________________ Mole Adsorption Capacity %Monomers Ratio Solvent Water Mineral Oil Gylcerine EHO__________________________________________________________________________DMAEMA/EGDM 20/80 Hexane 0 58.3 66.7 58.3DMAEMA/EGDM 40/60 Hexane 66.7 61.5 70.6 66.7DMAEMA/EGDM 60/40 Hexane 77.3 61.5 72.2 76.2DMAEMA/EGDM 80/20 Hexane 66.7 58.3 68.8 58.3TBAEMA/EGDM 20/80 Hexane 0 70.6 75 70.6TBAEMA/EGDM 40/60 Hexane 0 66.7 72.2 66.7TBAEMA/EGDM 60/40 Hexane 0 61.5 68.75 61.5TBAEMA/EGDM 80/20 Hexane 0 44.4 54.6 50TBAEMA/EGDM 80/20 Hexane 54.6 54.6 58.3 50__________________________________________________________________________
TABLE XIV__________________________________________________________________________ Adsorption Capacity %Monomers Mole Ratio Solvent Water Mineral Oil Glycerine EHO__________________________________________________________________________AMPS/EGDM 20/80 Xylene 84.3 83.3 85.3 83.3BMA/EGDM 20/80 Hexane 0 70.6 75 68.8BMA/EGDM 40/60 Hexane 0 70.6 77.3 70.6BMA/EGDM 40/60 Ethyl- 0 66.7 73.7 68.8 AlcoholBMA/EGDM 60/40 Hexane 0 72.2 0 73.7BMA/EGDM 80/20 Hexane 0 54.5 66.7 58.3__________________________________________________________________________
TABLE XV__________________________________________________________________________ Adsorption Capacity %Monomers Mole Ratio Solvent Water Mineral Oil Glycerine EHO__________________________________________________________________________2 EHMA/EGDM 20/80 IPA 0 68.8 66.7 64.32 EHMA/EGDM 30/70 IPA 0 68.8 66.7 64.32 EHMA/EGDM 40/60 IPA 0 66.7 66.7 70.62 EHMA/EGDM 50/50 IPA 0 64.3 68.3 61.52 EHMA/EGDM 60/40 IPA 0 61.5 64.3 502 EHMA/EGDM 70/30 IPA 0 58.3 64.3 502 EHMA/EGDM 80/20 IPA 0 58.3 64.3 50__________________________________________________________________________
TABLE XVI__________________________________________________________________________ Adsorption Capacity %Monomers Mole Ratio Solvent Water Mineral Oil Glycerine EHO__________________________________________________________________________MMA/EGDM 20/80 IPA 61.5 58.3 64.3 58.3MMA/EGDM 30/70 IPA 64.3 61.5 66.7 61.5MMA/EGDM 40/60 IPA 61.5 64.3 64.3 61.5MMA/EGDM 50/50 IPA 58.3 54.5 61.5 58.3MMA/EGDM 60/40 IPA 54.5 50 61.5 54.5MMA/EGDM 70/30 IPA 66.7 61.5 72.2 64.3MMA/EGDM 80/20 IPA 66.7 44.4 78.3 44.4__________________________________________________________________________
TABLE XVII__________________________________________________________________________ Adsorption Capacity %Monomers Mole Ratio Solvent Water PEG Glycerine EHO__________________________________________________________________________HEMA/EGDM 20/80 IPA 54.5 54.5 54.5 50HEMA/EGDM 30/70 IPA 58.3 64.3 58.3 54.5HEMA/EGDM 40/60 IPA 58.3 61.5 64.3 54.5HEMA/EGDM 50/50 IPA 61.5 61.5 61.5 50HEMA/EGDM 60/40 IPA 61.5 64.3 61.5 50HEMA/EGDM 70/30 IPA 58.3 64.3 58.3 50HEMA/EGDM 80/20 IPA 61.5 58.3 61.5 54.5__________________________________________________________________________
The water adsorbing porous polymeric materials produced above in some instances are to be contrasted with the water containing beads of U.S. Pat. No. 3,627,708, issued Dec. 14, 1971. The bead of the '708 patent is produced by "in situ" suspension polymerization, and is adapted to contain water only because of the presence of a solubilizer such as sodium bis(2-ethyl hexyl) sulfosuccinate. The materials of Example IV, on the other hand, are produced by a precipitation polymerization process, which contains no solubilizer, and produces a material in the form of a powder consisting of unit particles, agglomerates, and aggregates. Thus, these materials are very distinct from the materials of the '708 patent.
The particulates of the present invention can be used as a carrier and the particulate carrier means can be in the form of micron-sized beads, or the particulate carrier means can be in the form of a powder. In the latter case, the powder constitutes a combined system of particles, the system of powder particles including unit particles of a size less than about one micron in average diameter, agglomerates of fused unit particles of sizes in the range of about twenty to about eighty microns in average diameter, and aggregates of clusters of fused agglomerates of sizes in the range of about two hundred to about twelve hundred microns in average diameter.
As noted above, highly crosslinked, polymeric systems consisting of particles of submicron size, can be prepared from monomers having at least two polymerizable unsaturated bonds and containing no comonomers having monounsaturated moiety. These highly crosslinked systems can adsorb large quantities of active substances even of very different structures and properties.
Examples of such monomers are bis or poly acrylates, methacrylates or itaconates of ethylene glycol, propylene glycol, di-, tri-, tetra-, poly- ethylene glycol and propylene glycol, trimethylol propane, glycerine, erythritol, xylitol, pentaerythritol, di-pentaerythritol, sorbitol, mannitol, glucose, sucrose, cellulose, hydroxy cellulose, methyl cellulose, and 1,2; and 1,3-propanediol, 1,3; and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and cyclohexanediol, and triol. Similarly, bis acrylamido or methacrylamido compounds can be used, such as methylene bis acryl or methacrylamide, 1,2-dihydroxy ethylene bis-acryl or methacrylamide, and hexamethylene bis-acryl or methacrylamide. Another group of monomers are represented by di or poly vinyl esters such as divinyl oxalate, malonate, succinate glutarate, adipate, sebacate, divinyl maleate, fumarate, citraconate, and mesaconate.
Still another group of monomers is represented by di or poly vinyl ethers of ethylene, propylene, butylene, glycols of glycerine, pentaerythritol, sorbitol, divinyl ether, di or poly-allyl compounds based on glycols, and glycerine, or combinations of vinyl allyl or vinyl acryloyl compounds such as vinyl methacrylate, acrylate, allyl methacrylate, acrylate, and methallyl methacrylate, acrylate. Aromatic, cycloaliphatic or heterocyclic monomers such as divinyl benzene, toluene, diphenyl, cyclohexane, trivinyl benzene, divinyl pyridine, and piperidine, can also be used.
The polymerization is achieved by the use of a variety of free radical initiators which can be azo compounds, a peroxy dicarbonate, a peroxy ester, or a sulfonyl acid peroxide. Illustrative of free radical initiators in the process are 2,2'-azobis(2,4-dimethyl-4-methoxy valeronitrile), benzoyl peroxide, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, acetyl peroxide, 2-t-butylazo-2-cyano-4-methylpentane, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, diisononanyl peroxide, lauroyl peroxide, propinoyl peroxide, bis(4-t-butyl cyclohexyl)peroxy dicarbonate, di(sec-butyl) peroxy dicarbonate, diisopropyl peroxy carbonate, di(n-propyl) peroxy carbonate, di(2-ethylhexyl) peroxy carbonate, di(2-phenoxyethyl) peroxy carbonate, t-amyl peroxy pivatate, t-amyl perpivatate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy neodecanonate, t-amyl perneodecanonate, cumyl perneodecanonate, cumyl perpivate, 2,5-dimethyl-2,5-bis(2-ethyl hexanoyl peroxy) hexane, t-butylperoxy-2-ethylhexanoate, t-amyl peroxy (2-ethylhexanoate) and acetyl cyclohexyl sulfonyl peroxide.
Illustrative redox initiators 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 and dipentyl amine.
The plastic material in which the polymer containing the entrapped insect repellent is incorporated may constitute any of a wide variety of thermoplastic or thermosetting resins, with the proviso that the chemical repellent composition be compatible with the material selected. The resins may be in the form of pellets, granules, and powders. Exemplary materials are polyoxymethylene, acrylics, cellulosics, fluoroplastics, nitrile resins, Nylons, polyamide-imides, polyarylates, polybutylene, polycarbonates, polybutylene terephthalate, polyethylene terephthalate, polyetherimides, polyethylene, ethylene-ethyl-acrylate, polymethylpentene, polypropylene, acrylonitrile-butadiene-styrene, acrylic-styrene-acrylonitrile, polystyrene, styrene-acrylonitrile, styrene-butadiene, sulfone based resins, thermoplastic elastomers, vinyl based resins, epoxies, phenolic resins, and polyesters.
In the case of thermoplastic resins, the polymer containing the entrapped insect repellent is incorporated into the resin during the extrusion process. If other processes are used such as coating, molding, thermoforming, or calendering, the polymer containing the entrapped insect repellent is incorporated into the resin during such processes. In the case of thermosetting resins, the polymer is incorporated during the compression molding operation. It is preferable to incorporate the polymer into the resin prior to melt processing in order to insure a uniform dispersal in the resin matrix. The resins can then be blown or cast into film, injection or blow molded, or extruded. The effectiveness of products so produced will vary from a period of days in the case of thin films to years in compression molded wall panels. The polymer may also be incorporated into reinforced types of resins, if desired. The insect repellent may be entrapped into the macroporous polymer bead or powder of the present invention in accordance with the procedures of Example I or II in the case of a powder form, or Example III in the case of the bead form.
For purposes of the present invention, the term "unexpanded" is intended to mean plastics other than cellular materials containing an appreciable fraction of uniformly dispersed voids or cells whether classified as open-celled or closed-celled. Thus, open foams of the type in U.S. Pat. No. 4,828,542, issued May 9, 1989, would not be included among the types of plastic materials intended under the present invention.
As noted previously, the preferred chemical for use as the insect repellent is N,N-diethyl-m-toluamide, commonly referred to as DEET. Other repellent chemicals that may be employed include, for example, dimethyl phthalate; Rutgers 6-12 2-ethyl-1,3-hexanediol; Stabilene; MGK Repellent 326; Indalone; dibutyl phthalate; MGK Repellent 11; Citronyl; alicyclic piperidines; Permethrin; dibutyl succinate; hexahydrodibenzofuran carboxaldehyde-butadiene-furfural copolymer; tert-butyl N,N-dimethyldithiocarbamate; 2-hydroxyethyl n-octyl sulfide; pyrethrins; Diazinon; Aldicarb; pine oil; and anthrahydroquinones. Such chemicals are effective against various categories of mosquitos, ticks, chiggers, and cockroaches.
The following examples illustrate the concept of the present invention.
Into a mixing bowl was placed ten grams of the powder of Example I. To the powder was added forty grams of liquid insecticide diethyltoluamide. The mixture was blended with a spoon until uniform. The powder readily absorbed the liquid insecticide, entrapping the insecticide therein and yet remaining free flowing. The powder with the entrapped insecticide therein is suitable for incorporation into resin matrices for the production of insect repelling articles of manufacture. Larger quantities of the powder containing the entrapped insecticide may be produced by employing a Patterson-Kelly Twin Cone Blender.
A four liter polymer kettle containing two-hundred milliliters of distilled water and two-hundred milliliters of pine oil was flushed with nitrogen. The solution was mixed and the temperature raised to approximately eighty-five degrees Centigrade. To the kettle was added five-hundred milliliters of twenty percent by weight of divinylbenzene, five percent by weight of benzoyl peroxide, and the remainder styrene. After thirty minutes the polymerization ceased and the polymer bead entrapping the pine oil insecticide was collected by filtration.
A mixture of finely ground sulfonated styrene-divinylbenzene polymer containing fifteen percent divinylbenzene and polyethylene pellets was heated to one hundred-eighty degrees Centigrade, kneaded in a mixture, and pelletized to one sixteenth of an inch pellets. The pellets were fed to a screw extruder. Prior to extrusion into one mil sheets, particles of insecticide entrapped styrene-divinylbenzene beads prepared in accordance with Example VI were added. The resulting sheets were cut into strips and used as animal collars, and as insecticidal strips in homes and restaurant establishments.
While the foregoing disclosure specifies various uses of the materials of the present invention, as well as various types and compositions of ingredients which may be entrapped within these and similar materials, the patent literature is replete with uses and ingredients which may be entrapped in these and similar materials. For example, U.S. Pat. No. 4,690,825, discloses as active ingredients lubricants, emollients, moisturizers, pigments, insect or flea repellents, fragrances, vitamins, and drugs. When the active ingredient is a drug, it is said to include anti-infectives such as antibiotics, fungicides, scabicides, pediculicides, iodine, anti-inflammatory agents, antipruritics, astringents, anti-hidrotics, keratolytic agents, caustics, keratoplastic agents, rubefacients, sunscreens, demukents, protectants, and detergents. Uses of loaded beads includes cosmetic preparations such as hand creams, acne products, deodorants, antiperspirants, baby powders, foot powders, body powders, lip ices, lip sticks, baby creams and lotions, mouthwashes, dentifrices, medicated facial creams and lotions, shampoos, shaving creams, preand after-shave lotions, depilatories, and hairgrooming preparations.
U.S. Pat. No. 4,724,240, names as active ingredients ethylhexyl oxystearate, arachidyl propionate, ethylhexyl adipate, isopropyl myristate, ethanol, stearyl alcohol, propylene glycol, propionic acid, stearic acid, polyoxypropylene cetyl alcohol, carbowax, polyethylene glycol, petroleum jelly, mineral oil, mineral spirits, lanolin, acetylated lanolin, isopropyl lanolate, hexamethyl-disiloxane, cyclic polydimethylsiloxanes, polyphenylmethylsiloxanes, polydimethyl-trimethylsiloxanes; phenyl, ethyl, and vinyl-substituted polysilanes; and cosmetic dyes. Materials loaded with such ingredients are said to be useful in cosmetic, beauty, toiletry, and healthcare products, insecticides, disinfectants, flavors, perfumes, antiperspirant wax or oil base sticks, deodorants, colognes, pressed powders, and toilet soaps.
Entrapped functional materials in the Published European Application No. 0252463A2 are said to encompass pigments, perfumes, pheromones, synthetic insect attractants, pesticides including juvenile hormone analogs, herbicides, pharmaceuticals, antimicrobial agents, sunscreens, light stabilizers, fragrances, flavors including sweeteners, and various chemicals. Of the various chemicals disclosed are menthol, soybean oil, Vitamin E, salicylic acid, squalane, simethicon, bromochlorinated paraffin, benzophenone, petroleum distillate, jojoba oil, and citrus oil. The published application also specifically identifies and names four pheromones, twenty pesticides, twenty-three fragrances, about thirty-seven chemicals, and some twenty-two emollients, that may be entrapped in the materials as active ingredients.
In the Patent Cooperation Treaty International Publication No. WO/88/01164, there is also listed as specifically named ingredients which may be loaded into the beads approximately twenty-two ultraviolet absorbers, nineteen insect repellants, and thirty emollients. The publication also names several steriods including adrenocortical steroids such as fluocinolone, fluocinolone acetonide, triamcinolone acetonide, beta-methasone valerate, timobesone acetate, hydrocortisone, hydrocortisone acetate, triamcinolone, prednisolone, prednisolone acetate, dexamethasone, beclomethasone dipropionate, betamethasone diproprionate, betamethasone benzoate, clocorolone pivalate, halcinonide, flumethasone pivalate, and desonide.
European Published Application No. 0306236A2, published Mar. 3, 1989, discloses "in situ" and "post absorbed" suspension polymerized beads loaded with six different categories of active ingredients. The six categories of active ingredients are hair growth promoters, acne treatments, fragrances, vitamins, pain relievers, and epidermal lipid substitutes. The hair growth promoter is Minoxidil. For acne treatment there is employed benzoyl peroxide, salicylic acid, and resorcinol. Fragrances include flower oils, essential oils, animal and synthetic fragrances, and resinoids. Some thirty-nine specific fragrances are named. Vitamins include A, D, E, K, B1, B2, B12, B15, B17, C, niacin, folic acid, panthotenic acid, biotin, bioflavinoids, choline, inositol, and F. Cod liver oil and retinoids are also disclosed. Some twenty-two pain relievers, and some twenty-two mixtures and combinations of various pain relievers are disclosed, among which are menthol, camphor, and methyl salicylate. The epidermal lipid substitutes are squalane and squalene. The six categories of loaded beads may be used alone or as topical applications in creams, ointments, lotions, and oils. In addition, the fragrance loaded beads can be added to perfumes, colognes, cosmetics, soaps, paper products, detergents, and body and foot powders. The vitamin loaded beads also find application in lip balms, lipsticks, eye shadows, foundations, and blushers.
In U.S. Pat. No. 4,719,040, issued Jan. 12, 1988, a porous polymer powder laden with perfume is included as an ingredient in an aqueous air freshener gel. U.S. Pat. No. 4,764,362, issued Aug. 16, 1988, and a divisional thereof U.S. Pat. No. 4,813,976, issued Mar. 21, 1989, relate to emery boards including an emollient entrapped onto an absorbent acrylates copolymer powder. Filing of a nail releases the emollient which conditions and lubricates the nails and cuticles. A toothpaste containing dental flossing tape is disclosed in U.S. Pat. No. 4,776,358, issued Oct. 11, 1988. Included as an ingredient of the dentifrice are "microsponges" containing a flavor oil. In U.S. Pat. No. 4,828,542, issued May 9, 1989, particles entrapping various functional materials are bonded to the surfaces of an expanded reticulated polyurethane foam. Among the enumerated functional materials which may be entrapped are adhesives; pharmaceuticals such as insulin, interferon, albumin, hormones, and monoclonal antibodies; flavors; fragrances for perfume samplers, air fresheners, and drawer liners; colors; inks; liquid crystals; oils; waxes; solvents; resins; fire extinguishing agents; insect repellants for mothballs, and flea and tick applications; agricultural chemicals such as insecticides, fungicides, and heromones; disinfectants; cosmetics such as skin lotions, hair care products, sunscreens, and mouth wash; vitamins; antiperspirants; contraceptives; medicants such as Benzocaine, transdermal drugs, analgesics, allergy bacteria, methyl salicylate, and nitroglycerin.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions, and methods described herein without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are exemplary only and are not intended as limitations of the scope of the present invention.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US2809943 *||11 Sep 1952||15 Oct 1957||Dow Chemical Co||Weighted ion exchange resin granules and method of making same|
|US3418262 *||19 Abr 1967||24 Dic 1968||Diamond Shamrock Corp||Preparation of macroporous ion exchange resins|
|US3509078 *||19 Ago 1966||28 Abr 1970||Permutit Co Ltd||Cross linked macroporous polymers|
|US3608062 *||17 Dic 1968||21 Sep 1971||Bayer Ag||Shaped articles with long-term vapour emission|
|US3627708 *||5 Ago 1968||14 Dic 1971||Sybron Corp||Macroporous cross-linked copolymers and process therefor|
|US3637535 *||4 Mar 1958||25 Ene 1972||Bayer Ag||Anion exchanger with sponge structure|
|US3767600 *||11 May 1972||23 Oct 1973||Rohm & Haas||Porous polymers with ionic functional groups based on polyfunctional methacrylates|
|US3989649 *||3 Jun 1975||2 Nov 1976||Showa Denko Kabushiki Kaisha||Process for production of spherical porous fillers for liquid chromatography by suspension polymerization of monovinyl and polyvinyl aromatic monomers in the presence of paraffin wax|
|US4208309 *||18 Jun 1979||17 Jun 1980||Rohm Gmbh||Pearl polymer containing hollow pearls|
|US4224415 *||18 Jul 1958||23 Sep 1980||Rohm And Haas Company||Polymerization processes and products therefrom|
|US4661327 *||30 Mar 1983||28 Abr 1987||Phillips Petroleum Company||Recovery of mineral values using magnetically susceptible ion exchange agent|
|US4678684 *||21 Mar 1986||7 Jul 1987||Hercules Incorporated||Method for impregnating a thermoplastic polymer|
|US4690825 *||4 Oct 1985||1 Sep 1987||Advanced Polymer Systems, Inc.||Method for delivering an active ingredient by controlled time release utilizing a novel delivery vehicle which can be prepared by a process utilizing the active ingredient as a porogen|
|US4719040 *||12 Feb 1985||12 Ene 1988||Naarden International N.V.||Process for the preparation of air-freshener gels|
|US4724240 *||12 Dic 1984||9 Feb 1988||Wickhen Products, Inc.||Lattice-entrapped emollient-moisturizer composition|
|US4764362 *||22 Oct 1986||16 Ago 1988||The Cook Bates Company||Nail-conditioning emery boards and process for making them|
|US4776358 *||17 Mar 1988||11 Oct 1988||Leonard Lorch||Floss employing microporous tapes sandwiching paste dentifrice|
|US4806360 *||23 Oct 1987||21 Feb 1989||Advanced Polymer Systems||Synthetic melanin aggregates|
|US4813976 *||7 Abr 1988||21 Mar 1989||The Cook Bates Company||Nail-conditioning emery boards and process for making them|
|US4828542 *||29 Ago 1986||9 May 1989||Twin Rivers Engineering||Foam substrate and micropackaged active ingredient particle composite dispensing materials|
|US4855127 *||20 May 1987||8 Ago 1989||Dow Corning Corporation||Lattice-entrapped composition|
|USRE27026 *||20 Mar 1969||12 Ene 1971||Preparation of porous structures|
|CA1168157A *||22 Mar 1982||29 May 1984||Wickhen Products Inc||Polymer entrapped emollient-moisturizer composition|
|DE2608533A1 *||2 Mar 1976||30 Sep 1976||Airwick Ag||Verfahren zur herstellung eines festen diffusionssystems zur abgabe eines den geruch der luft verbessernden mittels, sowie damit erhaltene systeme|
|EP0061701A2 *||23 Mar 1982||6 Oct 1982||Wickhen Products, Inc.||A solid entrapped emollient-moisturizer composition and the use thereof|
|EP0252463A2 *||4 Jul 1987||13 Ene 1988||Dow Corning Corporation||Lattice-entrapped composition|
|EP0306236A2 *||26 Ago 1988||8 Mar 1989||Advanced Polymer Systems, Inc.||Controlled release formulations|
|WO1988001164A1 *||14 Ago 1987||25 Feb 1988||Advanced Polymer Systems, Inc.||Polymeric carrier compositions and methods for their preparation and use|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US5413790 *||3 Dic 1992||9 May 1995||Stewing Gmbh & Co. Kg Werk Berlin||Heat-shrinkable materials, especially for cable splices and junctions|
|US5510116 *||21 Jul 1993||23 Abr 1996||Advanced Polymer Systems, Inc.||Pressurized product delivery systems|
|US5591727 *||7 Feb 1995||7 Ene 1997||Perycut-Chemie Ag||Insecticidal composition|
|US5641499 *||12 Sep 1991||24 Jun 1997||Franz Bencsits||Insecticidal product|
|US5859057 *||27 Sep 1995||12 Ene 1999||Schwartz; Alan M.||Cockroach repellent|
|US6180127 *||6 Oct 1993||30 Ene 2001||Aquasource, Inc.||Slow release insect repellents|
|US6203856 *||14 Sep 1999||20 Mar 2001||Huels Aktiengesellschaft||Process for the preparation of antimicrobial plastics|
|US6332875||15 Abr 1999||25 Dic 2001||Thomas Randall Inkpen||Needle injection-facilitating device|
|US6719959||28 Nov 2000||13 Abr 2004||Avon Products, Inc.||Extended duration insect repellent composition and method of application to the skin|
|US6749861 *||20 Dic 2001||15 Jun 2004||Lenco Laboratories, Llc||Fragrance-containing insect repellant compositions|
|US6969521||28 Nov 2000||29 Nov 2005||Avon Products, Inc.||Aerosol insect repellent composition having low VOC content and method of applying same to the skin|
|US7150878||27 Nov 2001||19 Dic 2006||Avon Products, Inc.||Extended duration insect repellent composition and method of application to the skin|
|US7183249||14 Jun 2002||27 Feb 2007||Robertet Fragrances, Inc.||Fragrance compositions and delivery systems|
|US7299587 *||1 Jul 1999||27 Nov 2007||Ida Limited||Method and apparatus for controlling pests|
|US7343710 *||8 Abr 2004||18 Mar 2008||I.D.A Limited||Method and apparatus for controlling pests|
|US8206738||26 Jun 2012||Corium International, Inc.||Hydrogel compositions with an erodible backing member|
|US8273405||7 Oct 2011||25 Sep 2012||A.V. Topcheiv Institute of Petrochemical Synthesis, Russian Academy of Sciences||Water-absorbent adhesive compositions and associated methods of manufacture and use|
|US8481059||24 Jun 2009||9 Jul 2013||A.V. Topchiev Institute Of Petrochemical Synthesis, Russian Academy Of Sciences||Hydrogel compositions|
|US8481071||29 May 2012||9 Jul 2013||Corium International, Inc.||Hydrogel compositions with an erodible backing member|
|US8541021||17 May 2004||24 Sep 2013||A.V. Topchiev Institute Of Petrochemical Synthesis||Hydrogel compositions demonstrating phase separation on contact with aqueous media|
|US8617647||24 Ago 2012||31 Dic 2013||A.V. Topchiev Institutes of Petrochemical Synthesis, Russian Academy of Sciences||Water-absorbent adhesive compositions and associated methods of manufacture and use|
|US8658201||31 Ene 2005||25 Feb 2014||Corium International, Inc.||Rapidly dissolving film for delivery of an active agent|
|US8728445||1 May 2002||20 May 2014||A.V. Topchiev Institute Of Petrochemical Synthesis, Russian Academy Of Sciences||Hydrogel Compositions|
|US8741331||12 Jun 2013||3 Jun 2014||A. V. Topchiev Institute of Petrochemicals Synthesis, Russian Academy of Sciences||Hydrogel compositions with an erodible backing member|
|US8753669||20 Ago 2007||17 Jun 2014||A.V. Topchiev Institute Of Petrochemical Synthesis, Russian Academy Of Sciences||Two-phase, water-absorbent bioadhesive composition|
|US8784879||14 Ene 2010||22 Jul 2014||Corium International, Inc.||Transdermal administration of tamsulosin|
|US8821901||5 Abr 2010||2 Sep 2014||A.V. Topchiev Institute Of Petrochemical Synthesis Russian Academy Of Sciences||Method of preparing polymeric adhesive compositions utilizing the mechanism of interaction between the polymer components|
|US8840918||5 Feb 2003||23 Sep 2014||A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences||Hydrogel compositions for tooth whitening|
|US9084723||2 Jun 2014||21 Jul 2015||A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences||Hydrogel compositions with an erodible backing member|
|US9089481||6 Sep 2013||28 Jul 2015||A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences||Hydrogel compositions demonstrating phase separation on contact with aqueous media|
|US9127140||23 Dic 2013||8 Sep 2015||A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences||Water-absorbent adhesive compositions and associated methods of manufacture and use|
|US9144552||3 Feb 2014||29 Sep 2015||A.V. Topchiev Institute Of Petrochemical Synthesis, Russian Academy Of Sciences||Rapidly dissolving film for delivery of an active agent|
|US9242021||4 Ago 2005||26 Ene 2016||Corium International, Inc.||Adhesive composition|
|US9259504||10 May 2013||16 Feb 2016||A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences||Non-electrically conductive hydrogel composition|
|US20020198117 *||14 Jun 2002||26 Dic 2002||Dente Stephen V.||Fragrance compositions and delivery systems|
|US20030152528 *||5 Feb 2003||14 Ago 2003||Parminder Singh||Hydrogel compositions for tooth whitening|
|US20030170308 *||1 May 2002||11 Sep 2003||Cleary Gary W.||Hydrogel compositions|
|US20040105834 *||12 Sep 2003||3 Jun 2004||Corium International||Hydrogel compositions with an erodible backing member|
|US20040200128 *||8 Abr 2004||14 Oct 2004||Metcalfe Colin T.||Method and apparatus for controlling pests|
|US20040247635 *||23 Oct 2003||9 Dic 2004||Osamu Igarashi||Insect repelling resin system and insect repelling method using the same|
|US20040258723 *||17 May 2004||23 Dic 2004||Parminder Singh||Hydrogel compositions demonstrating phase separation on contact with aqueous media|
|US20050186238 *||22 Abr 2005||25 Ago 2005||Nix, Inc.||Universal insect repellant enclosure|
|US20060034905 *||4 Ago 2005||16 Feb 2006||Parminder Singh||Adhesive composition|
|US20060182788 *||27 Ene 2006||17 Ago 2006||Parminder Singh||Hydrophilic biocompatible adhesive formulations and uses|
|US20060201054 *||6 Mar 2006||14 Sep 2006||Nobuo Katsuura||Insect repelling or killing resin product|
|US20070074448 *||29 Sep 2006||5 Abr 2007||Nix, Inc.||Pest-control product|
|US20070269472 *||18 May 2006||22 Nov 2007||Osamu Igarashi||Pest-control product|
|US20080035640 *||9 Ago 2007||14 Feb 2008||Weber Marcia L||Washable trash-can cover that is secured to the can by its handles|
|US20080161492 *||20 Ago 2007||3 Jul 2008||Cleary Gary W||Two-phase, water-absorbent bioadhesive composition|
|US20080187564 *||7 Mar 2006||7 Ago 2008||Hidekazu Momiyama||Pest-Control Member|
|US20090200821 *||20 Jun 2008||13 Ago 2009||Kojima Press Industry Co., Ltd.||Part mounted on automotive compartment ceiling|
|US20100278757 *||12 Jul 2010||4 Nov 2010||Feldstein Mikhail M||Water-Absorbent Adhesive Compositions and Associated Methods of Manufacture and Use|
|US20100291186 *||18 Nov 2010||Parminder Singh||Transdermal Administration of Tamsulosin|
|US20150007487 *||3 Jul 2013||8 Ene 2015||Rockwell Automation Technologies, Inc.||System and method for incorporation of pest repellent with bus bar cover components|
|USRE44145||10 Jun 2005||9 Abr 2013||A.V. Topchiev Institute Of Petrochemical Synthesis||Preparation of hydrophilic pressure sensitive adhesives having optimized adhesive properties|
|USRE45666||6 Feb 2013||8 Sep 2015||A.V. Topchiev Institute Of Petrochemical Synthesis||Preparation of hydrophilic pressure sensitive adhesives having optimized adhesive properties|
|DE10157350A1 *||22 Nov 2001||28 May 2003||Stockhausen Chem Fab Gmbh||Production of controlled release plant treatment composition, comprises kneading water-absorbing polymer containing absorbed water with active agent, e.g. fungicide or insecticide|
|EP1247571A1 *||4 Abr 2002||9 Oct 2002||AFT Plasturgie||New fibre containing active elements, process for the preparation thereof and their uses, in particular in packaging|
|WO1996039821A1 *||5 Jun 1996||19 Dic 1996||Bsi Corporation||Virus inactivating coatings|
|Clasificación de EE.UU.||424/409, 424/419, 424/416, 424/411, 424/84, 424/405|
|Clasificación internacional||A61K9/14, A01N25/10|
|Clasificación cooperativa||A61K9/146, A01N25/10|
|Clasificación europea||A61K9/14H6, A01N25/10|
|8 Dic 1989||AS||Assignment|
Owner name: DOW CORNING CORPORATION, MICHIGAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GALLAGHER, MARGARETHE J.;REEL/FRAME:005213/0094
Effective date: 19891024
|5 Sep 1995||FPAY||Fee payment|
Year of fee payment: 4
|4 Oct 1999||FPAY||Fee payment|
Year of fee payment: 8
|6 Jun 2000||AS||Assignment|
Owner name: ADVANCED POLYMER SYSTEMS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DOW CORNING CORPORATION;REEL/FRAME:010676/0509
Effective date: 20000529
|7 Ago 2000||AS||Assignment|
Owner name: R.P. SCHERER SOUTH, INC., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ADVANCED POLYMER SYSTEMS, INC., A CORP. OF DELAWARE;REEL/FRAME:011111/0795
Effective date: 20000725
|7 Oct 2003||FPAY||Fee payment|
Year of fee payment: 12
|21 Dic 2004||AS||Assignment|
Owner name: AMCOL HEALTH & BEAUTY SOLUTIONS, INCORPORATED, ILL
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CARDINAL HEALTH 409, INC. (F/K/A R.P. SCHERER CORPORATION) AND CARDINAL HEALTH 403, INC.;REEL/FRAME:015478/0312
Effective date: 20031231