TW200909484A - Granular composites of inorganic particulates and redispersible latex powders and methods - Google Patents

Abstract

A granular composite comprising (a) an inorganic particulate, (b) a redispersible latex powder, and (c) one or more of a superabsorbent polymer (SAP), a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent and the process of making the same.

Description

200909484 IX. Description of the Invention: [Technical Field 3 of the Invention] Field of the Invention The present invention has a relationship with a granular composite and a method for producing a granular composite. [Background of the Invention] Background of the Invention For a multi-functional granular composite carrier for use in various household products and consumer products, for air filters for commercial or industrial use, water-liquid adsorbent 10 or oil absorbing particles, moisture adsorbing particles , and odor control particles, as well as other increased demand. The development of a mature composite carrier must have good processing properties, high water, moisture and/or oil absorption, as well as good malodor inhibition and/or volatile organic compound (VOC) control, as previously mentioned The utility of the application. 15 In the past, there have been efforts to solve this problem, but for improved performance such as higher moisture or water absorption, oil absorption and resistance at different pressures, and inhibition of odor and VOC. There is still a need for an effective binder for the particulate composite carrier. Such carriers provide an effective means of delivering the active ingredients more suitable. 20 SUMMARY OF THE INVENTION In one embodiment, the present invention provides a particulate composite comprising a) - inorganic particles, b) - a redispersible latex powder, and c) one or more superabsorbent polymers (SAP), a porosity enhancer, a water soluble polymer, a gas 2000909484 control agent, or an oil absorbent. In another embodiment, the invention provides a method of making a granular composite. The method comprises dry blending clay, a redispersible latex powder, and other components of the composite to form a mixture; wetting the mixture with water or an aqueous solution; extruding the wetting mixture to form a granular composite; The extruded material is dried; and sized and screened to form a composite. The method also includes rewetting and gas dedusting the composite. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the effect of varying degrees of redispersible latex powder (Dow of Dow powder, DLP) and synthetic urine content on the weight of the clot. I: Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In one embodiment, the present invention provides a particulate composite comprising a) - inorganic particles, b) - a redispersible latex powder, and c) one or more 15 S AP, a porosity enhancer, a water soluble polymer, an odor control agent, or an oil collector. The inorganic particles used in the present invention are solid compounds which are finely divided natural or synthetic substances, with or without undergoing chemical, physical, and/or mechanical surface modification. Different types of inorganic particles may be used, 20 including, for example, aluminum hydroxide, aluminum oxide, barium sulfate, borax, calcium citrate, calcium carbonate, calcium phosphate, calcium magnesium carbonate, calcium sulfate, copper hydroxide, oxidation. Copper, ferric hydroxide, iron oxide, lithium hydroxide, magnesium borate, magnesium carbonate, magnesium oxide, magnesium oxylate, galvanic acid, sand, glutinous stone, gas phase dioxide, sodium bicarbonate, sodium carbonate, Talc, titanium dioxide, synthetic and natural zeolites, 200909484 rushing stones, different types of clay (such as bentonite, kaolin and sepiolite), zinc oxide, and any of its water-soluble alkali metals or soil-measuring metal salts (such as clock vapors) , sulphates, sulphates and nitrates, sodium and potassium sulphates, sulphate salts, acid salts, percarbonates, peroxides, persulfates and phosphates, 5 and the like, Further, stepwise, magnesium chlorides and acid salts, the word chloride, sulphate and or sulfate, locked chlorides and sulphate, and the like). The inorganic particles are preferably metal oxide compounds containing - or a plurality of metal atoms and / or one or more oxygen atoms. In a preferred embodiment of the invention, the inorganic particles are clay. Clay is a common name for fine-sized particles of many sediments, soils, or rocks, and individual particles are generally less than 5 microns in diameter. Most clays are mainly composed of clay minerals' and soils such as shai contain such things as kaolin, smectite, chlorite and illite. Most of the clay is formed by surface weathering, for example, by the rocky state of the rock, such as limestone, and by rock or a group of rock minerals rich in sulphuric acid, such as The chemical decomposition of granite and feldspar. Clay is composed of different layered phthalates, known as sulphate ore (which contains cerium oxide, aluminum oxide, and hydroxide), which contain varying amounts of structured water. For example, kaolinite, also known as kaolin, combines 20 interconnected niobates with metal atoms of the second lamellar group, oxygen, and hydroxyl groups to form a bilayer mineral. Kaolinite is often present in the form of a hexagonal crystal like a plate. Kaolin is a preferred clay for use in the present invention. In another preferred embodiment of the invention, the inorganic particles are nano-bentonite clay. Bentonite has various synonyms and includes sodium montmorillonite, calcium monoxide 200909484 decalcification, magnesium bentonite, fuller's earth, Wyoming bentonite, expanded bentonite, and others. Calcium bentonite is generally characterized by very low expansion and liquid limits compared to natural sodium bentonite. Natural nanobentonite contains sodium as the main exchange cation. Na-bentonite is also known for its ability to swell. 5 It absorbs five to eight times its weight in water. Sodium-activated bentonite is made by replacing the mother ion with sodium ions. Such a transformation can be achieved by adding soluble sodium salts to the calcium bentonite. The particulate composite of the present invention generally comprises at least 1 w t. % of inorganic particles. Preferably, the composite comprises more than 20 wt.% of inorganic particles. More preferably, the composite contains more than 40 wt.% of inorganic particles. Moreover, the composite of the present invention generally contains less than 99 wt.% of inorganic particles. Preferably, the composite comprises less than 95 wt.% of inorganic particles. More preferably, the composite contains less than 80 wt.% of inorganic particles. The redispersible latex powder is an organic polymer powder obtained by mist drying of an aqueous dispersion containing a latex powder. U.S. Patent Publication No. 20060116446, the entire disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in the entire entire entire entire entire entire entire entire entire portion In the spray drying procedure, the redispersible latex powder having a primary particle size of from about 0.5 to 2 μm will agglomerate to a size of from about 50 to about 20 inches in diameter. This increased particle size improves the free flow of the powder and avoids dust formation. Unlike conventional latex powders, conventional latex powders have a tendency to coagulate in an unregulated and irreversible manner, and the redispersible latex powder particles disintegrate into a particle size of about 0.5 to 2 μm when in contact with water. The redispersible latex powder used in the present invention includes Dow Latex 200909484 powder (DLP, manufactured by The Dow Chemical Company). It comprises about 75 wt% dry latex powder, about 12 wt.% polyvinyl alcohol, and about i3 wt.% non-expanded clay, such as kaolin or other anti-clotting agents. WO 9738042 and U.S. Patent Publication No. 20020120043, hereby incorporated herein incorporated by reference by reference in its entirety in its entirety in the in the the the the the the the The composite of the present invention preferably contains at least l. lwt.% of a redispersible latex powder. Preferably, the composite comprises more than 1 wt.% of a redispersible latex powder. In general, the composite comprises less than 25 wt.% of a re-dispersible latex powder. Preferably, the composite comprises less than 15 wt.% of a redispersible latex powder. The superabsorbent polymer (SAP) particles used in the present invention are those which absorb more than twice their weight in moisture, in water, or in aqueous liquid. SAP particles swell as they absorb liquid. SAP is used in 15 applications including diapers, water-blocking applications in the construction industry, liquid absorbents in food packaging systems, and sanitary and medical applications. The SAP particles can be any known hydrophilic polymer that is crosslinked and can absorb a large amount of aqueous liquid, which in some instances will expand to several times its dry size. These polymers are well known in the art and are readily available from companies such as NorsocrylTM (Arkema Group), HySorbTM (BASF AG), FavorTM (Degussa AG), DRYTECHTM (Dow Chemical). K-SAMTM (Kolon Chemical Co. Ltd.), AqualicTM CA (Nippon Shokubai Ltd.) 'SanwetTM (Sanyo Chemical Industries) and Aqua KeepTM (Sumitomo Seika Chemicals). 9 200909484 Most SAP-based cross-linkers are partially neutralized and/or surface treated. Preferably, the degree of crosslinking is selected to provide the desired expansion characteristics for a particular application. Suitable SAP and procedures for preparing SAP (including gelation polymerization procedures) are disclosed in U.S. Patent Nos. 3,669,103, 5 3,670,731 ' 3,926,891 ' 3,935,099 ' 3,997,484 ' 4,076,663 ' 4,090,013, 4,093,776, 4,190,562, 4,286,082, 4,340,706, 4,446,261 4, 459, 396 ' 4, 654, 039 ' 4, 683, 274 ' 4, 708, 997 ' 4, 857, 610, 4, 985, 518, and 5, 145, 906, the entire disclosure of which is incorporated herein by reference. 10 The SAPs may be in the form of particles or other forms, such as fibrous. These SAPs may also be biodegradable. Preferably, the eight human lanthanides are comprised of a plurality of ethylenically unsaturated carboxyl-containing monomers, and optionally one or more comonomers copolymerizable with the carboxyl-containing monomer. The preferred SAP of the present invention has a centrifuge retention capacity (CRC) of less than 70 g/g as measured by a tea bag method in a 0.9 wt.% NaCl solution based on the dry weight of the particles. Less than 6 〇g/g, and more preferably less than 50 g/g. Preferably, the SAP of the present invention has a CRC of greater than about 7 g/g, preferably greater than about 1 g/g, measured by a tea bag method in a 0,9 wt.% NaCl solution based on the dry weight of the particles. g, more preferably greater than about i5 g/g. The preferred SAP of the present invention has a reduced absorption (AUL) under load based on the dry weight of the particles, measured in a 0-9 wt.% NaCl solution and a pressure of 磅3 psi. Preferably at 5〇g/g′ is less than 4〇g/g, and more preferably less than about 3〇g/g; the system is greater than 巧^, preferably greater than 7 g/g, and more preferably More than 1〇g/g. 200909484 The SAP of the present invention has a dry-base size measured by a sieve analysis method, which is less than 1000 microns, preferably less than 800 microns, and more preferably less than 500 microns, and is greater than 0.1 microns, preferably Greater than 10 microns, more preferably greater than 100 microns, and most preferably greater than 150 microns. 5 The composite of the present invention preferably contains at least 0.1 wt.% of SAP. More preferably, the composite contains more than 1 wt.% SAP. In general, the composite contains less than 99 wt.% SAP. Preferably, the composite comprises less than 50 wt.% SAP. The composite of the present invention has a granular structure that can be designed to exhibit a higher degree of porosity 10, which facilitates rapid absorption of liquid upon contact with water, aqueous solutions, and moisture or gas in the air stream. . The degree of porosity of the composite particles can be controlled by the type, shape and amount of the porosity enhancer, and the homogeneity of the distribution of the porosity enhancer in the matrix of the composite particles. 15 In principle, different types of substances can improve the porosity of the composite structure. It includes different types of thermoplastic and thermoset polymer microspheres; highly crosslinked polymer beads with or without internal pores; and water-insoluble organics of nano, submicron or micron size Or inorganic particulate matter, such as: glass beads, glass microspheres, sedimentary vermiculite, 20 cerium oxide, gas phase cerium oxide, water strontium soda and modified water soda shale, titanium dioxide, oxidation is , magnesium dioxide, dioxin, talc, carbonated I bow, mashed corn, mashed rice, chopped barley, fiber, starch, carbon tube, metal particles or metal microspheres, polymer fiber, natural fiber And others. Organic or inorganic porous improvers can be small plates, different 11 200909484 length of the tube, such as carbon nanotubes, cylinders, multi-cylinders, pellets, and spheres, such as fuller type, polyhedron, Disc, needle, multi-needle, cube, irregular, round, and other types. The porosity improving agent is used in an amount of less than 40% by weight based on the weight of the composite fine particles, and more preferably less than 20% by weight, and more preferably less than 10% by weight. Prior to use, the porosity enhancer may be subjected to some treatment, such as surface treatment. Preferred porosity enhancers are polymeric microspheres and glass microspheres. In general, a preferred polymer porosity enhancer is PERGOPAK® HP 10 (CAS No.: 9011-05-6, a trademark of Albemarle Corporation, Baton Rouge, Louisiana, USA). The PERGOPAK agent is a polymethyl urea resin containing a small amount of free, reactive methylol groups (about 0.6%) which additionally contributes to better crosslinkability in the matrix. The PERGOPAK agent is generally an aggregate of 3.5-6.50111 15 in diameter formed by particles of diameters of 〇.1-〇.15卜111. The water-soluble polymers and copolymers used in the present invention mean various macromolecules including naturally occurring polymers such as polysaccharides, and biopolymers such as polypeptides and proteins, and various types of synthetic polymers. , interpolymers and block copolymers (see "Water Soluble 20 Polymers," Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., Eds. Charles L. McCormick, Andrew B. Lowe, Neil Ayres) ° Preferred natural invention water soluble polymers include, for example, polynucleotide acids, polypeptides, proteins, enzymes, and polysaccharides. Commercially, the polysaccharide tradition 12 200909484 is obtained from renewable resources in plants and animals. In addition, microbial sources produce commercially useful polysaccharides such as polydextrose and trisin. Water-soluble polysaccharides include starch and starch derivatives, glycogen, polydextrose, alginic acid, red algae, pectin, vegetable gums, for example: gum arabic, hyaluronic acid and 5 synthetic polysaccharides. More preferred water-soluble polymers are synthetically modified. Some naturally occurring polysaccharides can be rendered water soluble by modification to generate charge or polar functionality. Traditionally modified polysaccharides are cellulose derivatives including carboxymethyl cellulose (CMC), or monovalent metal or ammonium salts thereof, hydroxyethyl cellulose (HEC) 10 and hydroxypropyl cellulose (HPC) ), methyl cellulose, hydroxypropyl methylcellulose (HPMC), cellulose sulfate and cellulose phosphate, and chitin derivatives with polyglucosamine. Preferred synthetically modified water-soluble polymers based on polysaccharides are WALOCELTM C and WALOCELTM CRT carboxymethylcellulose, 15 CELLOSIZETM hydroxyethylcellulose, and METHOCELTM cellulose ether (by Dow Chemical Company business obtained). The most preferred water soluble polymer is METHOCELTM cellulose ether which is a water soluble sulfhydryl cellulose and a hydroxypropyl fluorenyl cellulose polymer. Many commercially available nonionic synthetic water soluble polymers are available with copolymerized 20 systems, and the like include, for example, polyacrylamide, poly(ethylene oxide) such as: POLYOXTM (available from The Dow Chemical Company) Obtained), poly(vinyl alcohol), poly(fluorenyl vinyl ether), and poly(N-vinyl. pyrrolidone). Other preferred water soluble polymers are polymeric electrolytes which are polymers having a charge functional group attached to the chain. These polymers are usually classified by polyanion 13 200909484 and polycations. Preferred anionic water-soluble polymers are poly(acrylic acid) and its salts, poly(methacrylic acid) and its salts, poly(ethylenesulfonic acid) and its salts, poly(p-styrenesulfonic acid) and its Salts, poly(mercaptoacrylic acid 2_ethene sfecSg) 'poly(methyl acrylic acid 3-contigyl 2 propyl), and poly(2_prop-5 allylamino-2-methylpropane sulfonate) acid). Examples of preferred water-soluble polymers which can be used in the present invention include a cationic water-soluble polymer which is a linear polymer electrolyte having a cationic charge density. Examples of water-soluble cationic polymers are poly(2-(dimethylamine)ethyl methacrylate), poly(2-dimethylaminoethyl methacrylate), poly(methyl 10-acrylic acid N-[3] -(dimethylamine)propyl), polydimethyldiallyl ammonium salt, polyvinylpyridine, poly(4-vinylaniline), poly(ethyleneimine), polyvinylamine, cationic hydroxyl Cellulose, (eg UCARE JR-09, JR-400, R-400 and R-30M available from Amerrchol Corporation, USA), and chitosan iron alpha pirone ketone (according to Amerchol Corporation) 15 KYTAMERPC is commercially available, and the like. The solubility of the preferred water-soluble polymer is preferably at least 0.05 g, preferably 1 g, more preferably at least 2 g, at room temperature and atmospheric pressure. The polymer is soluble in 100 grams of deionized water. A water soluble polymer having a wide range of molecular weights is suitable for use in the present invention. Preferably, the water soluble polymer has an average molecular weight of from 500 to 10,000,000 per mole.克, preferably 2,000 to 2,000,000 grams per mole, and optimally 50,000 to 500,000 per mole Methods for determining the weight average molecular weight of water soluble polymers are well known in the art. For the purposes of the present invention, the weight average molecular weight is measured by gel permeation chromatography 14 200909484. In a preferred embodiment, the water-soluble polymer is preferably added in a powder. The water-soluble polymer is preferably used in an amount of 0.01 to 25 wt.%, preferably 0.5 to 0.5% by weight based on the total mass of the dry mixture. 10wt_°/〇5 parts are used, and more preferably used in an amount of 1 to 5 wt.%. Different types of water-soluble polymer mixtures can be used. The water-soluble polymer can be used for inorganic particles, redispersibility. Latex powder, SAP, odour control agents, and other powder form additives are blended simultaneously, before or after. Oil absorbing polymers are known in the art. Many polymers can absorb 10 times their original volume. Oil or organic liquid. The term "oil-absorbing polymer" as used herein means a substance that is substantially insoluble but absorbs (by expanding) one or more oils or organic liquids. : natural oil (from rapeseed, ramie, corn, cottonseed, olive, rapeseed, soybean, sunflower seed 'other vegetables and animal oils and fats), spices, gasoline, diesel 'lubricating oil, 15 kerosene, light oil, Heavy oils, aromatic solvents (such as benzene, toluene and xylene), and different gasification solvents (eg chloroform, tetra-carbonized carbon and their analogues), monoglycerides, triglycerides and their analogues Various compositions are available for preparing such oil absorbing polymer particles, and different oil absorbing polymer particles are taught in U.S. Patent Nos. 3,520,806, 3,686,827, 20 3,750,688 ' 3,881,295 ' 3,958,590 ' 3,999,653 > 4,024,882 > 4,019,628 ' 4,130,400 ' 4,172,031 ' 4,529,656 ' 5,628,110 ' 5,677,407, 5,712,358, 5,777,054 ' and 5,834,577. The teachings are hereby incorporated by reference. Preferred oil absorbing polymers in the present invention are those comprising from 100 to 55 wt.% 15 200909484 of isobornyl methacrylate and from about 0 to 45 wt.% of a polymerizable vinyl comonomer. An example of such a comonomer is an alkyl styrene or an alkyl ester derived from an alcohol of C1 to C24 and acrylic acid or methacrylic acid or a mixture thereof. The alkylstyrene has a alkyl group having 4 to 20 carbons and more preferably 5 to 12 carbons. Such a pyrene styrene includes a tertiary styrene styrene, the tertiary alkyl styrene p-tertiary-butyl styrene, p-tris-pentyl styrene, P-tris-hexyl styrene, P-third-octyl styrene, p-triple-dodecylstyrene, p-tris-octadecylstyrene, and p-tris-icosylstyrene; η- Alkyl styrene comprising η-butyl styrene, 10 η-dodecyl phenethyl hydrazine, η-octadeca styrene styrene, and η-teledecyl styrene; secondary-alkyl Styrene, which includes, for example, secondary-butyl styrene, secondary-hexyl styrene, secondary-octyl styrene, secondary-dodecyl styrene, secondary-octadecyl styrene, And secondary-eicosylstyrene; isoalkylstyrene, including, for example, isobutylstyrene, isoamylstyrene, 15 isohexylstyrene, isooctylstyrene, isododecyl Styrene, isostearyl styrene, and isostearyl styrene; and copolymers thereof. The alkyl esters derived from C1 to C24 alcohols and acrylic acid and methacrylic acid include hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate. , methacrylic acid 20 tauthyl group S, methacrylic acid laurel S, acrylic acid decyl S, acrylic lauryl ester, eicosyl acrylate, methacrylic acid eicos vinegar, or a mixture of such. Preferably, the oil absorbing polymer particles of the present invention are from 100% to about 55 wt.% of a crosslinked copolymer of isobornyl methacrylate and from 0 to 45 wt.% of lauryl methacrylate. 16 200909484 The degree of oil absorption (expansion capacity) is mainly determined by the percentage of cross-linking in the polymer particles. The amount of cross-linking agent applied should be sufficient to allow the polymer particles to absorb (expand) the polymer particles when exposed to an organic oily liquid, and to prevent the polymer particles from being dissolved by the organic oily liquid. Usually, the crosslinking agent is applied in a range of from 〇5 to about 2% by weight based on the total weight of the monomers or monomers. In general, the amount of the crosslinker used is less than! Percentage allows the polymer to readily swell and absorb appreciable amounts of organic liquid. Crosslinking agents which can be used to prepare polymers suitable for use in the present invention include polyvinyl unsaturated compounds such as divinylbenzene, diglyoxynium 10 dimethacrylate, and any other known to be polymerizable. A di- or poly-functional compound for use as a crosslinking agent in a vinyl addition composition. A preferred crosslinking agent is divinylbenzene. The degree of oil absorption is generally measured using a dry oil absorbing polymer, where the polymer particles are immersed in a liquid oil (eg, rapeseed oil) 15 while the added oil is partially introduced in part. Until the migratory liquid oil can be seen' then the absorption of the oil can be calculated as follows, per gram of dry oil absorbed polymer absorbed grams. Oil absorption (g/g) = (added oil in grams / calculated polymer in grams). Preferably, the oil absorbing polymer particles of the present invention have an oil 20 absorption enthalpy (based on the dry weight of the oil absorbing polymer) in the rapeseed oil of less than 4 g/g, preferably less than 3 Gg/g. More preferably, it is less than 2 Gg/g; and its system is greater than lg/g, preferably greater than 3 g/g, and more preferably greater than 5 g/g. In a preferred embodiment, the oil absorbing polymer is preferably added as a powder. The oil absorbing polymer 17 200909484 is preferably used in an amount of 0.01 to 5 〇 Wt·% based on the total weight of the dry granulated composite, more preferably 5% to 25 % by weight, and It is preferably used in an amount of 1 to 15 wt.%. Different types of oil absorbing polymer mixtures can be applied. The oil absorbing polymer is added before or after the powder is mixed with the inorganic granules, the redispersible emulsifiable powder, the SAP, the odor control agent, and the Z 5 other powder additives. The odour controlling agent for use in the present invention may comprise one or more activated carbons, such as powdered, granulated or extruded; cyclodextrin; porous polymeric adsorbent; ion exchange polymer; Bicarbonate; butterfly; peroxide, such as sodium, potassium or ammonium peroxycarbon g salt, peroxidation 10, peroxodisulfate and permanganate, such as sodium or bell Acid salt; biocide; plant extracts, such as green tea leaves, leaves, yucca, aloe and stone alkali wood extract and / or dry powder; citric acid; chelating agent; natural and ^ into Buddha stone; perfume Various metals and metal compounds, including copper sulfide, copper ruthenate, zinc sulfate, gasification, zinc linoleate, various forms of metal 15 and ionic silver (such as colloidal silver nanoparticles, silver acetate, two silver, And sulfur, .1·anthracene silver complex), ion exchanged zeolite powder with silver, copper, and/or ion, polyglucosamine, or a mixture thereof. In the preferred embodiment, the powdered odour controlling agent is preferably added as a powder, and the soluble metal salt is added as an aqueous solution. The bundled odor control agent is preferably used in an amount of from 0. 01 to 5 〇 wt·%, based on the total weight of the dry granulated composite, more preferably 〇.5 to 25 %%, 吏It is preferably used in an amount of from 1 to 15 wt.%. The soluble metal stepping gas uncontrolled agent, such as an alkali metal salt of a chelating agent, copper sulfate, vinegar-brewed steel, yam yum yin, zinc zinc ricinoleic acid, various types of metal or from 18 200909484 Silver (for example, colloidal nanoparticle silver, silver acetate, silver nitrate, or thiosulfate complex) is preferably used in an amount of 0.0001 to 15 wt. 〇/〇 based on the total weight of the dry granular composite. More preferably, it is used in the amount of 〇〇〇25 to 1 (^ 〇/0, preferably in the amount of 〇.〇5 to 5 wt.〇/0. A mixture of different types of odor controlling agents can be applied. Powder The odor control agent is added before, after or after the powder is blended with the inorganic granules, the redispersible latex powder, the SAP, the oil absorbent, and other powder additives. The metal salt odor control agent is generally wetted with an aqueous solution. Addition of the inorganic particles, redispersible latex powder, SAP, oil absorbent, and other additives. 0 纟 财 , , 提供 提供 - - - - - - - - - - - - - - - - Powder form of complex The sigma is formed by adding various powder components, such as inorganic particles, sAp, oil absorbing polymer, and a porosity enhancer to the dry mixer (having horizontal and vertical medullary and optionally (4) mouths. With mechanical heating 15 equipment, such as Loedige mixer, Forberg mixer, Hobat mixer,

Free flowing powder components can be used in this method

The powder components are mixed homogeneously. After the powder components are homogenically stirred, by water or aqueous solution

Bentonite type clay, partially expanded SAp, and/or partially hydrated water soluble 19 200909484 polymer particles' and/or oil absorbing polymer particles, and/or other components of the invention. Preferably, the humidified mixture comprises from 5 to 500 percent water (determined by the weight lost by the wetted mixture after at least one hour of drying over 100 tons). The humidified mixture is preferably changed to a coagulated particulate shape in the agitator during the wetting step to accelerate homogenous mixing of the admixture with water. The wetted material preferably has a particle size ranging from 〇〇1 to 10 15 20 10 cm. More preferably, the wetted material has a particle size ranging from 〇 5 to 5 cm, and most preferably from 〇.1 to 2.5 cm. The moisture content of the wetted material particles may be adjusted by drying and/or microwave prior to extrusion, or the moisture in the wetted material may be removed by methods known in the art. The step of extruding the wetted material is performed in an extrusion apparatus comprising a die-and-mandrel, by forcing the wetted material through the masking device and exiting the orifice to become an extruded product . The preferred extruders are media card low pressure blue extruders, Shugi blue crushers, single screw extruders or twin screw extruders. The die hole diameter is preferably 2 em or less, more preferably _ or less. Preferably, the singer is a larger straight, and more preferably has a larger diameter of 0. lem. The Lai Kong phase has various shapes such as a circle, an expanded circle, a square, a triangle, and the like. The temperature at which the extrusion occurs can be adjusted to remove the liquid (including water) for a reasonable period of time (10) to substantially reduce the subsequent radiant time or to further dry the extruded wetted material. Preferably, the temperature of the extruded material is 80 C or less, preferably. . ...... 5疋C or less, and the best is 10 or more. In order to extrude the wetted composite material, a hole (four) mold having any size can be used. In the case of squeezing _ can be powdered 妓 solution shaped money 20 200909484 with additional lubricants, such as poly-type polymer type polymers, such as. P〇LY〇XTM (commercially available from The Dow Chemical Company), or surface active The agent is based on the total amount of the dry material, and the amount ranges from 0.01 wt.% to 5 wt. /. . The extruded wet material exhibits an angel-like finish and can be of any length. Preferably, the extruded wet side has a crepe (10) or a longer length & is preferably 5 〇 or longer. Under the general condition, the length of the extruded wet surface characteristic, that is, the length of the leg paste material (or thickness) is 1 〇 or more, preferably 50 or more, and more preferably It is 1〇〇 or bigger. 10 15 20 After extrusion, the wet composite paste is passed through a dry environment to remove or reduce moisture. In general, the dry composite (iv) moisture content is between zero and 20 wt.%, preferably between 5 and _%. The drying process occurs at a temperature high enough to allow the water to be removed in the inter-segmental zone, but not so high as to degrade the compositive component of the granular composite. Preferably, the temperature of the resin particles during drying is 2 Torr or less, more preferably mrc or less. More desirably, the temperature during drying is thief or more, preferably 8 Gt or ❹, and more preferably (10). c or more. This dry time should be sufficient to remove substantially all of the water and lubricant solvent. Preferably, the minute time of the dry time is more, 15 minutes or more is preferred = « is 24 hours or less, more preferably 3 hours or less. In the preferred embodiment, the second: occurs in the driers, where the dried air is either coated or coated on the extruded wet material (the extruded body is blown through the fluid containing bed) Job, _ dry I a drying method..., H-baked phase, tray dryer, 21 200909484 or a barrel dryer. The preferred dryer is a fluid bed or a belt dryer. The final size of the granular composite is It is obtained after measuring and sieving. Preferably, the particle size reduction is performed by using a conventional particle size reduction method such as: honing, mashing, and/or cutting. The particle size of the particles is reduced to the size of the particles that are available for final use. In a preferred embodiment, the composite particles are honed and honed. The final particle size is preferably 2 cm or less, and more preferably. Preferably, the particle size is 0.01 cm or more, and more preferably 〇〇3 cm or more. Under normal conditions, the characteristic length of the final particle size, that is, 10 The ratio of long to diameter (or thickness) is 50 or less, preferably 2 〇 or Less, and the daring is 5 or less. Optimally, the characteristic length of the final particles is 丄 or greater. After measuring the size, the composite particles may be difficult to handle due to static electricity. It is desirable that the particles have a 15 effect to reduce or eliminate static electricity. In a preferred mode, the dry particles are in contact with water vapor of a sufficient amount but not so much that the particles are agglomerated to reduce Or to eliminate the effect of static electricity. In this procedure, the dry granules are wetted by 0.5 wt.% or more by weight of water, and preferably 1 or more by weight of water. The portion is wetted. Preferably, the dry micro-twisted particles are wetted with 10 wt.% or less of water, more preferably 7 wt.% or less of water. Alternatively, agglutination prevention may be added. Additives (anti-clotting agents) to the composite microparticles. Such anti-clotting additives are well known in the art and contain surfactants and inert inorganic particles, such as fine stones. Dust may be generated in the program (Feature 22 200909484 is based on very small particle sizes), for example, the particle size is less than or equal to ίομm. The amount of dust generated will vary depending on the manufacturing process. To reduce unbonded dust during processing of the composite material The amount and the suppression of the end of the connection dust generation, the dried granular particles can be contacted with an effective amount of dust control agent 5. The dust control agent (dedusting agent) is used to adhere the dust together to become a larger cluster. a polymer that adheres to the larger granular composite particles or adheres to the wall of the mixer or to the container where the composite particles are retained during processing, all of which change to reduce the result The amount of unbonded dust of the polymer product in different processing steps. In addition, the use of a dust control agent for the particulate composite microparticles does not adversely affect the performance or properties of the composite microparticles. A preferred dust control agent can be one of a hydrophobic material or a hydrophilic material. Exemplary hydrophobic water control agents may include aliphatic hydrophobic oils such as mineral oils, alkanes and alkenes having about 7 and 18 carbon atoms, natural 15 oils (eg, corn, olives, rapeseed, soybeans, sunflower seeds, Other vegetable and animal oils), as well as Shixi oxygen burning oil. The above compounds can be used in solution, mixture or emulsion. Generally, the amount is at least 100, preferably at least 200, more preferably at least 300 ppm, based on the weight of the polymer particles. The amount is less than 6,000, preferably less than 3,000, and more preferably less than 1,000 ppm based on the weight of the polymer microparticles. Exemplary hydrophilic dust control agents can include water soluble polymers such as propoxylated polyols (available from the Dow Chemical Company under the trade name VORANOL). An example of a preferred dust control agent may also be a polycationic water-soluble polymer, for example, polydimethyldiallyl ammonium hydride, cation 23 200909484 hydroxyethyl cellulose, for example: UCARE JR-09, JR -400, LR-400, JR-30M and KYTAMER PC (Amerchol Corporation, USA) and the like. The polycationic water-soluble polymer is used in an amount of about 500 to 2,500 ppm based on the weight of the dry composite granule. The concentration of the propoxylated polyol in water ranges from 0.1 to 10 wt.%, and more preferably from 1 to 5 wt.%. Typically, the composite of the present invention contains at least 0.1 wt.% of SAP, a microporous improver, a water soluble polymer, an odour control agent, or one or more of an oil absorbent. Preferably, the composite of the present invention contains one or more of SAP, a porosity improving agent, a water-soluble polymer, an odor controlling agent' or an oil absorbent, which is more than 〇·1 but less than 10% by weight. More preferably, the composite of the present invention contains more than one but less than 50 wt.% of SAP, a porosity enhancer, a water extract, an odor control agent, or one or more of an oil absorbent. . In a preferred embodiment, the present invention provides a granular composite comprising a clay and a redispersible latex powder, wherein the composite comprises a weight based on a combined weight of the clay and the redispersible silicone powder. More than 15 WtV° clay. Depending on the particular application, the composite of the present invention may further comprise a fragrance, a surfactant, a colorant, a dye, a moisture indicator, a pH indicator, or a mixture thereof. 20 In other embodiments, the present invention provides a granular composite comprising 3a) 1 to 99 wt% clay, b) 0.1 to 25.0 wt.% redispersible emulsion c' ).i_99wt ·% SAP 'd) 0.1-25wt·% water-soluble polymer, e) 0·01·25”·% porosity improver; f) 〇.〇l-25wt_% odor control agent; 乂 and g) 〇. 〇l-25wt·% water. 24 200909484 Depending on the needs of different applications, the composite may also comprise from 0.01% to 25wt.% of one or more low volatility organic humectants, eg glycerol , propylene glycol, sorbitol, xylitol and maltitol, glucose, citric acid, lactic acid or urea; from 0.01% to 5wt.% of 5 one or more added fragrances; from 0.01% to 5wt% or one or more Anionic, cationic, and/or nonionic and/or amphoteric surfactants, for example: alkali metal alkyl sulfate, alkyl ether sulfate, alkyl aryl salt, sulphate, fatty acid, or Tetraammonium compound, imidazoline, ifolin, or linear/branched oxidized alcohols, oxidative oxidizing base, burning oxidized sugar bitter, 1 0 or alkylpropylaminoalkyl betaines; from 0.001% to 5wt.% of one or more dyes; from 〇·〇〇1 to 5wt.% one or more colorants; from 0.01 to 5wt. % one or more moisture reaction indicators, such as anhydrous transition metal salts containing one or more metal ions such as: Cr3+, Fe2+, Co2+, Ni2+, or Cu2+; from 0.001 to 5 wt.% of one or more enzymes or Encapsulating the enzyme; and/or from 15 0.01 to 2 wt.% of one or more pH indicators. The granular composite of the present invention means a polyfunctional granular composite and can be used in many different applications. It is an example of some non-limiting uses of the granular composite of the present invention. The granular composition of the present invention can be used as an odor control 20 preparation in air filtration products for use in conventional household, school, office, commercial buildings, public baths. , restaurants, hospitals, assisted living and nursing homes, and, for example, the filtration/fresh commercial use of VOC in the interior of a passenger compartment, such as: cars, airplanes, trains, trucks, RVs, ships, and boats. Granular composite particles can be used In many applications, it is required in 25 200909484 to absorb water (such as water, urine and ★) or odor of bursting organic N or organic compounds (voc) and / or oily substances. Heart, cat litter And the granular composite of the present invention can also be used as an absorbent core and a female care product for personal baby diapers, adult incontinence products, and protective applications _ complexes can also be used in various health and hygiene related blood clots' Surgical masks, wound dressings, and mattresses; '... 10 The granular composites can also be used as corpses and animal barriers; and; meat 叩 'fruit, and poultry food packaging applications. It can also be used in natural mineral or synthetic insulating wool, ", money and concrete. The granular composite of the present invention can also be used in garden applications, in the release of moisture control and moisture activity, fertilizers, insecticides, herbicides, fungicides, and biocides. 15 粒Invented granular composites can also be used for agronomic or horticultural purposes (eg in the containment of livestock odors), as well as for consumer malodorous products such as the smell of bathroom smells, pet odors, cooking odors, refrigerator smells, furniture And cabinet deodorant, carpet deodorant, Weifang garbage bag, woman, sweat smell, clothing 'diaper bucket' laundry, waste container, ashtray, sports 20 clothes, anti-personnel clothing, meat and Fish trays, as well as carpet backing. The granular composite of the present invention can be used for industrial applications such as catalysts, food processing, waste disposal, landfill, water filtration, fire control, and paper and pulp manufacturing. Without further painstaking efforts, it is believed that those skilled in the relevant art will be able to use the invention to its broadest scope. The following examples are merely illustrative and are not intended to limit the scope of the disclosure in any way. EXAMPLE 5 The following examples are for illustrative purposes only and are not intended to limit the scope of the invention. Procedure for the preparation of granular composite samples A. Admixture material Nai bentonite (CAS No. 1302-78-9) was obtained from Black Hills 10 Bentonite, LLC (Mills, WY) and obtained therefrom. The status is used. The nano bentonite clay used in this research work is usually honed to 75-80% and passed through a 200 mesh screen (<〇.〇74mm or 74 microns). Redispersible Latex Powder - Different forms of Dow Latex Powder (hereinafter referred to as "DLP") are commercially available. In this example, DLP 220, which is a monovinyl acetate/ethylene copolymer', has a -2. (: glass transition temperature (Tg) and (TC film formation temperature (MFFT), used throughout the experiment. The content of the DLP powder is changed from 0 to 2.5 to 5 wt.% based on the weight of the overall dry material. Superabsorbent polymer (SAP) material · Micronized SAP material 2〇 (DRYTECHTM ST10 micro-type, then referred to as “micro-type”) was obtained from DRYTECH Midland SAP factory and used throughout the experiment. The typical particle size of the fine materials used in the experiments was less than 300 microns. In yet another experiment, fragments with full cut-off dimensions of between about 100 and 850 microns were used. 27 200909484 Addition of phornish PERGOPAKTMM - PERGOPAKTM Μ (trademark of Albemarle Corporation, Baton Rouge, LA) is added to bentonite at a content of 5 wt.%·. PERGOPAK M is a polyfluorenyl urea resin (urea-furfural-condensate product) containing a small amount of Free methylol group 5 (0.66%) and can be used in the obtained form (CAS No.: 9011-05-6). 掺 Blend all materials in a large sealed plastic bag and Hand crank for about 3 to 5 minutes until the whole The materials were clearly combined in appearance and consistency. C. Wetting of the material used for extrusion 10 parts of 2 kg of material were placed in a 16 X 24" plastic tray to evenly distribute the material to a depth of about %". The previously weighed deionized room temperature water was added to the material to a weight ratio of 1:1. The water was compressed at 25 psi by a compressed air atomizer equipped with a 8〇〇4 fan-shaped mist cone nozzle. The surface is evenly sprayed until the degree of consistent wetting is 'not allowed to be visible to the naked eye. The material is then hand mixed in the pan to blend the wetted material with the underlying dry layer. Repeat the spray/hand mixing steps until the entire amount of water is kneaded into the dry material. The finished product becomes a mass, pea size (or smaller) material. If the material is over-mixed or Excessive treatment results in a more viscous and larger mass that cannot be smoothly extruded. The material is placed in a plastic cloth for about 30 minutes to be in equilibrium before extrusion. Wet material extruded using Nika low pressure basket (Nica E14〇extruder, Aeromatic-Fielder. Ltd.) Eastleigh, Hants, UK) and 28 200909484 1.2 m size sieve was extruded. The material was all added to the basket - the material was satisfactorily extruded ' If the long angel has a fine surface, the material is collected and carefully placed on a stainless steel tray covered with a nylon screen, which is then placed in a drying oven. Gently press the extruded 5 pellets to make sure they have dried properly. The extrusion was used throughout the experiment unless otherwise specified. E. Drying The extruded material was gently placed on a drying tray to ensure it dried on average, and the tray was then fed into 55 ovens overnight. The 1 〇 product is then carefully shaken to aid and accelerate drying. The time to completely dry is about 24 hours. The average humidity is about 7 wt.% (the oven is dried at 105 °c for 2 hours). F. Screening The β-dry material was then crushed and placed in a G1att sieve equipped with a 2 mm salmon bone 5 sieve and placed in a plastic bag. During the process, the material was properly crushed and very fine dust was observed. This material is hereinafter referred to as a "A-type" granular composite and has a diameter of about 1 mm and a length of from about 1 mm to about 15 mm. G. Honing 2 0 .. In some cases, the granular composite particles will be further honed with a coffee grinder after the respective size and over-steps. The procedure of the granule honing of the composite is carried out to reduce the length of the granules to produce granules having the same diameter but short rutting. After honing, the small size fragments that can pass through the screen (100 mesh screen or 疋 150 microns) are discarded, and the larger particles obtained are retained in 29 200909484 and weighed and supplied to obtain an average and medium number. They are narrow particle size distributions of 1090 μm and 1066 μm, respectively. This material is hereinafter referred to as "Β-type, granular composite. Table 1 shows that the composite particles are sieved with a 1 mesh screen after honing" using an LS particle size analyzer (Beckman Coulter LS 13 5 320) Particle size and distribution after measurement. Table 1: Percentage of particle size fragments of the ground granular composite (Type B) <10% <25% <50% <75% <90 % Particle size 743.4 μηη 898.5 μιη 1066 μιη 1269 μηι 1495 μιη Test procedure for sample properties Acceptance test: Centrifuge retention capacity (CRC) step 10 parts of a 300 mg granular composite (Type A) were placed in a heat-sealed tea bag. The tea bag is 59 mm by 75 mm (Grade 7291, available from Ahlstrom Fiber Composites, Chirnside, Dunes Berwickshire, Scotland). The edge is heat sealed with an iron to allow the tea bag to be completely sealed. By holding it vertically and gently The tea bag was tapped so that the granular composite particles 15 were evenly dispersed throughout the bag. 0.9% of the salt solution was poured into a glass dish of about 3 〇cm χ 19 cm x 5 cm. The tea bag was immersed in a salt solution. In the middle of the time ^ factory time. The tea The bag was then removed from the solution and centrifuged at 16 rpm for 3 minutes. Next, the tea bag was weighed. The original weight of the tea bag with dried pellets and the wet tea bag after centrifugation The weight difference of the wet pellets is 2, and the weight of the absorbed salt solution is measured. The weight ratio of the absorbed salt solution to the weight of the dry composite microparticles is the centrifugal retention capacity (CRc), and it is per The number of grams of dry granular composite particles is recorded (g/g). 30 200909484 Cover test. Exaggeration: Absorbent under load (AUL) step 400 mg of granular composite sample is evenly spread on "AUL" The bottom of the chamber is a hollow plastic cylinder with a plastic outer diameter of 31 mni and an inner diameter of 25 mm. The chamber is 33 mm high. The bottom of the chamber is covered with a slim nylon mesh. After the addition of the composite particles, a A plastic piston is placed on the pellets to record the weight of the chamber with the pellets and the piston. Next, the weight of l〇〇g is placed on the piston in the chamber. The weight of the 1 〇〇g and the total weight of the piston are l 〇 9.4g, providing 2.1kPa (0.3 lb / The load is loaded on the particles, etc. An analysis disk (24 cm x 24 cm X 2.5 cm) is used, which has 16 holes drilled into the cover. The holes have a diameter of 31 coffee and are circumferential. The holes are defined in a circle having a diameter of 124 mm. The cover is removed and a glass scorpion (124 mm in diameter, 12 mm high) is placed in the tray and located below the six holes in the tray cover. 〇.9% of the salt solution was added to the tray until it was equal to the top of the Foz but would not be covered. Place a 15 124 mm diameter crepe paper over the Foz. If the operation is broken, the salt solution will humidify the paper through the Foz. The tray cover is then placed over the tray. The AUL chamber is then placed across the bore so that it is above the filter paper above the Foz. The cells are added two times at the next time and placed on opposite sides of each other. The pellets were given for two hours to absorb 20 grams of gluten. After 1 hour, the chamber was removed from the tray. The 100 g weight is then removed from the chamber and the chamber is weighed. The difference in wet weight to dry weight of the chamber provides the quality of the solution absorbed by the composite particles. This value is divided by the original mass of the hetero-complex particles to give the unit AUL. 31 200909484 Clot Absorbency Test Procedure Mark a 2·5 X 2吋 plastic hexagonal weighing disc. Approximately 2 grams of composite particulate material is placed in the corresponding weighing vessel. Each granulated sample was administered 2 mL (about 2 g) of synthetic urine (made with 2.1 mL of 28% aqueous ammonia solution, 5 50_4 g of urea '4.3 g of CaCl 2 * 2H20, and 5 mL of water). A one hour waiting time is provided to allow the urine to be absorbed to form a clot. After the waiting time has elapsed, each sample is placed in a laboratory balance and the balance is reset to zero. Use a spatula to gently remove the clot. Record the reduced weight on the balance as the weight of the clot. Finally, the length, width and depth of each clot are recorded in millimeters. Based on the above test, the clot absorbency of the synthetic urine solution per gram of the dry granular composite particles can be calculated as follows. Clot absorptivity (g/g) = 2 g / (clot weight - 2) g. Clot absorptivity is a measure of the amount of liquid absorbed by a granular composite particle upon brief contact with a liquid. A lower clot weight (g) results in higher clot absorbency (g/g). For the sake of simplicity, the clot weight (g) is used in all of the present invention. A-flavor control #能.消丨Μ Two different methods were used to evaluate odour control performance·smell test and gas chromatography (GC). Olfactory test 20 A 30 g portion of the composite granules was placed in a 10 mL glass flask. The test solution was prepared by adding 800 ppm of tridecylamine (TMA) to synthetic urine. Add 2 mL of urine/TMA solution to each liter of sample. The sniffing test was performed at room temperature using the following scores at room temperature. 〇 = no malodor; 1 = slight malodor; 2 = malodor; 3 = strong malodor 32 200909484 Gas chromatographic analysis (GC) measured in some examples, using TMA, dimercapto disulfide (DMDS), formaldehyde , styrene monomer, and dimethyl phthalate (DMp) to measure the effectiveness of the granular composite to control malodor and volatile organic compounds (v〇c). 5 General procedure for preparing + bottles Vials were prepared by weighing 〇·1 g of granular composite granules into a vial of 22 mL headspace. The a-type granular composite was used in all of the GC tests. Next, a 2 mL vial was submerged into the headspace vial. After this, the lpL solution is typically added to a 2 mL vial. Next, cover the top 10 vials. This step avoids any liquid contact between the solution and the particulate composite particles. Any interaction can only be obtained from vaporized gases. The vial was left at room temperature for several hours prior to sampling. The analyte in the headspace is detected by GC by either mass spectrometry (MS) or flame ionization detection (FID). 15 The composition of the solution used with each compound is provided in Table 2. 33 200909484 Table 2: Details of each compound Compound Solution composition Trimethylamine (TMA) 2_1% TMA is soluble in water. The initial test used ι〇μ [solution and the second test used bL solution v dimethyl disulfide (DMDS) 250pg/mL DMDS in water containing 1% DMF formaldehyde. Initial test using 37% meth, 12% methanol In the water. The second set of experiments used 3.9% formaldehyde, 1% methanol dissolved in water styrene 〇 _ lmL volume 〇. 1% styrene dissolved in water containing 丨% DMF dimethyl phthalate (DMP) undiluted for each supply The conditions for the four compounds are provided below. Table 3: Instrumental conditions for TMA, formaldehyde and DMP LEAP/CTC CombiPal oven at room temperature (unheated, 22T) Injection temperature TMA and formaldehyde are 80 ° C, DMP is 50 ° C Injection volume TMA and furfural For 500 μΙ^, DMP is 2000 μί. Between the TMA solutions, rinse the headspace vial with a concentrated ammonia solution diluted to 1:4 with water at 50 °C. Gas chromatograph analyzer Agilent 6890 tube column formaldehyde and DM^: J&WSciDB-5 30mx0.25mm, Ιμιη film TMA 'Varian CP-7447 Volamine 30m x 0.32mm inlet 200°C, split, DMP 20:1 split, Formaldehyde 50:1 split, TMA 10:1 shunt column flow He, stable flow DMP and furfural: 1.0mL/min, TMA: 1.9mL/min oven DMP: 200°C, 10°C/min to 250° C Formaldehyde: 35°C, 5min, 10°C/min to 100°C TMA: 60°C, 4min maintenance, KTC/min to 110°C DMP and brewing: Mass Spec Agilent 5973 DMP: selected from Ion Monitoring with 163 And 194 m/z furfural: 20-50 scan m/z, quantify TMA FID 250 °C, 40.0 mL/min H2, 400 mL/min air, 45 mL/min N2 stable at 30 m/z selected Flow 34 200909484 Table 4: Instrument Conditioner for DMDS and Styrene PerkinElmer TurboMatrix 40 Oven Close (28-29T) Needle 80°C Transfer Line Restek 0.25mm Siltek ? 90°C Injection Time 0.07min Column Pressure 30psig Gas Phase Layer Analyzer Agilent 6890 Columns Restek Rtx-35 30m x 0.25mm, Ιμηι Film Oven DMDS : 40°C, l(TC/min200°C Styrene : 5(TC,l .Omin maintenance, 15 ° C / min to 20 (TC column pressure He, 20 psig, constant pressure inlet 200 ° C, split, set the GC ratio to 1.0 flame ionization detector (FID) 250 ° C, 40.0mL /min H2,400mL/min air, 40mL/min Stable N2 flow, range=〇Large capacity odor test Use a one gallon cylindrical plastic container (high 93⁄4", diameter 53Λ) as the 5 test equipment. Install a name accessory (3D dimensions: ring-outer diameter 1 1/8", inner diameter W; fittings - outer diameter 1 1/8,,, wire diameter ι/2", outer tube connection diameter 5/16"; inner diameter!/4&quot ;, 1% higher, line height 1/2") on the corresponding cover, the cover has a W hole cut in the cover. Tighten the accessory with your fingers. Next, a 4 long TYGONTM (trademark of Saint-Gobain Corporation) 10 pipe (outer diameter (0D): 3/8 inch, inner diameter (ID): 1/4 inch, and wall thickness 1/1611 inch) Attached to the outside part of the accessory. A plastic clip is placed in the center of the tube and tightened to close it. A 5 gram granular composite (or other material) was added to the vessel to homogenize the granules of the 2009 2009 484 complex at the bottom of the granulator. The vials were placed in large & and some servings and types of malodor were added to the vials. In the Pirates, the right 'not special · ^ 5 Ming' uses ammonia containing l2 〇 0PPm (based on the weight of the solution: 1200PPm TMA volume 600 liters of 〇 · 9% salt solution as a control group: odor solution. The container Immediately and with an aluminum fitting, the end of the TYGON tubing is located above the lid. The tube cutter is used to break the two tips of the appropriate Draeger short-term gas detector tube. The end is inserted into Tygon tubing so the flow indicator is pointing away from the test equipment. 10 After the appropriate time, the outer end of the gas detection tube is inserted into the hand pump and the cooling on the tubing is released. The hand pump is fully depressed (in At this point 'the number of counters above the pump is increased one by one and then released' and allows air to flow through the tube. Each cycle has a flow of one hundred cubic centimeters through the tube. When the indicator on the position pump becomes The white cycle ends when the white cycle ends. The material in the tube changes color to indicate the gas detection result. The gradient from the tube side is recorded in ppm. Ammonia tube (part number CH20507, range 5-70ppm, color Yellow change to blue) and TEA tube (test TMA; part number 67184〇1, range 5-6 mouth 0111, color change from yellow to blue) Measure the amount of ppm level. Manual pump pressure and display odor level Repeat four times 2 times or more, record after each cycle (hit), and cause a total of 500cm3 of air pump to pass through the gas detection tube. In-line transition test boat _ placed an aluminum fitting On the cap of a 1-gallon plastic container (large container), a hole is cut in the center of the lid of the container, and then the fitting is firmly tightened with fingers 36 200909484. Next, the 4" long TygonTM tubing (outer diameter (〇 d): 3/8吋' inner diameter (ID): 1/4 inch, and wall thickness l/l64) (trademark of Saint_G〇bain Corporation) is attached to the outer part of the fitting. Place a plastic clip The tube is centered and tightened inwardly to close it. The vial is placed in a large 5 container, and some portions and types of malodor are added to the vial. If not specified, use 1200 ppm ammonia (by solution weight) For the benchmark) or 1200Ppm TMA volume 6 〇〇 microliters 〇.9 The % salt solution is used as the control group malodorous solution. The container is immediately sealed with a lid of an aluminum fitting. The filter material is added to the in-line filter so that it is flush with the upper end of the metal ring. 10 Record the weight. The three-dimensional dimensions of the filter assembly are as follows: Outer fitting: 〇D = i 1/2"; Large 1〇 = i 1/4"; Small 1〇 = 3/4"; High = 5/8" Inner fitting: 〇 D = i 1/2"; line 〇 D = 丨 1/4 „ ; ID = %” ; height 5/8, 15

20 consecutive,. Pieces. 〇D - slightly less than W; D tube = slightly less and slightly more than ι/4"; high = 7/8" metal ring: od = 7/8"; ID = 3/4"; /4,, 〇-ring: OD=iy4,, ;id=13/16” 13⁄4 screen · 〇D = 1 The positive care is grouped and then attached to the outer 118 of the top of the cover. End. Use a tube cutter to break open the two tips of the appropriate Draeger. The end is inserted into the Tygon tubing so the flow indicates difficulty to the __ test equipment. After the appropriate phase (usually 3 hours, if + surname It will be noted that the outer end 37 of the gas detection tube, 200909484, is inserted into the hand pump, and the clamp on the pipe is released. The hand pump is completely depressed (at this time, the counter at the upper end of the pump) The number is increased one by one and then released, and air is allowed to flow through the tube. One hundred cubic centimeters of air per cycle flows through the tube. The cycle ends when the indicator at the upper end of the pump becomes 5 white. The material will change color to indicate the gas detection result. Record the gradient ppm level from the tube side. Ammonia tube (part number CH20 507, range 5-70PPm, color changes from yellow to blue) and TEA tube (detection TMA; part number 67184 (Π, range 5_6〇ppm, color changes from yellow to blue) measures the number of ppm levels. Manual pump Pressing and displaying the level of odor 10 is repeated four times or more, owing after each (four) (hit), and causing a total of 500 cm3 of air pump to pass through the gas detection tube. Example i: Using KITC Brain AID Extrusion of the granular composite sample of the TM agitator 15 20 The fine-sized SAP material ("fine type") was prepared differently from the normal SAp according to the description (4). The amount of DLp was maintained at MW. And the fine SAP is 25wt·%. The blended compound (see table) uses the KitehenAid vertical swimmer to “extend the auxiliary. ^ Slow motor” and slowly add 200g (2 times the dry plant) (4) The sub-water money is mixed with the towel. The water is mixed with the dry (four) parts to form a condensate and metaplastic material. When fully mixed, the motor is turned off, ^ the wet material is located at the win The food on the honing appendage, using the disc with a larger hole (about 6 mm in diameter. The material was dried at 105 C for several hours. a 38 200909484 Table 5: Granular composite samples prepared using the KITCHENAIDTM type extruder

Sample Naphthene Bentonite DLP 220 SAP Normal SAP 72.5g 2.5g 25g Normal SAP Micro-SAP ---- 72.5g 2_5g 25g Fine SAP Compared with a mixture containing fine S AP, the mixture of normal S AP is separated and More difficult to squeeze. The use of SAP microfabrication is uniform and easy to operate. The clot absorption test of the granular composite sample from the Kitchen Aid extrusion apparatus was carried out using a synthetic urine solution, and the results are shown in Table 6. Table 6: Clot absorption test of granular composite sample Clot weight (g) Length (mm) Width (mm) Depth (mm) Normal SAP 6.321 17 22 14 Micro SAP 5.656 20 25 16 to 5 The results in Table 6 indicate that the nano-bentonite clay composite containing DLP is likely to have an extremely high absorption function. The resulting composition from the KitchenAid test also showed good clot formation of the composite granules with the synthetic urine solution. Example 2: Extrusion of a granular composite using a Nika low pressure basket extruder Two samples were prepared' based on the total weight of the dry blend, but using different amounts of Pergopak (〇 or 5 Wt·%). Pergopak® was added to the blend (2.〇kg) before being wetted with water (2.〇kg). In both cases, DLP was maintained at 2.5 wt.%. 39 200909484 Table 7: Extrusion sample of granular composite sample (type A) using Nica low pressure basket extruder Nano-bentonite DLP 220 SAP Fine Pergopak M 〇wt.% Pergopak Μ 72.5wt.% 2.5wt .% 25 wt.% Owt·% 5wt·% Pergopak Μ 67.5wt.% 2.5wt.% 25 wt.% 5wt.% Example 3: Centrifugal retention capacity (CRC) of composite granules and absorption force under load Absorbency of the granular composite sample (type A) of Example 2. CRC measurements were carried out in a solution containing 0.9% salt and deionized water, and the results are shown in Table 8. These poor materials exhibit an average quality of repeated measurements. Aul was measured using a 9%.9% NaCl solution. Table 8: Absorbance results of composite granules Sample CRC (g/g) CRC (g/g) in H20 in 0.9% NaCl AUL (g/g) at 0.9% NaCl t Owt.% Pergopak M 84.3 8.9 5.8 5wt.% Pergopak M 68.3 7.7 6.1 1〇 Although the fraction of SAP (ie, 25 wt%) in the composite granules is small, the composite granules exhibit high absorption. The effect of salt concentration on absorbency is shown in Table 8, for example, water versus saline. The composite granules do not appear to be too negative for the negative effects of stress. The presence of (4) at 5 wt%, M, which is a non-expandable material, appears to reduce the absorbency (dilution effect) of the sample containing Pergopak®. The free expansion of the pure nano bentonite in water is expected to be about 7.5-8.0 g/g. Uncontrolled clc and aul data for pure bentonite are available. However, the CRC and 40 200909484 AUL values for bentonite in salt water towels are expected to be much smaller than the free expansion capacity of bentonite in water. The absorption data of the two composite granules indirectly indicate that the superabsorbency in the granules of the composite is not impaired. Example 4: Agglutination Absorption Test and Effect of PERGOPAKTM 5 5 In Table 9, shows the agglutination absorbance and effect of a composite sample (Α type) containing no pergopak® and Pergopak®. The values are the average of five independent tests and the parentheses are the standard deviation of five independent tests. The clot obtained from the composite granules (type A) has a slightly cylindrical shape as indicated in Table 9. Samples containing Pergopak® absorb much more quickly because the 10 clots are shallower. Composite pellets containing Pergopak® appear to be more useful than pellets of samples that do not contain Pergopak® because they exhibit a lower clot weight. Table 9: Pergopak effect on agglutination absorption Sample clot weight (g) Length (mm) Width (mm) Depth (mm) 0 wt.% Pergopak Μ 7.533 (0.266) 32.8(1.3) 26.4 P.9) 21.0(1.4) 5 wt.% Pergopak M 6.107 (0.086) 27.2 (3.0) 22.6 (2.8) 25.2 (3.0) 15 Example 5: Effect of Pergopak on absorption rate

The findings in Table 9 seem to indicate a rapid absorption due to the preferred porosity on the surface. This finding also indicates that the permeability of the liquid leading edge is longer than that of the PergGpak®-containing sample (Type A) obtained from Example 2 for samples without Perg〇pak® (see Table 7). In order to check this effect, a test such as 20 was carried out. Approximately 70 mL of the composite granules were added to two 8 烧 beakers to a depth of about 80 mm (one with Pergopak M, the other without), and 2 mL of 41 200909484 was added and the urine was added to each beaker. After -hour, the clot was removed, weighed and measured. The results are summarized in Table 10. Table 10: Effect of PergopakM on absorption speed

5 Based on the penetration of the liquid leading edge (deep)' The liquid leading edge penetrates freely through the pellet sample without Perg〇pak M compared to the sample containing Perg〇PakM. Example 6: Extrusion Test and Effect of DLP In the test shown in Table 11, the amount of DLP was varied from 〇 to 5 wt.%. In all the examples, perg〇pak μ was maintained at 5 wt.% based on the total weight of the dry-fit material. In the 12th table, 'the results of the different complex granules (type a)' suspect test were shown. Values are the average of five independent experiments. Table 11: Extrusion test sample Nana bentonite DLP 220 with different amounts of DLP using Nika low pressure basket extruder. SAP Fine Pergopak M Hand compound 0 70 wt.% 0 wt.% 25 wt.% 5 wt. % Blend 2.5 67.5 wt.% 2.5 wt.% 25 wt.% 5 wt.% Hand compound 5 65 wt.% 5.0 wt.% 25 wt.% 5 wt.% 42 15 200909484 Table 12: Synthesis Urine plus agglutination absorption test sample added to the composite granules Clot weight (g) Length (mm) Width (mm) Depth (mm) Blend 0 8.564 35.4 28.2 23.0 Blend 2.5 7.370 29.0 25.0 24.2 Blending Item 5 6.441 28.4 25.0 23.6 Scoop Away 7.466 27.4 25.8 Change from 17 to 5 In the test shown in Table 12, Scoop AwayTM Clorox Company was used as the control group. A granular composite 5 sample containing DLP in Table 12, such as Blend 2.5 and Blend 5, outperformed the Scoop Away sample in terms of agglutination absorbability. The Scoop Away cat litter is made in a hemispherical shape with a deeper center and a shallower edge. Because it is not a cylinder, these values are measured at both the center and the edge. Example 7: Effect of different amounts of liquid 10 In another test, the small sample with different amounts of DLP (as shown in Table 11) was added to a synthetic artificial urine ranging from 1 to 5 mL for Agglutination absorbency test. The results are summarized in Table 13. 43 200909484 Table 13: Agglutination Absorption Test Results in Synthetic Urine of Different Servings----" Sample Addition Synthetic Urine (mL) Clot Weight (g) Blend 〇1 4.804 Blend 〇 2 9.273 Blend 〇3 13.454 Blend 〇5 22.308 Blend 2.5 1 3.937 Blend 2_5 2 7.534 Blend 2.5 3 11.121 Blend 2.5 5 18.988 Blend 5 1 3.346 Blend 5 2 6.681 Blend 5 3 10.244 Blend 5 5 16.728 The trend in Figure 1 shows a good correlation between the weight of the clot and the amount of synthetic urine added (R squares). The results in Table 13 and Figure 1 show that as the amount of DLP increases, the composite granules produce less clot weight and, therefore, the granulated complex has a higher agglutination absorbency. Example 8: Odour Control Effect The odor control effect of the complex shown in Table 11 was tested at a TMA concentration of 800 ppm based on the weight of the synthetic urine solution. This odour control effect is next compared to Scoop Away ("Fresh Scent, Maximum Odor Control"), which is a commercial cat litter product from Clorox Company. 44 200909484 The results of the odour control effects of different composite samples (type A) are summarized in Table 14. Table 14: Results of odour control complex granules (A crack) at 800 ppm TMA. Sample time 0 1 hour 3 hours 5 hours 7 hours] 16 hours 2 曰 7 曰 exchange compound 0 2 0 0 0 0 0 0 0 Blend 2.5 2 0 0 0 0 0 0 0 Blend 5 2 0 0 0 0 0 0 0 Scoop Away 2 2 1.5 1.5 1.5 1.5 1.5 1.5 5 Overall results indicate that the granular composite of the present invention is used in different applications The stench control potential of the field, including use in air care, for example, in the field of air filtration. Odour control is important in cat litter applications, and the granular composite of the present invention exhibits an odor control effect that exceeds Scoop Away. 10 Example 9: Test using a Nika low pressure basket extruder with the effect of a porous polymer adsorbent and MethocelTM 4. Porous polymer adsorbent Dow OptiporeTM V503 (hereinafter V503) was obtained from Dow Chemical The company, while MethocelTM A4M is used in powder form '5wt.% and 2.5wt.%, respectively, in the composite granules for 15 as a special additive. The extrusion test is shown in Table 15. 45 200909484 Table 15: Extrusion sample additive using the Nika low pressure basket extruder (Type A) sample Additive Bentonite DLP 220 CAP Micro-Pergopak M Granular composite without 65 wt.% 5 wt. % 25 wt.% 5 wt·% Polymer adsorbent V503 5 wt.% V503a) 60 wt.% 5 wt.% 25 wt.% 5 wt.% Methocel A4M 2.5wt.% Methocel 4AMb) 62.5 wt.% 5 Wt.% 25 wt.% 5 wt.% a) used in honed <250 micron format, b) used in powder obtained 5 composite sample containing polymer adsorbent V503 and Methocel provides granularity The composite sample is a slightly non-stick extruded strand. The addition of the porous polymer adsorbent V503 and Methocel showed no change in extrusion processing properties. The clot weight of the sample containing the polymer adsorbent and Methocel is comparable to that of the granular composite sample system. 10 Example 10: GC test for TMA The results of the interaction between the TMA and the composite sample (Type A granular composite, see Table 5) are summarized in Table 16 below. The values in parentheses are the percent TMA reduction relative to the control group (TMA vial). In the case of the GC test, the amount of 2_1〇/〇TMA/water solution per vial of Ιμί is completed at intervals of 15 nights at equilibrium} The results show that the average peak area from the same test to control injection (ΤΜΑ exists, no granular composite) is 187876 . No defects were detected in the blank vials (no sputum, sorbent), and all three sample vials (ΤΜΑ and composite granules) were not related to the form of the additive in Table 15. The GC test was repeated with an increased amount of hydrazine/water solution. As the last measurement of 20' this step is the same except that the amount of 2.1% ΤΜΑ/46 200909484 aqueous solution per vial is increased from Ιμί to 10μί. Also, the balance time is replaced by 3 to 4 hours overnight. Table 16: Results of GC test for sputum Sample TMA Peak Area Control Group (TM A vial) 2501768 (0%) Granular Complex 27454 (98.9 Percent) Polymer Adsorbent V503 11435 (99.5 Percent) Methocel A4M NDa) (1%) A) No measurable 5 The results of Table 16 show that all of the granular composite samples significantly reduced the TMA concentration in the headspace. For example, the solution controlled headspace malodor TMA concentration is reduced by 98 to 1% by the presence of the granular composite. The effect of the sample containing Methocel A4M appeared to be slightly better than the granular chelating sample containing the polymer adsorbing 10 doses of V503 or the granular composite sample of the present invention. Example 11 • GC test for DMDS The peak area is provided in Table 17 for the study of the interaction of DMDS in a composite sample (see Table 15). The values in parentheses are the percent reduction in DMDS relative to the control group (DMDS vials). The values are derived from the average of the repeated 15 tests. 47 200909484 Table 17: GC test results for DMDS Sample DMDS peak area control group (DMDS vial) 3358 (0%) a) Granular composite---- 3450 (+2.7%) Polymer adsorbent V503 --- 227 (93.2 percent) Methocel A4M 3393 (+1·0 percent) a) The second measurement did not detect the absorption of the granular composite and the Methocel A4M sample. However, the malodorous DMDS concentration in the top region of the solution control group was significantly reduced by the granular composite containing the polymeric adsorbent V503, for example, by 93%. Example 12: GC test for formaldehyde The formaldehyde peak in the presence of a sample of the composite (type A) (see Table 15) 10 is provided in Table 18 below. This value is obtained by one measurement. Table 18: Results of GC test for furfural Sample peak area control solution (3.9% furfural vial) 731339 (0%) Granular composite / 3.9% furfural NDA) (100%) Polymer adsorption Agent V503Α/3.9% Formaldehyde 275123 (62.4%) Methocel Α4Μ/3.9% Awakening · 303351 (58. 5 percentage) Control solution (37% furfural vial) 5807503 (0%) Granular complex / 37% Furfural 1742701 (70%) Polymer adsorbent V503A/37% furfural 2582106 (55.55%) Methocel A4M/37% Awake 1983864 (65.88%) a) Undetectable 48 200909484 This data shows all three The composite sample reduced the formaldehyde concentration in the headspace, independent of the formaldehyde concentration. When a 3 9% furfural solution is used, the granular composite outperforms other complexes containing Methocel A4M or polymeric adsorbent V503. When a 37% formaldehyde solution is used, the granular composite exhibits a slightly better composite than other compositions containing Meth〇cel A4M or a polymeric adsorbent 乂5〇3. Example 13: Gc test for stupid ethylene monomer The results of the interaction of styrene monomer with a composite sample (see Table 15) are summarized below in Table B. These results were obtained from repeated tests. The values in parentheses are the stupid reductions relative to the control group (styrene monomer). Table 19: 〇 for styrene monomer (: test sample styrene peak area control group (styrene vial) 202101 (0%) ~~~^ granular composite 110811 (41.7 percent) polymer adsorption Agent V503 939 (99.5 percent) Methocel A4M 112399 (44.4%) ------- All compositions further reduce the concentration of styrene monomer 15 in the headspace. For example, the top of the control group solution The spatial styrene concentration was reduced by 44 to 99.5 percent due to the presence of the particulate composite. The effect of the polymer adsorbent V503 complex significantly enhanced the performance of the granular composite or the 厘1〇(^1Α4Μ sample). Example 14: GC test for DMP 49 200909484 The results of the interaction of DMP with complex samples (see Table 15) are summarized below in Table 20. These results were obtained by repeated experiments. The value is the DMP reduction relative to the control group (DMP). Table 20: GC test control group (DMP vial) for dimethyl phthalate (DMP) 2137042 (0%) a) Shape composite 847155 (60.4%) polymer adsorbent V503 705346 (67. 0%) Methocel A4M 1067728 (50.0%) 5 a) Results from three repeated tests All composite samples significantly reduced the concentration of DMP in the headspace. For example, the headspace DMP concentration of the control group is reduced by 50 to 67 percent due to the presence of the particulate composite sample. The effect of the polymer adsorbent V503 and the granular 10 composite sample showed a better performance than the composite sample with Methocel. Example 15: Test using Nika low pressure basket extruder with effect of citric acid and glass beads Powder form citric acid (CAS # 77-92-9, ACS reagent, Aldrich) 15 was 25 wt.% Used as a special additive. Glass beads (CAS#: 65997-17-3, P0040; size: 〇·1 mm or finer) from Porter Industries (Westlake, OH 44145) at 5 wt·% and 10 wt·%, respectively The amount is used as a special additive for the composite granules. The extrusion test is shown in Table 21. 50 20 200909484 Table 21: Extrusion sample of the composite sample using Nicole low pressure basket extruder Additive bentonite DLP 220 SAP Fine Pergopak M 5% glass beads 5wt.% glass beads P0040 65wt.% 5wt.% 25 wt.% Owt.% 10% glass beads 10wt.% glass beads P0040 60wt.% 5wt·% 25wt·% Owt.% Citric acid 25wt.% citric acid 65wt.°/〇5wt.% Owt .% 5wt.% The composite containing glass beads provides a normal extruded strand, while the citric acid-containing composite provides a strand that is slightly more viscous than the granular composite sample. 5 There is no difference in the processing properties of citric acid and glass beads added to the extrusion. The dried composite material is honed and then sieved through a 150- and 1200-micron screen prior to use (see Table 22). Example 16: Ammonia Concentration (ppm) gas detection test for large containers at the headspace and the effect of citric acid and glass beads 10 Table 22 below provides ammonia to composite samples in the headspace of large vessels (see Table 21). ) Interaction studies in concentration testing. The values in Table 22 are the parts per million (ppm). A 0.9% salt solution (600 microliters) containing 1200 ppm ammonia was used as the control group malodorous solution. 51 200909484 Table 22: Results of gas detection test for ammonia concentration (ppm) in the headspace of large vessels

The data showed that the malodorous solution was added to the ammonia concentration in the headspace, while the fish time threshold was increased. The m-degree of agriculture was about 3 to 6 hours after the arrival of 52 5 200909484. The control group malodorous solution The data also shows that the ammonia concentration in the headspace will decrease slightly, which seems to be because the ammonia gas molecules are absorbed by the walls of the large vessel. This is visible overnight, usually in a 16 hour time zone. The sample of the complex is reduced to 5 degrees of ammonia in the headspace. It is irrelevant to time. With the increase of time, a high-performance malodor control agent was found. The two granular composites containing glass beads showed slightly better than the granular composite. The efficacy of the 10% glass bead complex seems to enhance its performance' over the granular composite and the 5% glass bead complex. The granulated complex containing citric acid is significantly lower than the top. Ammonia concentration in space. The efficiency of a granular composite containing lime 10 citric acid seems to outweigh the performance of a granular composite or a granular composite containing glass beads. Example 17: Using a Fujitsu high pressure extruder Potassium Hydroxide Debris Form (CAS# 1310-58-3, Professional Grade, JT Baker) in the form of micro-debris in effect with potassium hydroxide was used as a special additive for the composite granules in an amount of 10 wt.%. The wetted material used was a high-pressure extruder of Fuji Business Co., Ltd. (type: EXD-60, Fujisho, Osaka, Sakamoto). The extrusion test is shown in Table 23. Table 23: Composite using a high-pressure extruder of Fuji Business Co., Ltd. Extrusion sample add-on sample bentonite DLP 220 cap Micro-type Pergopak M KOH with SAP 10wt% KOH fine flakes 60wt.% 5wt.% 25wt.% Owt.% KOH No SAP 10wt.% KOH Fine flakes 80wt.% 5wt .% Owt.% 5wt.% The sample containing potassium hydroxide provides a normal extruded strand. The extrusion time 20 is quite fast, about 5 minutes, and the extruded product is normally dried. Add 53 200909484 Potassium Hydroxide The process does not alter the processing properties of the extrusion. The dried composite material is honed and sieved through a 150- and 1200-micron screen prior to use (see Table 24). Example 18: Large container headspace ammonia Concentration (ppm) gas detection test with hydrogen and oxygen 5 potassium and lemon Acid performance test different granular composite samples, including ammonia malodorous solution, granular composite, granular composite sample containing potassium hydroxide (with or without SAP), and citric acid granular composite sample ( See Table 21), at different times, for example: 1 to 16 hours (overnight) of ammonia malodor efficiency. 0.9% salt solution (600 μl) containing 10 1200 ppm of ammonia was used as the control group malodorous solution. Shown in the 24th table. 54 200909484 Table 24: Ammonia concentration (ppm) in the headspace of large containers Gas test results Sample time 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control group malodorous solution 1 hour 6 12 17 21 24 3 hours 11 21 30 37 44 6 Hours 11 22 32 39 45 Overnight 7 14 21 26 31 Granular composite 1 hour 1.5 2.5 3.5 4.5 5 3 hours 1 2 3 4 5 6 hours 0.5 1 1.5 2 2.5 Overnight 0 0.5 1 1.5 2 KOH granular composite SAP% 1 hour 4 7 11 15 19 3 hours 10 19 27 33 40 6 hours 11 21 27 33 39 overnight 7 14 20 25 30 ΚΌΗ granules | fit no SAP% 1 hour 3 7 10 13 15 3 hours 7 14 20 25 30 6 hours 7 14 20 27 33 Overnight 5 10 14 19 23 # 酸酸粒状复合 a), b) 1 hour 0.5 1 1.5 2.5 3 3 hours 0 0 0.5 0.5 1 6 hours 0 0 0 0 0.5 Overnight 0 0 0 0 0 a) The particle size range is between 150 microns and 1200 microns. b) Samples taken from Table 21. Independent measurement. The data in Table 24 shows that the control group malodorous solution increased the ammonia concentration in the headspace with an increased number of shots, but was not correlated with time. Ammonia concentration 55 200909484 reached its peak after about 3 to 6 hours. The control malodorous solution data also shows a slight natural decrease in ammonia concentration in the headspace because the ammonia gas molecules are absorbed by the walls of the large vessel. This is visible in the case of overnight, usually in a 16 hour time zone. Furthermore, as time increases, higher levels of odor control are found. The granular composite containing citric acid further significantly reduces the concentration of ammonia in the headspace. The citric acid-containing granular composite appeared to outperform the granular composite, which is consistent with the results shown in Table 22. The granular composite containing potassium hydroxide, irrespective of the presence or absence of SAP, exhibits a basic malodor (e.g., ammonia used in the test) which is inferior to the granular composite 10 and the citric acid-containing granular composite. Example 19: Granular composite coated with citrus essential oil for odour control efficacy using orange essential oil (CAS#: 8008-57-9, cold pressed, California, Aldrich) at 2 wt% (in granular composite) The amount based on the dry weight is a special additive. The dry and dry composite material (1 gram) having a particle size of 150 micrometers and 1200 micrometers is placed in a 5 inch mL PE bottle, and a few drops of pine tangerine oil are added to the surface thereof, and the cover is covered. The bottle was shaken for 3 to 5 minutes. This step was repeated until all of the citrus essential oil was used up. This coating step results in a free L-assisted non-condensed granule and is hereinafter referred to as a fragrant granular composite. Example 20: Large container headspace ammonia concentration (ppm) gas detection test and citrus essential oil flavor efficacy The citrus essential oil treated aromatic granule complex & body was tested at two different times, for example: 1 hour and 3 hours. 0.9% salt containing 1200 ppm ammonia 56 200909484 Solution (600 μL) was used as the control group malodorous solution. The results are shown in Table 25 and compared with those obtained from the granular composite under the same conditions. Table 25: Large container headspace ammonia concentration (ppm) gas detection test and citrus essential oil fragrance efficacy sample time 100cm3 air 200cm3 air 300cm3 air 400cm3 air 500cm3 air control malodorous solution 1 hour 7 13 19 25 30 3 hours 7 13 19 25 30 Aromatic granular composite a) 1 hour 1.5 3 4.5 5.5 7 3 hours 0 0.5 0.5 1 1 5 a) The particle size range is between 150 microns and 1200 microns. The data shows that the control malodorous solution increases the ammonia concentration in the headspace with an increased number of shots. The control group malodorous solution detected a slightly lower ammonia concentration after 3 hours. However, the aromatic granular composite sample reduced the ammonia concentration in the headspace of 10, irrespective of time. In addition, as the time increases, a higher malodor control efficiency is found. Example 21: Large container headspace TMA concentration (ppm) gas detection test and citrus essential oil fragrance efficacy Test the aromatic granular composite treated with citrus 15 orange essential oil at two different times, for example: 1 hour and 3 hours TMA performance. The results are shown in Table 26 and compared to those obtained from the granular composite under the same conditions. A 0.9% salt solution (6 Torr microliters) containing 1200 ppm of TMA was used as the control group malodorous solution. 57 200909484 Table 26: Large container headspace TMA concentration (ppm) Gas detection test sample time 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control malodorous solution 1 hour 7 13 20 η 33 3 hours 13 26 38 47 56 Aromatic granular Complex a) 1 hour 2 4 6 8 10 3 hours 2 4 5.5 7 8 a) The particle size range is between 150 microns and 1200 microns. The data shows that the control group malodorous solution increases the concentration of TM A 5 in the headspace, regardless of time. The control group malodorous solution was increased to a higher concentration after 3 hours. The fragrant granular composite sample reduced the concentration of TMA in the headspace, regardless of time. As time went on, the odor control efficacy of the aromatic granular composite was found to be more southerly. Example 22: Aromatic Odour Control Particles and Comparison with Cat Litter 1 The odor control efficacy of the composite sample and the aromatic complex sample was tested at a TMA concentration of 1200 ppm based on the weight of the synthetic urine solution. This odour control performance was next compared to Scoop AwayTM ("Fresh Scent, Maximum Odor Control"), which is a commercial cat litter product of the Clorox Company, and the results are shown in Table 27. 58 200909484 Table 27: granulated complex and aromatic granular composite at i2〇〇ppm _ degree of treatment time 0 15 minutes 1 hour 3 hours 5 hours 7 hours 16 hours Scoop Away3) 3 2 2 1.5 1.5 1.5 1.5 Granular complex b) 2 1.5 0.5 0.5 0.5 0.5 0 Aromatic granular composite ^ — 2 1.5 ---- 0 0 0 0 0 a) Use in the form obtained. b) The particle size range is between 150 microns and 1200 microns. The results shown in Table 27 indicate that the aromatic granular composite exhibits a synergistic effect with malodor control. The results also point to different air care applications, such as air fresheners, where it is necessary to release aroma and have a potential malodor control agent. In the case of litter, the granular composite of the present invention and the 10 aromatic granular composites all exhibited significantly better than the scoop control efficacy of Scoop Away. Example 23: Large container headspace ammonia concentration (ppm) gas detection test and baking soda performance in a composite sample with ARM & HAMMERTM baking soda, its 15 Church & Dwight Co_ commercial deodorant product interaction study The ammonia measured in the headspace of the large container is shown in Table 28. The values in Table 28 are the parts per million (ppm). A 0.9% salt solution (600 μl) containing 1200 ppm of ammonia was used as the control group malodorous solution. 59 200909484 Table 28: Ammonia concentration (ppm) in the headspace of large containers Gas test results Sample time 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control group odor solution 3 hours 5 10 12 15 20 3曰3 5 6 6 8 Baking soda a) 3 hours 5 10 15 18 21 3 a 3 5 6 7 8 Granular complex b) 3 hours 0 0 0.5 1 2 3曰0 0 0 0 0 a) Use according to the obtained form. b) The particle size fraction is between 150 microns and 1200 microns. The data in Table 28 shows that the control group malodorous solution increases the ammonia concentration in the headspace by an increased number of hits' irrespective of time. The control group malodorous solution data for more than three days seems to show a strong natural decrease in the ammonia concentration in the headspace due to the absorption of ammonia gas molecules on the walls of the large vessel. The fine baking soda powder sample did not reduce the ammonia concentration in the headspace, irrespective of time. The ammonia concentration in the headspace was found to be almost the same as the malodorous group control solution. The granular composite sample reduces the ammonia concentration in the headspace, regardless of time. Furthermore, as time goes on, it shows a higher efficiency of malodor control. Example 24: Test with Nicole Low Pressure Basket Extrusion Machine and Effect of Activated Carbon PAC200 15 Activated Carbon PAC200 in powder form at 20 wt.% (CAS#: 7440-44-0; Norit Americas Inc ., Τχ 75670, USA) as a special addition to the composite granules. The activated carbon powder is used in the form obtained. The extrusion test is shown in Table 29. 60 200909484 Table 29: Using Nicole Low Pressure Basket Extrusion Machine Complex Sample Extrusion Sample Additive Naphthene Bentonite DLP 220 SAP Fine Pergopak Μ 20% PAC200 20wt·% Activated Carbon PAC 200 45wt.% 5wt.% 25wt. % 5wt.% The activated carbon composite sample provides a normal extruded strand. The addition of citric acid and glass beads does not alter the extrusion processability. The dried composite body material was honed and sieved through a 150- and 1200-micron screen prior to use (see Table 30). Example 25: Large container headspace ammonia concentration (ppm) gas detection test and activated carbon efficiency The odor of a composite sample containing activated carbon was measured at a concentration of 1200 ppm ammonia at a time ranging from 1 hour to 5 days. Control performance. The odour control efficacy was compared with pure activated carbon powder PAC200, and the results are shown in Table 30. The data for this location presents the average of repeated trials. A 0.9% salt concentrate having a 1200 ppm ammonia concentration of 3.6 was used as the control group malodorous solution. 15 61 200909484 Table 30: Ammonia concentration (ppm) gas test result at the top of large container Sample time 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control group malodorous solution 1 hour 11 21 28 37 47 3 hours 25 46 65 >70 a) >70 a) 3曰14 28 42 54 65 5曰9 18 23 28 34 Granular complex b) 1 hour 2 4 5 6 7 3 hours 4 6 8 10 11 3曰0 0 0 0 0 5曰0 0 0 0 0 Pure activity _ PAC200cJ 1 hour 1 2 3 4 4 3 hours 2 4 6 7 8 3曰5 8 13 16 20 5曰3 4 5 6 7 20%PAC200 Granular complex b) 1 hour 2 4 5 6 7 3 hours 3 4 5 6 6 3曰0 0 1 1 2 5曰0 0 1 2 2 a) Slightly exceed the Drageger tube range from Oppm to 70ppm. b) The particle size range is between 150 microns and 1200 microns. c) Formed for use as obtained. Very fine powder, less than 45 microns (min. 50%), less than 75 5 microns (88%) and less than 150 microns (96%); iodine value (mg/g) = 900 minutes. These data indicate that the control group malodorous solution increases the ammonia concentration in the headspace with an increased number of shots, regardless of time. The ammonia gas concentration shows a high ammonia concentration after a time of 3 hours to 3 days. And the control group malodorous solution data 10 appears for an extended period of time (e.g., 5 days) to show that the ammonia concentration is substantially reduced from 62 200909484 due to the absorption of ammonia gas molecules located on the walls of the large vessel. The granular composite sample reduced the ammonia concentration in the headspace. As the time increases, a higher malodor control efficiency is found, and no ammonia is detected for, for example, 3 days and 5 曰. 5 Pure activated carbon PAC200 samples were significantly reduced in ammonia concentration in the headspace within the first few hours, such as enthalpy and 3 hours. The performance of the pure activated carbon powder sample PAC 200 appeared to be slightly better than that of the granular composite based on its higher surface area than that of the granular composite up to 3 hours ago. However, the performance of the pure activated carbon powder sample PA C 200 seems to decrease with time, and 10 becomes worse than the granular composite on or after 3 days. Interestingly, there was a strong increase in the 3 曰 hour, which was slightly less on the 5th, partly because of the natural reduction effect, but still higher than the granular composite. Even more interesting is that the odor control effect of the activated carbon-containing composite sample (based on the dry weight of the granular composite sample, 20% by weight of activated carbon) can be between the two samples at the beginning of several hours ( Pure activated carbon powder PAC200 and granular composite). The 20% PAC 200 granular composite sample did not appear to be as effective as the granular composite, but it appeared to outperform the pure activated carbon powder PAC sample on or after 3 days. Example 26: In-Line Over-Evaluation Test of Various Activated Carbon Granular Composite Samples 20 Different concentrations of active-breaking samples and Fossil samples were tested by in-line filtration tests at an ammonia concentration of 12 〇〇 Ppm (Abscents 3000, obtained from UOP Company, particle diameter approx. 3 microns; CAS#: 76774-74-8) The test activated carbon sample consists of pure activated carbon powder PAC200, Norit RBAA1 extruded pellets and Norit RO 〇8 extruded pellets . The serving size is 63 200909484 5.4 mL of a 0.9% salt solution containing 1200 ppm ammonia concentration is used as the control group malodorous solution. The test time was kept at 3 hours. The results are shown in Table 31. The weight of each material used in the in-line filtration test is also shown in Table 31. 5 Table 31: Intraline filtration test results of ammonia concentration (ppm) Sample 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control group malodorous solution 10 21 32 43 54 Citric acid granular composite a) (0.796 g) 1.5 3 4.5 6 7 Citric acid granular composite fine R (0.591 g) 0 0 0 0 0 pure activated carbon PAC200c) (0.278 g) 4 8 12 16 21 Norit RBAA1 d) (0.531 g) 5 11 18 25 32 Norit RO 0.8 e) (0_306 g) 9 19 28 38 48 Abscents 3000 ^ (0.355 g) 0 0 1 3 5 a) Particle size between 150 μm and 1200 μm. b) <150 micron c) very fine powder, less than 45 microns (min. 50%), less than 75 microns (88%) and less than 150 microns (96%); moth (mg/g) = 900 Min. 10 d) extruded pellets; apparent density = 53.53g/cm3 e) extruded pellets; apparent density = 〇.4〇g/cm3; BET = 1300m2/gf) particle diameter of about 3 microns After the ultrafine powder was filtered through the pipeline, the different activated carbon samples showed a phase 15 high ammonia concentration irrespective of the form of activated carbon. When the relative coarse particle size is also used, for example between 15 〇 and 1200 particles, the effect of pure zeolite Abscents 3000 seems to match or slightly exceed the citric acid-containing granules 64 200909484 complex. However, the performance of the fine-sized citric acid-containing granulated composite seems to be more effective, so that no ammonia is detected. Example 27. Various In-Line Filtration Tests Containing Pre-Activated Activated Carbon The odour control efficiency of the activated carbon filter for use as an air cleaner was examined by an in-line filtration test at an ammonia concentration of 1200 ppm. The test sample contained the Hamilton Beach TmeAir Air Cleaner pre-filter. The active slave pre-twist is cut into 5/8" rounds and placed in the pipeline. The serving size is 600 μl of 〇.9〇/ containing 1200 ppm ammonia concentration. The salt solution was used as a control group malodorous solution. The test time was kept at 3 hours. The results are shown in Table 32. 10 Table 32: Ammonia concentration in the headspace (ppm) Filtration in the headspace Gas detection test results Sample 100cm3 Air 200cm3 Air 300cm3 Air 400cm3 Air 500cm3 Air control group malodorous solution 6 11 15 20 24 Granular composite Finesa) ( 466.466grams) 0 0 0 0 0 Hmnilton Beach TrueAir Air Cleaner Pre-filter b) 5 10 14 19 22 a) <150 μm b) Containing activated carbon Air detergent instead of prefilter, purchased from L〇wes retail market With 5 liters of activated carbon pre-conditioner, Hamilton Beach True Air Pre-filter 'shows a relatively high ammonia concentration when used as a filter medium in in-line filtration. The effectiveness of the granular composite fine form (particle size less than 150 microns) is shown in Table 32. The fine-sized granular composite appears to be an effective filter medium, and it is understood that the invention is not limited to the embodiments specifically exemplified herein. This variation of the invention is highly apparent to those skilled in the art. Such changes and improvements do not fall short of the scope of the patent application attached. In addition, each of the recited ranges includes combinations of ranges and subgroups, as well as specific numbers included therein. In addition, each of the patents, patent applications, and patent publications, which are incorporated herein by reference in its entirety herein in its entirety herein in its entirety herein in [Simple description of the figure 3 Figure 1 is a graph showing the effect of different degrees of redispersible latex powder (Dow of Dow powder, DLP) and the amount of synthetic urine on the weight of the clot. [Main component symbol description] (none) 66

Claims (1)

200909484 X. Patent application scope: 1. A granular composite comprising a) - inorganic particles, b) - redispersible latex powder, and c) one or more superabsorbent polymers, a porosity improver , a water soluble polymer, and an odor control agent, or a 5-oil absorbent. 2. The composite of claim 1, wherein the inorganic particles are clay. 3. The composite of any one of claims 1 to 2 wherein the inorganic particles are nano-bentonite clay. The composite of any one of claims 1 to 3, wherein the composite comprises at least 1 wt.% of inorganic particles. 5. The composite of any one of claims 1 to 4, wherein the composite comprises at least 0.1% by weight of a redispersible latex powder. 6. The composite of any one of claims 1 to 5, wherein the complex comprises at least 0.1 wt.% of a superabsorbent polymer. 7. A granular composite comprising a) a clay, and b) a redispersible latex powder, wherein the composite comprises a plurality of weights based on a combined weight of the clay and the redispersible latex powder At 15wt.% clay. 8. The composite according to any one of claims 1 to 7, further comprising 20 an alcohol, a fragrance, a surfactant, a colorant, a dye, a moisture reaction indicator, a pH indicator, or Its mixture. 9. The composite of claim 1, comprising an odor controlling agent, wherein the odor controlling agent is activated carbon; a cyclodextrin; a porous polymer adsorbent; an ion exchange polymer; sodium bicarbonate; borax; Peroxide, 67 200909484 5 10 15 20 Peroxycarbonate, peroxide, peroxodisulfate and permanganate such as sodium, bell or sulphur; biocide; plant extracts such as: green tea Extraction of leaves, olive leaves, yucca, aloe and stone alkali and/or dry powder; citric acid; chelating agent; natural and synthetic zeolite; perfume; various metals and metal compounds; metal and ionic silver in various forms; Amino sugar, or a mixture thereof. 10. A granular composite comprising: a) from 1 to 99 wt.% of clay; b) from 0.1 to 25.0 wt.% of redispersible latex powder; c) from 0.1 to 99 wt% of superabsorbent polymer (SAP); d) 0.1-25 wt.% water-soluble polymer; e) 0_01-25 wt_% porosity enhancer; f) 0.01-25 wt.% odor control agent; and g) 0.01-25 wt.% water. A method of producing a composite according to any one of claims 1 to 10, which comprises drying a blended clay, a redispersible latex powder, and other components of the composite to form a mixture; Water or an aqueous solution wets the mixture; extruding the wetting mixture to form a granular composite; drying the extruded material; measuring dimensions and screening to form a composite; rewetting the composite; and dusting the composite gas . 68 200909484 12. An article comprising a granular composite according to any one of claims 1 to 10. 69