Source: https://patents.google.com/patent/US8173209
Timestamp: 2018-03-17 16:41:28
Document Index: 471366692

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'art 1', 'Application No. 200780041720', 'Application No. 200780041720', 'Application No. 200780041720', 'Application No. 200780041720', 'Application No. 07838034', 'Application No. 2009', 'Application No. 10', 'Application No. 10', 'application No. 2009113623', 'Application No. 200780041720', 'Application No. 200780041720', 'Application No. 2009', 'Application No. 10', 'Application No. 2009113623']

US8173209B2 - Polyolefin dispersion technology used for resin coated sand - Google Patents
US8173209B2
US8173209B2 US11900401 US90040107A US8173209B2 US 8173209 B2 US8173209 B2 US 8173209B2 US 11900401 US11900401 US 11900401 US 90040107 A US90040107 A US 90040107A US 8173209 B2 US8173209 B2 US 8173209B2
US11900401
US20080182040A1 (en )
Loic F. Chereau
Julien H. J. M. Damen
A polymer-coated particulate material having: a particulate substrate; and an applied compound, wherein the applied compound coats at least 50% of the surface of the particulate substrate, and wherein, at the time of application, the applied compound includes a dispersion including: a thermoplastic polymer; and a stabilizing compound. In another aspect, embodiments disclosed herein relate to a method of forming a polymer-coated particulate material, the method including the steps of: incorporating a particulate substrate and a dispersion, the dispersion comprising: a thermoplastic polymer; a stabilizing compound; and a dispersion medium selected from the group consisting of an organic solvent, water, and combinations thereof; removing at least a portion of the dispersion medium.
This application claims priority to U.S. Provisional Patent Application No. 60/843,682, filed Sep. 11, 2006, the disclosure of which is incorporated herein by reference.
As one example of materials used as infill, U.S. Patent Application Publication No. 20060100342 describes infill formed by coating silica sand with either elastomeric materials or thermoplastic polymers. The infill granules are formed by first heating a portion of the silica to a temperature between 200° C. and 300° C., placing the sand in a mixer, and adding elastomer or thermoplastic polymer pellets while mixing. The thermoplastic polymer then melts, coating the sand. The contents of the mixture are then cooled using a water spray and air flowing through the mixer. The exact amount and timing of the water spray is critical to result in a free-flowing material without significant formation of agglomerates.
In one aspect, embodiments disclosed herein relate to a polymer-coated particulate material having: a particulate substrate; and an applied compound, wherein the applied compound coats at least 50% of the surface of the particulate substrate, and wherein, at the time of application, the applied compound includes a dispersion including: a thermoplastic polymer; and a stabilizing compound.
In one aspect, embodiments described herein relate to polymer coated particulate materials. In another aspect, embodiments described herein relate to a process to produce polymer coated particulate materials. In more specific aspects, embodiments described herein relate to particulate materials such as polymer coated sands. The sands or other particulate materials may be coated or incorporated with a polymer or polymeric mixture, where the polymer or mixture of polymers may be supplied as an aqueous dispersion.
In another embodiment, the thermoplastic resin may include an ethylene-carboxylic acid copolymer, such as, ethylene-vinyl acetate (EVA) copolymers, ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers such as, for example, those available under the tradenames PRIMACOR™ from the Dow Chemical Company, NUCREL™ from DuPont, and ESCOR™ from ExxonMobil, and described in U.S. Pat. Nos. 4,599,392, 4,988,781, and 5,384,373, each of which is incorporated herein by reference in its entirety. Exemplary polymers include polypropylene, (both impact modifying polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene/propylene copolymers), various types of polyethylene, including high pressure, free-radical LDPE, Ziegler Natta LLDPE, metallocene PE, including multiple reactor PE (“in reactor”) blends of Ziegler-Natta PE and metallocene PE, such as products disclosed in U.S. Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341. Homogeneous polymers such as olefin plastomers and elastomers, ethylene and propylene-based copolymers (for example polymers available under the trade designation VERSIFY™ available from The Dow Chemical Company and VISTAMAXX™ available from ExxonMobil) may also be useful in some embodiments. Of course, blends of polymers may be used as well. In some embodiments, the blends include two different Ziegler-Natta polymers. In other embodiments, the blends may include blends of a Ziegler-Natta and a metallocene polymer. In still other embodiments, the thermoplastic resin used herein may be a blend of two different metallocene polymers.
Embodiments disclosed herein may also include a polymeric component that may include at least one multi-block olefin interpolymer. Suitable multi-block olefin interpolymers may include those described in U.S. Provisional Patent Application No. 60/818,911, for example. The term “multi-block copolymer” or refers to a polymer comprising two or more chemically distinct regions or segments (referred to as “blocks”) preferably joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In certain embodiments, the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property. The multi-block copolymers are characterized by unique distributions of polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers. More specifically, when produced in a continuous process, embodiments of the polymers may possess a PDI ranging from about 1.7 to about 8; from about 1.7 to about 3.5 in other embodiments; from about 1.7 to about 2.5 in other embodiments; and from about 1.8 to about 2.5 or from about 1.8 to about 2.1 in yet other embodiments. When produced in a batch or semi-batch process, embodiments of the polymers may possess a PDI ranging from about 1.0 to about 2.9; from about 1.3 to about 2.5 in other embodiments; from about 1.4 to about 2.0 in other embodiments; and from about 1.4 to about 1.8 in yet other embodiments.
The multi-block interpolymers may be characterized by an average block index, ABI, ranging from greater than zero to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3. The average block index, ABI, is the weight average of the block index (“BI”) for each of the polymer fractions obtained in preparative TREF from 20° C. and 110° C., with an increment of 5° C.:
B ⁢ ⁢ I = 1 / T X - 1 / T XO 1 / T A - 1 / T AB ⁢ ⁢ or ⁢ ⁢ B ⁢ ⁢ I = - LnP X - LnP XO LnP A - LnP AB
In some embodiments, the polymers described herein may have a storage modulus ratio, G′(25° C.)/G′(100° C.), from 1 to 50; from 1 to 20 in other embodiments; and from 1 to 10 in yet other embodiments. In some embodiments, the polymers may have a 70° C. compression set of less than 80 percent; less than 70 percent in other embodiments; less than 60 percent in other embodiments; and, less than 50 percent, less than 40 percent, down to a compression set of 0 percent in yet other embodiments.
In some embodiments, block polymers made with two catalysts incorporating differing quantities of comonomer may have a weight ratio of blocks formed thereby ranging from 95:5 to 5:95. The elastomeric interpolymers, in some embodiments, have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefin content of from 10 to 80 percent, based on the total weight of the polymer. In other embodiments, the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefin content of from 10 to 40 percent, based on the total weight of the polymer. In other embodiments, the interpolymer may have a Mooney viscosity (ML (1+4) 125° C.) ranging from 1 to 250. In other embodiments, such polymers may have an ethylene content from 65 to 75 percent, a diene content from 0 to 6 percent, and an α-olefin content from 20 to 35 percent.
In certain embodiments, the polymer may be a propylene-ethylene copolymer or interpolymer having an ethylene content between 5 and 20% by weight and a melt flow rate (230° C. with 2.16 kg weight) from 0.5 to 300 g/10 min. In other embodiments, the propylene-ethylene copolymer or interpolymer may have an ethylene content between 9 and 12% by weight and a melt flow rate (230° C. with 2.16 kg weight) from 1 to 100 g/10 min.
In some particular embodiments, the polymer is a propylene-based copolymer or interpolymer. In certain embodiments, the propylene-based copolymer may be a propylene-α olefin copolymer. In some embodiments, a propylene/ethylene copolymer or interpolymer is characterized as having substantially isotactic propylene sequences. The term “substantially isotactic propylene sequences” and similar terms mean that the sequences have an isotactic triad (mm) measured by 13C NMR of greater than about 0.85, preferably greater than about 0.90, more preferably greater than about 0.92 and most preferably greater than about 0.93. Isotactic triads are well-known in the art and are described in, for example, U.S. Pat. No. 5,504,172 and WO 00/01745, which refer to the isotactic sequence in terms of a triad unit in the copolymer molecular chain as determined by 13C NMR spectra. In other particular embodiments, the ethylene-α olefin copolymer may be ethylene-butene, ethylene-hexene, or ethylene-octene copolymers or interpolymers. In other particular embodiments, the propylene-α olefin copolymer may be a propylene-ethylene or a propylene-ethylene-butene copolymer or interpolymer.
The resin may also have a relatively low melting point in some embodiments. For instance, the melting point of the polymers described herein may be less than about 160° C., such as less than 130° C., such as less than 120° C. For instance, in one embodiment, the melting point may be less than about 100° C.; in another embodiment, the melting point may be less than about 90° C.; less than 80° C. in other embodiments; and less than 70° C. in yet other embodiments. The glass transition temperature of the polymer resin may also be relatively low. For instance, the glass transition temperature may be less than about 50° C., such as less than about 40° C.
Embodiments disclosed herein may use one or more stabilizing agents to promote the formation of a stable dispersion or emulsion. In some embodiments, the stabilizing agent may be a surfactant, dispersing agent, emulsifier, or a polymer (different from the base polymer detailed above), or mixtures thereof. In certain embodiments, the polymer may be a polar polymer, having a polar group as either a comonomer or grafted monomer. In preferred embodiments, the stabilizing agent comprises one or more polar polyolefins, having a polar group as either a comonomer or grafted monomer. Typical polymers include ethylene-acrylic acid (EAA) and ethylene-methacrylic acid copolymers, such as those available under the trademarks PRIMACOR™ (trademark of The Dow Chemical Company), NUCREL™ (trademark of E.I. DuPont de Nemours), and ESCOR™ (trademark of ExxonMobil) and described in U.S. Pat. Nos. 4,599,392, 4,988,781, and 5,938,437, each of which is incorporated herein by reference in its entirety. Other polymers include ethylene ethyl acrylate (EEA) copolymer, ethylene methyl methacrylate (EMMA), and ethylene butyl acrylate (EBA). Other ethylene-carboxylic acid copolymer may also be used. Those having ordinary skill in the art will recognize that a number of other useful polymers may also be used.
Suitable conventional block copolymers which may be blended with the polymers disclosed herein may possess a Mooney viscosity (ML 1+4 @ 100° C.) in the range from 10 to 135 in some embodiments; from 25 to 100 in other embodiments; and from 30 to 80 in yet other embodiments. Suitable polyolefins especially include linear or low density polyethylene, polypropylene (including atactic, isotactic, syndiotactic and impact modified versions thereof) and poly(4-methyl-1-pentene). Suitable styrenic polymers include polystyrene, rubber modified polystyrene (HIPS), styrene/acrylonitrile copolymers (SAN), rubber modified SAN (ABS or AES) and styrene maleic anhydride copolymers.
Compositions, including thermoplastic blends according to embodiments of the invention may also contain anti-ozonants or anti-oxidants that are known to a rubber chemist of ordinary skill. The anti-ozonants may be physical protectants such as waxy materials that come to the surface and protect the part from oxygen or ozone or they may be chemical protectors that react with oxygen or ozone. Suitable chemical protectors include styrenated phenols, butylated octylated phenol, butylated di(dimethylbenzyl) phenol, p-phenylenediamines, butylated reaction products of p-cresol and dicyclopentadiene (DCPD), polyphenolic anitioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants, thioester antioxidants, and blends thereof. Some representative trade names of such products are WINGSTAY™ S antioxidant, POLYSTAY™ 100 antioxidant, POLYSTAY™ 100 AZ antioxidant, POLYSTAY™ 200 antioxidant, WINGSTAY™ L antioxidant, WINGSTAY™ LHLS antioxidant, WINGSTAY™ K antioxidant, WINGSTAY™ 29 antioxidant, WINGSTAY™ SN-1 antioxidant, and IRGANOX™ antioxidants. In some applications, the anti-oxidants and anti-ozonants used will preferably be non-staining and non-migratory.
For providing additional stability against UV radiation, hindered amine light stabilizers (HALS) and UV absorbers may be also used. Suitable examples include TINUVIN™ 123, TINUVIN™ 144, TINUVIN™ 622, TINUVIN™ 765, TINUVIN™ 770, and TINUVIN™ 780, available from Ciba Specialty Chemicals, and CHEMISORB™ T944, available from Cytex Plastics, Houston Tex., USA. A Lewis acid may be additionally included with a HALS compound in order to achieve superior surface quality, as disclosed in U.S. Pat. No. 6,051,681. Other embodiments may include a heat stabilizer, such as IRGANOX™ PS 802 FL, for example.
When sulfur based curing agents are employed, accelerators and cure activators may be used as well. Accelerators are used to control the time and/or temperature required for dynamic vulcanization and to improve the properties of the resulting cross-linked article. In one embodiment, a single accelerator or primary accelerator is used. The primary accelerator(s) may be used in total amounts ranging from about 0.5 to about 4, preferably about 0.8 to about 1.5 phr, based on total composition weight. In another embodiment, combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in smaller amounts, such as from about 0.05 to about 3 phr, in order to activate and to improve the properties of the cured article. Combinations of accelerators generally produce articles having properties that are somewhat better than those produced by use of a single accelerator. In addition, delayed action accelerators may be used which are not affected by normal processing temperatures yet produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders might also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound. Certain processing aids and cure activators such as stearic acid and ZnO may also be used. When peroxide based curing agents are used, co-activators or coagents may be used in combination therewith. Suitable coagents include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), among others. Use of peroxide crosslinkers and optional coagents used for partial or complete dynamic vulcanization are known in the art and disclosed for example in the publication, “Peroxide Vulcanization of Elastomer”, Vol. 74, No 3, July-August 2001.
Dispersions, both aqueous and non-aqueous, may be formed using the polymers described above or formulations comprising the same. Aqueous dispersions, for example, may be formed using a base polymer, as described above, a stabilizing agent, and water. Non-aqueous dispersions, for example, may be formed using a base polymer, a stabilizing agent, and an organic solvent, where the organic solvent may include low-boiling point (<100° C.) organic compounds, such as toluene, methylene chloride, and other common organic solvents known to those skilled in the art.
Dispersions formed in accordance with embodiments of the present invention are characterized in having an average particle size of between about 0.1 to about 5.0 microns. In other embodiments, dispersions have an average particle size of from about 0.5 μm to about 2.7 μm. In other embodiments, from about 0.8 μm to about 1.2 μm. By “average particle size”, the present invention means the volume-mean particle size. In order to measure the particle size, laser-diffraction techniques may be employed for example. A particle size in this description refers to the diameter of the polymer in the dispersion. For polymer particles that are not spherical, the diameter of the particle is the average of the long and short axes of the particle. Particle sizes may be measured on a Beckman-Coulter LS230 laser-diffraction particle size analyzer or other suitable device. The particle size distribution of the polymer particles in the dispersion may be less than or equal to about 2.0, such as less than 1.9, 1.7 or 1.5.
Furthermore, embodiments of the present invention may optionally include a thickener. Thickeners may be useful in the present invention to increase the viscosity of low viscosity dispersions. Thickeners suitable for use in the practice of the present invention may be any known in the art such as for instance polyacrylate type or associated non ionic thickeners such as modified cellulose ethers. For example, suitable thickeners include ALCOGUM™ VEP-II (trademark of Alco Chemical Corporation), RHEOVIS™ and VISCALEX™ (trademarks of Ciba Ceigy), UCAR™ Thickener 146, or ETHOCEL™ or METHOCEL™ (trademarks of the The Dow Chemical Company) and PARAGUM™ 241 (trademarks of Para-Chem Southern, Inc.), or BERMACOL™ (trademark of Akzo Nobel) or AQUALON™ (trademark of Hercules) or ACUSOL® (trademark of Rohm and Haas). Thickeners may be used in any amount necessary to prepare a dispersion of desired viscosity.
While any method may be used to produce the aqueous dispersion, in one embodiment, the dispersion may be formed through a melt-kneading process. For example, the kneader may comprise a BANBURY® mixer, single-screw extruder or a multi-screw extruder. The melt-kneading may be conducted under the conditions which are typically used for melt-kneading the one or more thermoplastic resins.
The temperature of the pre-heated particles may be sufficient to evaporate at least a portion of the water in the aqueous dispersion. The particulate material may be pre-heated to a temperature between about 110° C. and 350° C., in some embodiments, where the temperature may be based upon the amount of water to be evaporated. Water vapor produced during the addition of the dispersion to the particles may be removed from the mixer. In other embodiments, the sand or other particulate materials may be pre-heated to a temperature between about 60° C. and 300° C.; between 140° C. and 250° C. in other embodiments; and between about 160° C. and 230° C. in yet other embodiments. In other embodiments, a mixture of the particulate substrate and the dispersion may be heated to the above described temperatures to volatilize the solvent and/or water.
The coated particles may then be cooled to a temperature of less than 100° C., after which the coated particles may be collected for use as infill or in other suitable applications. Although use of a dispersion to coat the particles may result in a free-flowing material, any agglomerates that may have formed may be segregated from the free-flowing material by sieving the particles, and the agglomerates may be discarded or may be de-agglomerated for use as infill.
In some embodiments, the above described coated particles may be used as infill in a synthetic turf. Deformation of a synthetic turf system after long-time use may depend on the pile height, tufting density, and yarn strength. The type and volume of infill material also influence the final deformation resistance of the turf significantly. The Lisport test may be used to analyze wear performance, and is helpful to design an effective turf system. Additionally, tests may be performed to analyze temperature performance and aging, as well as the bounce and spin properties of the resulting turf. With regard to each of these properties, turf containing the infill materials as described above may meet FIFA specifications for use of the turf in football fields (see, for example, the “March 2006 FIFA Quality Concept Requirements for Artificial Turf Surfaces,” the FIFA handbook of test methods and requirements for artificial football turf, which is fully incorporated herein by reference).
Embodiments of the polymer coated substrates described herein may have a color change according to test method EN ISO 20105-A02 of greater than or equal to grey scale 3. Other embodiments of the polymer coated substrates may meet the FIFA requirements for particle size, particle shape, and bulk density, as tested using test methods EN 933—Part 1, prEN 14955, and EN 13041, respectively. The polymer coated substrates may also comply with the DIN V 18035-7-2002-06 requirements for environmental compatibility.
Dispersion 1: An aqueous dispersion of a propylene-ethylene copolymer was formed in accordance with the procedures as described in WO2005021638. Dispersion 1 was formed using a propylene-ethylene copolymer (approximately 9 weight percent ethylene, MI2 of 25 dg/min, and a density of 0.876 g/cc). The surfactant system used was PRIMACOR™ 59801 (an ethylene acrylic acid copolymer available from The Dow Chemical Company). PRIMACOR™ was used at a loading of 17 weight percent based on the weight of the propylene-ethylene copolymer.
The propylene-ethylene copolymer was dry blended with the surfactant. The mixture was then extruded at 4.5 kg/h (10 lbs/h) using a Berstorff ZE25 (36 L/D, 450 rpm) and a Schenck Mechatron loss-in-weight feeder. An ISCO dual-syringe pump metered a 45% (w/w) potassium hydroxide solution at 0.9 cc/min and DI water at 1.2 cc/min. The potassium hydroxide solution and DI water were mixed and pre-heated through a 24 inch core/shell heat exchanger (20 foot ⅛ inch tubing core) tempered by a DC200 silicone oil bath set at 150° C. and fed to the initial aqueous (IA) injector. Dilution water was delivered to the dilution water injector at a rate of 100 cc/min using an ISCO dual syringe pump. The dilution water was also passed through a similar pre-heater set at 150° C. Back pressure on the barrel was provided via a GO (Circor) BP-60 back-pressure regulator adjusted to maintain about 17.2 barg (250 psig) upstream pressure.
Dispersion 2: Dispersion 2 was also formed in accordance with the procedures as described in WO2005021638 using an ethylene-octene copolymer (ENGAGE™ 8200, available from The Dow Chemical Company, having a MI2 of 5.0 dg/min and a density of 0.870 g/cc). The surfactant system used was PRIMACOR™ 5980I (as described above). PRIMACOR™ was used at a loading of 15 weight percent based on the weight of the ethylene-octene interpolymer.
The ethylene-octene copolymer was dry blended with the surfactant. The mixture was then extruded at 4.5 kg/h (10 lbs/h) using a Berstorff ZE25 (36 L/D, 450 rpm) and a Schenck Mechatron loss-in-weight feeder. An ISCO dual-syringe pump metered a 45% (w/w) potassium hydroxide solution at 0.9 cc/min and DI water at 1.2 cc/min. The potassium hydroxide solution and DI water were mixed and pre-heated through a 24 inch core/shell heat exchanger (20 foot ⅛ inch tubing core) tempered by a DC200 silicone oil bath set at 150° C. and fed to the initial aqueous (IA) injector. Dilution water was delivered to the dilution water injector at a rate of 100 cc/min using an ISCO dual syringe pump. The dilution water was also passed through a similar pre-heater set at 150° C. Back pressure on the barrel was provided via a GO (Circor) BP-60 back-pressure regulator adjusted to maintain about 17.2 barg (250 psig) upstream pressure.
The above described dispersions were used to form polymer coated sands. A silica based sand was heated to a temperature of 220° C. in a pre-heating unit. The pre-heated sand and an aqueous dispersion were then incorporated in a tumble mixer. Water vapor generated as a result of contacting the dispersion with the pre-heated sand was removed from the tumbler during mixing. The mixture formed was then cooled to a temperature of approximately 60° C. by directing air at ambient temperature through the mixer. The cooled mixture was then passed over a shaking sieve having 2 mm openings to separate free flowing particles from any agglomerates that may have formed during the process.
1. A method of forming a polymer-coated particulate material, the method comprising:
preparing a dispersion, the dispersion comprising:
preheating a particulate substrate material to from 60° C. to 350° C.,
mixing the preheated particulate material and the dispersion with agitation,
allowing at least a portion of the dispersion medium to evaporate,
removing at least a portion of the evaporated dispersion medium,
and cooling the polymer-coated particulate material.
2. The method of claim 1, further comprising preheating the particulate substrate to a temperature greater than 100° C.
3. The method of claim 1, further comprising heating the mixture of the particulate substrate material and the dispersion to a temperature greater than 100° C.
4. The method of claim 1, wherein the thermoplastic polymer is selected from the group consisting of: propylene-based homopolymers, copolymers, interpolymers, and multi-block interpolymers; ethylene-based homopolymers, copolymers, interpolymers, and multi-block interpolymers; and combinations thereof.
5. The method of claim 1, wherein the thermoplastic polymer is selected from the group consisting of propylene-based multi-block interpolymers, ethylene-based multi-block interpolymers and combinations thereof.
6. The method of claim 1, wherein the particulate substrate is selected from the group consisting of mineral grains, sands, and rubber particles.
7. The method of claim 1, wherein the particulate substrate is a silica-based sand.
8. The method of claim 1, further comprising frothing the aqueous dispersion.
9. The method of claim 1, further comprising combining an adhesion promoter with the particulate substrate.
10. The method of claim 1, further comprising cross-linking at least a portion of the thermoplastic polymer.
11. The method of claim 1, wherein the applied compound further comprises one or more ultraviolet inhibitors.
12. The method of claim 1, wherein the applied compound further comprises an algae inhibitor, an antimicrobiological agent, a biocide, a fungicide, or combinations thereof.
US11900401 2006-09-11 2007-09-11 Polyolefin dispersion technology used for resin coated sand Active 2030-07-19 US8173209B2 (en)
US84368206 true 2006-09-11 2006-09-11
US11900401 US8173209B2 (en) 2006-09-11 2007-09-11 Polyolefin dispersion technology used for resin coated sand
US13432665 US8568879B2 (en) 2006-09-11 2012-03-28 Polyolefin dispersion technology used for resin coated sand
US13432665 Division US8568879B2 (en) 2006-09-11 2012-03-28 Polyolefin dispersion technology used for resin coated sand
US20080182040A1 true US20080182040A1 (en) 2008-07-31
US8173209B2 true US8173209B2 (en) 2012-05-08
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US11900401 Active 2030-07-19 US8173209B2 (en) 2006-09-11 2007-09-11 Polyolefin dispersion technology used for resin coated sand
US13432665 Active 2027-09-22 US8568879B2 (en) 2006-09-11 2012-03-28 Polyolefin dispersion technology used for resin coated sand
US (2) US8173209B2 (en)
JP (2) JP5535630B2 (en)
KR (1) KR101110923B1 (en)
CN (2) CN105131311A (en)
EP (1) EP2066744A2 (en)
RU (1) RU2418012C2 (en)
WO (1) WO2008033343A3 (en)
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