Molded artificial polymeric articles

Abstract

1. Use of porous metal oxide microspheres as a light stabilizer for molded artificial polymer articles, wherein the porous metal oxide microspheres are prepared by a process comprising the steps of forming a liquid dispersion of polymer nanoparticles and a metal oxide, forming droplets of the dispersion, drying the droplets to obtain polymer template microspheres comprising the polymer nanospheres, and removing the polymer nanospheres from the template microspheres to obtain the porous metal oxide microspheres.

Description

[Technical field]

[0001] The present invention relates to the use of certain porous metal oxide spheres (e.g., microspheres) as light stabilizers for molded man-made polymer articles, and corresponding molded man-made polymer articles and corresponding extruded, cast, spun, molded or calendered polymer compositions. [Background technology]

[0002] It has now been found that certain porous metal oxide spheres are particularly effective in stabilizing polymers against degradation, particularly UV light induced degradation, and in addition, they have been found to exhibit a synergistic effect on such stabilization in combination with other UV absorbers. Summary of the Invention [Means for solving the problem]

[0003] The present invention relates in particular to the use of porous metal oxide spheres as light stabilizers for molded artificial polymeric articles, comprising: the polymer is a synthetic polymer and / or a natural or synthetic elastomer; The porous metal oxide spheres include a metal oxide and are, for example forming a liquid dispersion of polymer particles (e.g., nanoparticles) and a metal oxide; forming droplets of the dispersion; drying the droplets to obtain polymer spheres (e.g. nanospheres) and polymer template spheres (e.g. microspheres) comprising the metal oxide; and Removing the polymer spheres from the template spheres to obtain porous metal oxide spheres. and preparing the product by a process comprising: A sphere, for example Average diameter between 0.5 μm and 100 μm, an average porosity of 0.10 to 0.80; and The use relates to a porous membrane having an average pore size of 50 nm to 999 nm.

[0004] The disclosure described herein is illustrated, by way of example and not limitation, in the accompanying drawings. For simplicity and clarity of illustration, features shown in the drawings have not necessarily been drawn to scale. For example, dimensions of some features may be exaggerated relative to other features for clarity. Furthermore, where considered appropriate, reference numerals may be repeated among the drawings to indicate corresponding or similar elements. [Brief description of the drawings]

[0005] [Figure 1] FIG. 1 shows a general overview of the preparation of porous microspheres according to one embodiment of the present invention. [Diagram 2] 1 is a scanning electron microscope (SEM) image of a polymer templated microsphere according to one embodiment of the present invention. [Diagram 3] 1 is a SEM image of porous silica microspheres according to one embodiment of the present invention. [Figure 4] FIG. 1 illustrates a spray drying process according to some embodiments of the present invention. [Diagram 5] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 6] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 7] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 8] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 9] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 10] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 11] FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. [Figure 12]FIG. 1 shows transmission curves as a result of UV measurements for the specified applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] The porous metal oxide spheres or photonic balls can be prepared using a polymer sacrificial template. In one embodiment, an aqueous colloidal dispersion containing polymer particles and a metal oxide is prepared, where the polymer particles are typically nanoscale. The aqueous colloidal dispersion can be mixed with a continuous oil phase, for example in a microfluidic device, to produce a water-in-oil emulsion. The emulsion droplets are prepared, collected and dried to form spheres (typically microscale) containing the polymer particles and the metal oxide. The polymer particles (spheres) are then removed, for example by calcination, to obtain spherical metal oxide particles (spheres) containing high porosity and typically nanoscale pores. The spheres can contain uniform pore sizes, which is a result of the polymer particles being spherical and monodisperse.

[0007] Figure 1 shows a general overview of the preparation of the present porous microspheres. The emulsion droplets containing the polymer nanospheres and metal oxide are dried to remove the solvent to provide structured microspheres containing the polymer nanospheres with the metal oxide in the interstitial spaces between the polymer nanospheres (template microspheres or "direct structure"). The polymer nanospheres define the interstitial spaces. Calcination results in the removal of the polymer and provides the present metal oxide microspheres with high porosity or void volume (inverse structure).

[0008] The porous metal oxide spheres are advantageously sintered to produce a continuous solid structure that is thermally and mechanically stable.

[0009] In some embodiments, droplet formation and collection occurs in a microfluidic device. A microfluidic device is a narrow channel device with a droplet junction on the micron scale suitable for generating droplets of uniform size, for example connected to a collection reservoir. The microfluidic device contains a droplet junction with a channel width of, for example, about 10 μm to about 100 μm. The device is made of, for example, polydimethylsiloxane (PDMS) and can be prepared, for example, by soft lithography. An emulsion can be prepared in the device by pumping an aqueous dispersed phase and an oil continuous phase at a specific speed into the device, where mixing occurs, to obtain emulsion droplets. Alternatively, an oil-in-water emulsion can be utilized.

[0010] In some embodiments, vibrating nozzle techniques can be used. In these techniques, a liquid dispersion is prepared, droplets are formed and dropped into a bath of a continuous phase. The droplets are then dried, followed by removal of the polymer. Vibrating nozzle instruments are available from Buchi, and include, for example, a syringe pump and a pulsation unit. The vibrating nozzle instrument can also include a pressure control valve.

[0011] The polymer particles have, for example, an average diameter of about 50 nm to about 999 nm and are monodisperse.

[0012] Suitable template polymers for the spheres include thermoplastic polymers, for example, the template polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polyester, polyurethane, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, polyvinyl ether, derivatives thereof, salts thereof, copolymers thereof, and combinations thereof. For example, the polymer is selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, poly(n-butyl methacrylate), polystyrene, poly(chloro-styrene), poly(alpha-methylstyrene), poly(N-methylolacrylamide), styrene / methyl methacrylate copolymer, polyalkylated acrylates, polyhydroxyl acrylates, polyaminoacrylates, polycyanoacrylates, polyfluorinated acrylates, poly(N-methylolacrylamide), polyacrylic acid, polymethacrylic acid, methyl methacrylate / ethyl acrylate / acrylic acid copolymer, styrene / methyl methacrylate / acrylic acid copolymer, polyvinyl acetate, polyvinylpyrrolidone, polyvinylcaprolactone, polyvinylcaprolactam, derivatives thereof, salts thereof, and combinations thereof.

[0013] In certain embodiments, the polymeric template includes polystyrenes, including polystyrene and polystyrene copolymers, including copolymers with water-soluble monomers, such as polystyrene / acrylic acid, polystyrene / poly(ethylene glycol) methacrylate, and polystyrene / styrene sulfonate.

[0014] The metal oxides include transition metal, semi-metal and rare earth oxides, such as silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, mixed metal oxides, combinations thereof, etc. Metal oxides selected from the group consisting of silica, titania, alumina and combinations thereof are preferred.

[0015] The wt / wt (weight / weight) ratio of polymer particles to metal oxide is, for example, from 0.1 / 1 to 10.0 / 1 or from 0.5 / 1 to 10.0 / 1.

[0016] The continuous oil phase may include, for example, organic solvents, silicone oils or fluorine oils. According to the present invention, "oil" means an organic phase that is immiscible with water. Organic solvents include hydrocarbons such as heptane, hexane, toluene, xylene, etc., and alkanols such as methanol, ethanol, propanol, etc.

[0017] The emulsion droplets are collected and dried to remove the polymer, for example by microwave irradiation, in a heated oven, under vacuum, in the presence of a desiccant, or a combination thereof.

[0018] Polymer removal can be accomplished, for example, by calcination, pyrolysis, or with a solvent (solvent stripping). Calcination, in some embodiments, is carried out at a temperature of at least about 200° C., at least about 500° C., at least about 1000° C., from about 200° C. to about 1200° C., or from about 200° C. to about 700° C. Calcination can be for a suitable period of time, such as from about 0.1 hours to about 12 hours, or from about 1 hour to about 8.0 hours. In other embodiments, calcination can be for at least about 0.1 hours, at least about 1 hour, at least about 5 hours, or at least about 10 hours.

[0019] Alternatively, a liquid dispersion containing polymeric nanoparticles and a metal oxide is formed with an oil dispersed phase and a continuous water phase to form an oil-in-water emulsion. The oil droplets can be collected and dried in the same way as water droplets.

[0020] Alternatively, a liquid dispersion of polymer particles (e.g., nanoparticles) and metal oxide is prepared and spray-dried to form polymer template spheres (e.g., spherules) without forming a liquid-in-liquid emulsion. In certain embodiments of the spray-drying technique, a liquid solution or dispersion is fed (e.g., pumped) into an atomizing nozzle with a compressed gas inlet. The feed is pumped through the atomizing nozzle to form droplets. The droplets are surrounded by preheated gas in an evaporation chamber, resulting in evaporation of the solvent to produce solid particles. The dried particles are carried by the drying gas through a cyclone and deposited in a collection chamber. The gas includes nitrogen and / or air. In one embodiment of the present spray-drying method, the liquid feed contains a water or oil phase, polymer particles, and a metal oxide. In one embodiment of the present spray-drying method, the liquid feed contains a water or oil phase, polymer particles, and optionally a metal oxide. Polymer template spheres are provided that contain polymer spheres with a metal oxide in the intermediate space between the polymer spheres. The polymer spheres define the intermediate space. Spray-drying techniques include inkjet spray-drying methods and devices.

[0021] In this spray drying technique, air can be considered as the continuous phase (liquid-in-gas emulsion) with a dispersed liquid phase. In certain embodiments, the spray drying comprises an inlet temperature of about 100°C, about 105°C, about 110°C, about 115°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, or about 170°C to about 180°C, about 190°C, about 200°C, about 210°C, about 215°C, or about 220°C. In some embodiments, pumping rates (feed flow rates) of about 1 mL / min, about 2 mL / min, about 5 mL / min, about 6 mL / min, about 8 mL / min, about 10 mL / min, about 12 mL / min, about 14 mL / min, or about 16 mL / min to about 18 mL / min, about 20 mL / min, about 22 mL / min, about 24 mL / min, about 26 mL / min, about 28 mL / min, or about 30 mL / min are utilized. Spray drying techniques are disclosed, for example, in US2016 / 0170091.

[0022] FIG. 4 is a representation of a spray drying process according to some embodiments of the present invention.

[0023] The spheres are spherical or sphere-like, and in certain embodiments are micron-scale, e.g., having an average diameter of about 0.5 microns (μm) to about 100 μm. The polymer particles utilized as templates are also spherical, and in certain embodiments are nano-scale and monodisperse, e.g., having an average diameter of about 50 nm to about 999 nm. The metal oxide utilized may also be in particulate form, and the particles may be nano-scale.

[0024] The metal oxide of the dispersion may be provided as the metal oxide or may be provided from a metal oxide precursor, for example by sol-gel techniques.

[0025] Drying of the polymer / metal oxide droplets, followed by removal of the polymer, provides spheres with uniform voids (pores). Typically, in this method, each droplet provides a single sphere. The pore size depends on the size of the polymer particle. Some "shrinkage" or compaction occurs during polymer removal, and the size of the pores may be somewhat smaller than the original polymer particle size, for example, about 10% to about 40% smaller than the polymer particle size. The pore size is uniform, as is the shape and size of the polymer particles.

[0026] The pore size, in some embodiments, may range from about 50 nm to about 999 nm.

[0027] The average porosity of the metal oxide spheres can be relatively high. The average porosity of a sphere refers to the total pore volume as a fraction of the total volume of the sphere. The average porosity is sometimes referred to as the "volume fraction."

[0028] In some embodiments, the porous sphere can have a solid core (center) and the porosity is generally to the exterior surface of the sphere. In other embodiments, the porous sphere can have a hollow core and the majority of the porosity is to the interior of the sphere. In other embodiments, the porosity can be distributed throughout the volume of the sphere. In other embodiments, the porosity can exist as a gradient, with more porosity towards the exterior surface of the sphere and less or no porosity towards the center (solid), or less porosity towards the exterior surface of the sphere and more or complete porosity towards the center (hollow).

[0029] For any porous sphere, the average sphere diameter is preferably greater than the average pore size, for example, the average sphere diameter is at least about 25 times, at least about 30 times, at least about 35 times, or at least about 40 times greater than the average pore size.

[0030] In some embodiments, the ratio of the average sphere size to the average pore size is, for example, about 40 / 1, about 50 / 1, about 60 / 1, about 70 / 1, about 80 / 1, about 90 / 1, about 100 / 1, about 110 / 1, about 120 / 1, about 130 / 1, about 140 / 1, about 150 / 1, about 160 / 1, about 170 / 1, about 180 / 1, or about 190 / 1 to about 200 / 1, about 210 / 1, about 220 / 1, about 230 / 1, about 240 / 1, about 250 / 1, about 260 / 1, about 270 / 1, about 280 / 1, about 290 / 1, about 300 / 1, about 310 / 1, about 320 / 1, about 330 / 1, about 340 / 1, or about 350 / 1.

[0031] Polymer template spheres, including monodisperse polymer spheres, can provide metal oxide spheres having pores with generally similar pore sizes when the polymer is removed.

[0032] The average diameter of the spheres (eg, microspheres) may be from 0.5 μm to 100 μm, or from 1 μm to 75 μm, or from 4.5 μm to 9.9 μm.

[0033] The average porosity of the spheres (eg, spherules) may be from 0.10 to 0.90, or from 0.10 to 0.80, or from 0.45 to 0.65.

[0034] The average pore size of the spheres (eg, microspheres) may be from 50 nm to 999 nm, from 50 nm to 800 nm, and from 220 nm to 300 nm.

[0035] Certain embodiments are directed to porous microspheres, the microspheres having an average diameter of 0.5 μm to 100 μm, an average porosity of 0.10 to 0.90 or 0.10 to 0.80, and an average pore size of 50 nm to 999 nm.

[0036] Other embodiments are directed to porous metal oxide spheres having an average diameter of 1 μm to 75 μm, an average porosity of 0.45 to 0.65, and an average pore size of 50 nm to 800 nm.

[0037] A further embodiment is directed to porous metal oxide spheres having an average diameter of 4.5 μm to 9.9 μm, an average porosity of 0.45 to 0.65, and an average pore size of 220 nm to 300 nm.

[0038] Without wishing to be bound by theory, it is believed that bulk samples of spheres will exhibit absorption if the porosity and / or sphere diameter and / or pore size are within certain ranges.

[0039] The porous spheres may primarily comprise metal oxide, i.e., they may consist essentially of or consist of metal oxide. The amount of metal oxide in the spheres may be, for example, 50 to 99.9% by weight based on the weight of the sphere. Certain embodiments have a lower limit of 60%, or 70%, or 90%, or 95% by weight.

[0040] Advantageously, the porous spheres (eg, microspheres) may also be monodisperse.

[0041] According to the present invention, particle size is synonymous with particle diameter, and is determined, for example, by scanning electron microscopy (SEM) or transmission electron microscopy (TEM). Average particle size is synonymous with D50, meaning that half of the population is above this point and half is below. Particle size refers to primary particles. Particle size can be measured by laser light scattering techniques using dispersions or dry powders.

[0042] Mercury porosimetry analysis was used to characterize the porosity of the microspheres. Mercury porosimetry applies a controlled pressure to a sample submerged in mercury. An external pressure is applied to the mercury, which penetrates into the voids / pores of the material. The amount of pressure required to penetrate into the voids / pores is inversely proportional to the size of the voids / pores. Mercury porosimetry generates a volume and pore size distribution from the pressure vs. penetration data generated by the instrument using the Washburn equation. For example, porous silica microspheres containing voids / pores with an average size of 165 nm have an average porosity of 0.8.

[0043] The term "bulk sample" refers to a population of spheres. For example, a bulk sample of microspheres is simply a bulk population of microspheres, e.g., ≧0.1 mg, ≧0.2 mg, ≧0.3 mg, ≧0.4 mg, ≧0.5 mg, ≧0.7 mg, ≧1.0 mg, ≧2.5 mg, ≧5.0 mg, ≧10.0 mg, or ≧25.0 mg. A bulk sample of spheres may be essentially free of other components. The terms "porous spheres" or "porous microspheres" may refer to a bulk sample.

[0044] The term "of" can mean "comprises," for example, "a liquid dispersion of" can be interpreted as "a liquid dispersion comprising."

[0045] The terms "microspheres," "nanospheres," "droplets," and the like, as referred to herein, can refer to, for example, a plurality thereof, a collection thereof, a population thereof, a sample thereof, or a bulk sample thereof.

[0046] The term "micro" or "microscale" means from about 0.5 μm to about 999 μm. The term "nano" or "nanoscale" means from about 1 nm to about 999 nm.

[0047] The terms "sphere" and "particle" may be interchangeable.

[0048] The term "monodisperse" in reference to a population of spheres or spheres means particles having a generally uniform shape and a generally uniform diameter. A monodisperse population of the present microspheres or nanospheres can have, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of the particles having a diameter within ±7%, ±6%, ±5%, ±4%, ±3%, ±2%, or ±1% of the average diameter of the population.

[0049] Removal of the monodisperse population of polymer spheres provides porous metal oxide spheres having a corresponding population of pores having an average pore size.

[0050] The term "essentially free of other components" means, for example, containing ≦5% by weight, ≦4% by weight, ≦3% by weight, ≦2% by weight, ≦1% by weight, or ≦0.5% by weight of other components.

[0051] The articles "a" and "an" herein refer to one or more than one (e.g., at least one) of the grammatical object. Any ranges cited herein are inclusive. The term "about" used throughout is used to describe and account for small variations. For example, "about" can mean a numerical value that can be modified by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, ±0.1%, or ±0.05%. A numerical value modified by the term "about" includes the particular specified value. For example, "about 5.0" includes 5.0.

[0052] All parts and percentages are by weight unless otherwise noted. Weight percent (wt%) is of the total composition unless otherwise noted.

[0053] A non-limiting set of embodiments of the present invention are directed to a method of preparing porous metal oxide spheres comprising:

[0054] In a first embodiment, a method of preparing porous metal oxide microspheres comprising a metal oxide is disclosed, the method comprising forming a liquid dispersion of polymer nanoparticles and a metal oxide, forming droplets of the dispersion, drying the droplets to obtain polymer template microspheres comprising the polymer nanospheres and the metal oxide, and removing the polymer nanospheres from the template microspheres to obtain porous metal oxide microspheres.

[0055] In a second embodiment, the method of the first embodiment includes forming a liquid dispersion of polymeric nanoparticles and a metal oxide, spray drying the liquid dispersion to obtain polymeric template microspheres, and removing the polymeric nanospheres from the template microspheres.

[0056] In a third embodiment, the method of the first embodiment includes forming the droplets using a vibrating nozzle. In a fourth embodiment, the method of the first to third embodiments, the droplets are water droplets. In a fifth embodiment, the method of the first to third embodiments, the droplets are oil droplets.

[0057] In a sixth embodiment, the method of embodiment 1 comprises providing a continuous phase and mixing a liquid dispersion with the continuous phase to form an emulsion containing dispersed liquid dispersion droplets. In a seventh embodiment, the method of embodiment 6 comprises providing a continuous oil phase and mixing an aqueous dispersion with the continuous oil phase to form a water-in-oil emulsion containing water droplets. In an eighth embodiment, the method of embodiment 6 comprises providing a continuous aqueous phase and mixing an oil dispersion with the continuous phase to form an oil-in-water emulsion containing oil droplets.

[0058] In a ninth embodiment, the method of any one of embodiments 6 to 8 further comprises collecting the droplets. In a tenth embodiment, the method of embodiment 9 further comprises drying the droplets to obtain polymer template microspheres comprising polymer nanospheres and metal oxide, and removing the polymer nanospheres from the template microspheres.

[0059] In an eleventh embodiment, the method according to any one of embodiments 6 to 10, wherein the step of drying the droplets comprises microwave irradiation, oven drying, drying under vacuum, drying in the presence of a desiccant, or a combination thereof.

[0060] In a twelfth embodiment, the method according to any of the seventh to eleventh embodiments, wherein the oil phase or dispersion comprises a hydrocarbon, a silicone oil or a fluoro oil. In a thirteenth embodiment, the method according to any of the sixth to twelve embodiments, wherein the step of forming the droplets occurs in a microfluidic device. In a fourteenth embodiment, the method according to any of the sixth to thirteenth embodiments, wherein the step of forming the droplets occurs in a microfluidic device containing a droplet junction having a channel width of about 10 μm, about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm or about 45 μm to about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, about 95 μm or about 100 μm. A channel width of 10 μm to 100 μm is preferred. In a fifteenth embodiment, the method according to any of the thirteenth or fourteenth embodiments, comprising a step of collecting the droplets from the microfluidic device.

[0061] In a sixteenth embodiment, the method of any one of the preceding embodiments, wherein the wt / wt ratio of polymeric nanoparticles to metal oxide is from about 0.1 / 1, about 0.5 / 1, about 1.0 / 1, about 1.5 / 1, about 2.0 / 1, about 2.5 / 1 or about 3.0 / 1 to about 3.5 / 1, about 4.0 / 1, about 5.0 / 1, about 5.5 / 1, about 6.0 / 1, about 6.5 / 1, about 7.0 / 1, about 8.0 / 1, about 9.0 / 1 or about 10.0 / 1. Ratios of 0.1 / 1 to 10 / 1 are preferred.

[0062] In a seventeenth embodiment, the method of any one of the preceding embodiments, wherein the polymeric nanoparticles have an average diameter of about 50 nm, about 75 nm, about 100 nm, about 130 nm, about 160 nm, about 190 nm, about 210 nm, about 240 nm, about 270 nm, about 300 nm, about 330 nm, about 360 nm, about 390 nm, about 410 nm, about 440 nm, about 470 nm, about 500 nm, about 530 nm, about 560 nm, about 590 nm, or about 620 nm to about 650 nm, about 680 nm, about 710 nm, about 740 nm, about 770 nm, about 800 nm, about 830 nm, about 860 nm, about 890 nm, about 910 nm, about 940 nm, about 970 nm, or about 990 nm.

[0063] In an eighteenth embodiment, the method of any one of the preceding embodiments, wherein the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylate, polystyrene, polyacrylamide, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, derivatives thereof, salts thereof, copolymers thereof, and combinations thereof.

[0064] In a nineteenth embodiment, the method of any one of the preceding embodiments, wherein the polymer is selected from the group consisting of polystyrene, e.g., a polystyrene copolymer, e.g., polystyrene / acrylic acid, polystyrene / poly(ethylene glycol) methacrylate, or polystyrene / styrene sulfonate. In a twentieth embodiment, the method of any one of the preceding embodiments, wherein the metal oxide is one or more of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, or chromium oxide.

[0065] In a twenty-first embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres have an average diameter of about 0.5 μm to about 100 μm, an average porosity of about 0.10 to about 0.90 or about 0.10 to about 0.80, and an average pore size of about 50 nm to about 999 nm.

[0066] In a twenty-second embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres have an average diameter of about 1 μm to about 75 μm, about 2 μm to about 70 μm, about 3 μm to about 65 μm, about 4 μm to about 60 μm, about 5 μm to about 55 μm or about 5 μm to about 50 μm, such as about 5 μm, about 6 μm, about 7 μm, about 8 μm, about 9 μm, about 10 μm, about 11 μm, about 12 μm, about 13 μm, about 14 μm or about 15 μm to about 16 μm, about 17 μm, about 18 μm, about 19 μm, about 20 μm, about 21 μm, about 22 μm, about 23 μm, about 24 μm or about 25 μm.

[0067] In a twenty-third embodiment, the porous microspheres have a molecular weight of about 0.10, about 0.12, about 0.14, about 0.16, about 0.18, about 0.20, about 0.22, about 0.24, about 0.26, about 0.28, about 0.30, about 0.32, about 0.34, about 0.36, about 0.38, about 0.40, about 0.42, about 0.44, about 0.46, about 0.48, about 0.5 3. The method of any one of the preceding embodiments, wherein the porous membrane has an average porosity of from any of 0, about 0.52, about 0.54, about 0.56, about 0.58, or about 0.60 to any of about 0.62, about 0.64, about 0.66, about 0.68, about 0.70, about 0.72, about 0.74, about 0.76, about 0.78, about 0.80, or about 0.90.

[0068] In a twenty-fourth embodiment, the porous microspheres have a diameter of about 50 nm, about 60 nm, about 70 nm, 80 nm, about 100 nm, about 120 nm, about 140 nm, about 160 nm, about 180 nm, about 200 nm, about 220 nm, about 240 nm, about 260 nm, about 280 nm, about 300 nm, about 320 nm, about 340 nm, about 360 nm, about 380 nm, about 400 nm, about 420 nm, or about 440 nm. The method of any one of the preceding embodiments, wherein the average pore diameter is any of about 460 nm, about 480 nm, about 500 nm, about 520 nm, about 540 nm, about 560 nm, about 580 nm, about 600 nm, about 620 nm, about 640 nm, about 660 nm, about 680 nm, about 700 nm, about 720 nm, about 740 nm, about 760 nm, about 780 nm, or about 800 nm.

[0069] In a twenty-fifth embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres have an average diameter of about 4.5 μm, about 4.8 μm, about 5.1 μm, about 5.4 μm, about 5.7 μm, about 6.0 μm, about 6.3 μm, about 6.6 μm, about 6.9 μm, about 7.2 μm or about 7.5 μm to about 7.8 μm, about 8.1 μm, about 8.4 μm, about 8.7 μm, about 9.0 μm, about 9.3 μm, about 9.6 μm or about 9.9 μm.

[0070] In a twenty-sixth embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres have an average porosity of from about 0.45, about 0.47, about 0.49, about 0.51, about 0.53, about 0.55 or about 0.57 to about 0.59, about 0.61, about 0.63 or about 0.65.

[0071] In a twenty-seventh embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres have an average pore diameter of from about 220 nm, about 225 nm, about 230 nm, about 235 nm, about 240 nm, about 245 nm, or about 250 nm to about 255 nm, about 260 nm, about 265 nm, about 270 nm, about 275 nm, about 280 nm, about 285 nm, about 290 nm, about 295 nm, or about 300 nm.

[0072] In a twenty-eighth embodiment, the porous microspheres have an average diameter of about 4.5 μm, about 4.8 μm, about 5.1 μm, about 5.4 μm, about 5.7 μm, about 6.0 μm, about 6.3 μm, about 6.6 μm, about 6.9 μm, about 7.2 μm, or about 7.5 μm to about 7.8 μm, about 8.1 μm, about 8.4 μm, about 8.7 μm, about 9.0 μm, about 9.3 μm, about 9.6 μm, or about 9.9 μm, about 0.45, about 0.47, about 0.49, about 0.51, about 0.53, about 0.55, or about 0.5 7 to any of about 0.59, about 0.61, about 0.63 or about 0.65, and an average pore size of about 220 nm, about 225 nm, about 230 nm, about 235 nm, about 240 nm, about 245 nm or about 250 nm to any of about 255 nm, about 260 nm, about 265 nm, about 270 nm, about 275 nm, about 280 nm, about 285 nm, about 290 nm, about 295 nm or about 300 nm.

[0073] In a twenty-ninth embodiment, the method of any one of the preceding embodiments, wherein the porous microspheres comprise from about 60.0 wt% to about 99.9 wt% of any metal oxide, for example from about 60.0 wt%, about 64.0 wt%, about 67.0 wt%, about 70.0 wt%, about 73.0 wt%, about 76.0 wt%, about 79.0 wt%, about 82.0 wt%, or about 85.0 wt% to about 88.0 wt%, about 91.0 wt%, about 94.0 wt%, about 97.0 wt%, about 98.0 wt%, about 99.0 wt%, or about 99.9 wt% of any metal oxide, based on the total weight of the microspheres.

[0074] In a thirtieth embodiment, the porous microspheres include from about 0.1 wt % to about 40.0 wt % of one or more light absorbing agents, based on the total weight of the microsphere, for example, about 0.1 wt %, about 0.3 wt %, about 0.5 wt %, about 0.7 wt %, about 0.9 wt %, about 1.0 wt %, about 1.5 wt %, about 2.0 wt %, about 2.5 wt %, about 5.0 wt %, about 7.5 wt %, about 10.0 wt %, about 13 wt %, about 20 wt %, about 30 wt %, about 40 wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt %, about 100 wt %, about 150 wt %, about 200 wt %, about 300 wt %, about 400 wt %, about 500 wt %, about 600 wt %, about 700 wt %, about 800 wt %, about 900 wt %, about 1000 wt %, about 15 ... The method of any one of the preceding embodiments, comprising from about 0.0 wt%, about 17.0 wt%, about 20.0 wt%, or about 22.0 wt%, to about 24.0 wt%, about 27.0 wt%, about 29.0 wt%, about 31.0 wt%, about 33.0 wt%, about 35.0 wt%, about 37.0 wt%, about 39.0 wt%, or about 40.0 wt% of one or more light absorbers.

[0075] In a thirty-first embodiment, the method of any of the preceding embodiments, wherein the porous microspheres are monodisperse. In a thirty-second embodiment, the method of any of the preceding embodiments, wherein the porous metal oxide microspheres are a bulk sample of microspheres.

[0076] In a thirty-third embodiment, the method of any of the preceding embodiments, wherein removing the polymer nanospheres from the template microspheres comprises calcination, pyrolysis, or solvent removal.

[0077] In a thirty-fourth embodiment, the method of any one of the preceding embodiments, wherein the step of removing the polymer nanospheres comprises calcining the template microspheres at a temperature of about 200° C., about 350° C., about 400° C., about 450° C., about 500° C., or about 550° C. to about 600° C., about 650° C., about 700° C., or about 1200° C. for a period of about 0.1 hour (hour), 1 hour, about 1.5 hours, about 2.0 hours, about 2.5 hours, about 3.0 hours, about 3.5 hours, or about 4.0 hours to about 4.5 hours, about 5.0 hours, about 5.5 hours, about 6.0 hours, about 6.5 hours, about 7.0 hours, about 7.5 hours, about 8.0 hours, or about 12 hours. Alternatively, calcination may be at a temperature of at least about 200° C., at least about 500° C., or at least about 1000° C. for a suitable period of time, such as at least about 0.1 hours, at least about 1 hour, at least about 5 hours, or at least about 10 hours.

[0078] The porous metal oxide spheres are preferably used at a concentration of 0.01 wt% to 40.0 wt%, or 0.01 wt% to 20.0 wt%, based on the weight of the molded artificial polymeric article. Other ranges include 0.1 wt% to 20.0 wt%, or 0.1 wt% to 10.0 concentrations, or 0.25 wt% to 10.0 wt%, or 0.5 wt% to 10.0 wt%.

[0079] The porous metal oxide microspheres can be used in combination with one or more UV absorbers selected from the group consisting of 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones, oxalanilides, cinnamates and benzoates.

[0080] The one or more UV absorbers are preferably used in a concentration of 0.01 wt% to 40.0 wt%, especially 0.01 wt% to 20.0 wt%, based on the weight of the molded artificial polymeric article. Concentrations of 0.1 wt% to 20.0 wt%, especially 0.1 wt% to 10.0 wt%, are more preferred.

[0081] The benzotriazole for combination with the porous metal oxide microspheres preferably has the formula (Ia): [ka] (Wherein, T1 is hydrogen, C1 to C 18 C1-C substituted with alkyl or phenyl 18 Is it an alkyl group? or T1 is of the formula [ka] Based on L1 is a divalent group, e.g. -(CH2) n - where n ranges from 1 to 8; T2 is hydrogen, C1-C 18 Alkyl or COOT5, C1-C 18 Alkoxy, hydroxyl, phenyl or C2-C 18 C1-C substituted with acyloxy 18 is alkyl, T3 is hydrogen, halogen, C1-C 18 Alkyl, C1-C 18 Alkoxy, C2-C 18 acyloxy, perfluoroalkyl of 1 to 12 carbon atoms, e.g., -CF3, or T3 is phenyl; T5 is an alkyl group having one or more O inserted therein and / or an OH or group [ka] Substituted by, C1-C 18 Alkyl or C4-C 50 (It is alkyl) It is of the following.

[0082] Examples of such benzotriazoles are Tinuvin® PA 328 and Tinuvin® 326 and the corresponding UV absorbers listed below.

[0083] The 2-hydroxybenzophenone for combination with the porous metal oxide microspheres is preferably of formula (Ib): [ka] (In the formula, G1, G2 and G3 are independently hydrogen, hydroxy or C1-C 18 (alkoxy) It is of the following.

[0084] Examples of such 2-hydroxybenzophenones are Chimassorb® 81 and the corresponding UV absorbers listed below.

[0085] The oxalanilide for combination with the porous metal oxide microspheres preferably has the formula (Ic): [ka] (In the formula, G4, G5, G6 and G7 are independently hydrogen, C1 to C 12 Alkyl or C1-C 12 (alkoxy) It is of the following.

[0086] Examples are the corresponding UV absorbers listed below.

[0087] The cinnamate for combination with the porous metal oxide microspheres preferably has the formula (Id): [ka] (In the formula, m is an integer from 1 to 4; G 15 is hydrogen or phenyl; If m is 1, then G 16 is COO-G 19 and If m is 2, then G 16 is C2~C 12 alkane-dioxycarbonyl, If m is 3, then G16 is C3~C 12 alkane-trioxycarbonyl, If m is 4, then G 16 is C4~C 12 alkane-tetraoxycarbonyl, G 17 is hydrogen, CN, or COO-G 19 and G 18 is hydrogen or methoxy, G 19 is C1~C 18 (It is alkyl) It is of the following.

[0088] An example of such a cinnamate is Uvinul® 3035 and the corresponding UV absorbers listed below.

[0089] The benzoate for combination with the porous metal oxide microspheres preferably has the formula (Ie) [ka] (In the formula, k is 1 or 2; If k is 1, then G 20 is C1~C 18 Alkyl, phenyl or C1-C 12 phenyl substituted with alkyl; G 21 is hydrogen, If k is 2, then G 20 and G 21 together form a tetravalent radical [ka] and G 22 and G 24 are independently hydrogen or C1-C8 alkyl; G 23 is hydrogen or hydroxyl) It is of the following.

[0090] Examples of such benzoates are the corresponding UV absorbers listed below.

[0091] The 2-hydroxyphenyltriazine for combination with the porous metal oxide microspheres preferably has the formula (If): [ka] (In the formula, G8 is C1~C 18 Alkyl, or COO, OCO, or O is inserted, or O is inserted and replaced by OH, C4-C 18 is alkyl, G9, G 10 , G 11 and G 12 are independently hydrogen, methyl, hydroxy or OG8. or formula (Ig) [ka] (Wherein, R is C1 to C 12 Alkyl, (CH2-CH2-O-) n -R2, -CH2-CH(OH)-CH2-O-R2; or -CH(R3)-CO-O-R4, n is 0 or 1, and R2 is C1 to C 13 Alkyl or C2-C 20 Alkenyl or C6-C 12 Aryl or CO-C1-C 18 R3 is H or C1-C8 alkyl, and R4 is C1-C 12 Alkyl or C2-C 12 alkenyl or C5-C6 cycloalkyl) It is of the following.

[0092] Examples of such 2-hydroxyphenyltriazines are Tinuvin® 1577 and Tinuvin® 1600 and the corresponding UV absorbers listed below.

[0093] In the context of the given definitions, including R2, R3 or R4, alkyl is, for example, branched or unbranched alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.

[0094] An alkyl group having two or more O inserted therein is, for example, a polyoxyalkylene group, such as a polyethylene glycol residue.

[0095] Aryl is generally an aromatic hydrocarbon group, for example phenyl, biphenylyl or naphthyl.

[0096] Within the context of the given definition, alkenyl is especially vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl.

[0097] Halogen is primarily fluoro, chloro, bromo or iodo, in particular chloro.

[0098] C5-C6 cycloalkyl is primarily cyclopentyl and cyclohexyl.

[0099] C2~C 18 Acyloxy is, for example, alkanoyloxy, benzoyloxy or alkenyloxy, such as acryloyloxy or methacryloyloxy.

[0100] Divalent C2~C 12 An example of an alkane-dioxycarbonyl is -COO-CH2CH2-OCO-; Trivalent C3~C 12 An example of an alkane-trioxycarbonyl is -COO-CH-CH(OCO-)CH-OCO-; Tetravalent C4~C 12 An example of an alkane-tetraoxycarbonyl is (-COO-CH2)4C.

[0101] Preferably, the one or more UV absorbers for combination with the porous metal oxide microspheres include one or more compounds selected from (i) to (lv):

[0102] i. 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, ii. 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, iii. 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, iv. 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, v. 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol], vi. Transesterification products of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; vii. 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, viii. 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, ix. 2-(2'-hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole, x. 2-(2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole, xi. 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-alkyloxyphenyl)-1,3,5-triazine, where alkyl is a mixture of C8 alkyl groups (CAS numbers 137759-38-7, 85099-51-0, 85099-50-9); xii. 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine (CAS number 2725-22-6), xiii. 2,4-diphenyl-6-(2-hydroxy-4-[α-ethylhexanoyloxyethyl]phenyl)-1,3,5-triazine, xiv. 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, xv. 2,4,6-tris(2-hydroxy-4-[1-ethoxycarbonylethoxy]phenyl)-1,3,5-triazine, xvi. Reaction products of tris(2,4-dihydroxyphenyl)-1,3,5-triazine with a mixture of α-chloropropionic acid esters (prepared from an isomeric mixture of C7-C9 alcohols); xvii. 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, xviii. 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, xix. 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, xx. 2-(3'-tert.butyl-5'-methyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, xxi. 2-(3'-sec.butyl-5'-tert.butyl-2'-hydroxyphenyl)-benzotriazole, xxii. 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, xxiii. 2-(5'-tert.octyl-2'-hydroxyphenyl)-benzotriazole, xxiv. 2-(3'-dodecyl-5'-methyl-2'-hydroxyphenyl)-benzotriazole, xxv. 2-(3'-tert.butyl-5'-(2-octyloxycarbonylethyl)-2'-hydroxyphenyl)-5-chloro-benzotriazole, xxvi. 2-(5'-methyl-2'-hydroxyphenyl)-benzotriazole, xxvii. 2-(5'-tert.butyl-2'-hydroxyphenyl)-benzotriazole, [ka] Compounds of xxxi. expression [ka] Compounds of xxxii. 2-Ethylhexyl-p-methoxycinnamate (CAS number 5466-77-3), xxxiii. 2,4-dihydroxybenzophenone, xxxiv. 2-hydroxy-4-methoxybenzophenone, xxxv. 2-hydroxy-4-dodecyloxybenzophenone, xxxvi. 2-hydroxy-4-octyloxybenzophenone, xxxvii. 2,2'-dihydroxy-4-methoxybenzophenone, xxxviii. formula [ka] Compounds of xxxix. expression [ka] Compounds of xl. expression [ka] Compounds of xli. expression [ka] Compounds of xlii. expression [ka] Compounds of xliiii. expression [ka] Compounds of xliv. expression [ka] Compounds of xlv. expression [ka] Compounds of xlvi. xlvi. expression [ka] Compound xlvii. expression [ka] Compound xlviii. expression [ka] Compound xlix. expression [ka] Compound l. expression [ka] Compound li. Expressions [ka] Compound lii. Expression [ka] Compound liii. expression [ka] Compound liv. expression [ka] Compound lv. expression [ka] Compound lvi. Dodecanedioic acid, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl] ester (CAS number 1482217-03-7) lvii. expression [ka] Compound lviii. expression [ka] Compound

[0103] In one embodiment, UV absorbers i-xx and xlvi are preferred.

[0104] In certain embodiments, UV absorbers i-iv, vi-xi, xiii-xviii, xx, xxiii-xxxix, xlvi, especially ii, iii, iv, vi, vii, viii, xx, xxv, xxxvii, xlvi are preferred.

[0105] In a further embodiment, i to x, xii, xiii, xix to xxiii, xxv to xxvii, xxx to xxxvi, xl to xlv and xlvi, in particular i, ii, iii, v, vi, viii, xii, xiii, xix, xx, xxii, xxiii, xxvi, xxx, xxxi, xxxiv, xxxvi, xl, xli, xlii, xliii, xliv, xlv and xlvi are preferred.

[0106] Highly preferred 2-hydroxyphenyltriazines are xii, xlviii and xlvi.

[0107] Preferred are 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones and benzoates, especially 2-hydroxyphenyltriazines, benzotriazoles and 2-hydroxybenzophenones.More preferred are benzotriazoles and 2-hydroxybenzophenones, especially benzotriazoles.

[0108] Specific examples of synthetic polymers or natural or synthetic elastomers for molded man-made polymeric articles are: 1. Polymers of mono- and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or poly-butadiene, polyhexene, polyoctene, and polymers of cycloolefins, such as cyclopentene, cyclohexene, cyclooctene or norbornene, polyethylenes, optionally crosslinked, such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra-high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0109] Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraphs, preferably polyethylene and polypropylene, can be prepared by various methods, in particular by the following methods: a) Radical polymerization (typically under high pressure and temperature). b) Catalytic polymerizations using catalysts that typically contain one or more metals from groups IVb, Vb, VIb or VIII of the periodic table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π or σ coordinated. These metal complexes may be in free form or fixed on substrates, typically activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts may be used as such in the polymerization or may use further activators, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of groups Ia, IIa and / or IIIa of the periodic table. The activators may be conveniently modified with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0110] 2. Mixtures of the polymers mentioned in 1), such as mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (e.g. PP / HDPE, PP / LDPE), and mixtures of different types of polyethylene (e.g. LDPE / HDPE).

[0111] 3. Copolymers of mono- and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and their mixtures with low density polyethylene (LDPE), very low density polyethylene, propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers, ethylene / cycloolefin copolymers (e.g. ethylene / norbornene, such as COC), ethylene / 1-olefin copolymers, where the 1-olefin is generated in-situ; propylene / butadiene copolymers, isobutylene / isoprene copolymers. polymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and dienes, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers mentioned under 1) above, such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, such as polyamides.

[0112] 4. Hydrocarbon resins (e.g. C5-C9) including their hydrogenated modifications (e.g. tackifiers) and mixtures of polyalkylenes with starch.

[0113] The homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndiotactic, isotactic, hemiisotactic or atactic, with atactic polymers being preferred. Stereoblock polymers are also included. The copolymers from 1.)-4.) may be random or block copolymers, homo- or heterophasic, or highly crystalline homopolymers.

[0114] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0115] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and all isomers of vinylanthracene, and mixtures thereof. The homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemiisotactic, or atactic, with atactic polymers being preferred. Stereoblock polymers are also included.

[0116] 6a. The above vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydride, maleimides, vinyl acetate and vinyl chloride, or acrylic derivatives and mixtures thereof, such as copolymers containing styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymers), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact mixtures of styrene copolymers with other polymers, such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / isoprene / butadiene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene, HIPS, ABS, ASA, AES.

[0117] 6b. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers mentioned in 6.), including in particular polycyclohexylethylene (PCHE), which is prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

[0118] 6c. Hydrogenated aromatic polymers resulting from the hydrogenation of the polymers mentioned in 6a.).

[0119] The homopolymers and copolymers may have any stereochemistry including syndiotactic, isotactic, hemiisotactic or atactic, with atactic polymers being preferred. Stereoblock polymers are also included.

[0120] 7. Graft copolymers of vinyl aromatic monomers, such as styrene or α-methylstyrene, e.g. styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with the copolymers listed under 6), such as the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

[0121] 8. Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. The polyvinyl chloride may be rigid or flexible (plasticized).

[0122] 9. Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, impact modified with butyl acrylate.

[0123] 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

[0124] 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and their copolymers with the olefins mentioned under 1) above.

[0125] 12. Cyclic ethers, such as homopolymers and copolymers of polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers thereof with bisglycidyl ethers.

[0126] 13. Polyacetals, such as polyoxymethylene and polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0127] 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

[0128] 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters, or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, as well as their precursors: (1) Polyurethanes formed by the reaction of diisocyanates with short-chain diols (chain extenders) and (2) diisocyanates with long-chain diols (thermoplastic polyurethanes, TPUs).

[0129] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6 / 6, 6 / 10, 6 / 9, 6 / 12, 4 / 6, 12 / 12, polyamide 11, polyamide 12, aromatic polyamides based on m-xylylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid with or without elastomers as modifiers, such as poly-2,4,4,-trimethylolpropanediamine. Methylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). The polyamides may be amorphous.

[0130] 17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

[0131] 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones or lactides, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polypropylene terephthalate, polyalkylene naphthalates and polyhydroxybenzoates, and copolyetheresters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonate or MBS. Copolyesters may include, for example, but are not limited to, polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, polybutylene succinate / adipate, polybutylene succinate / carbonate, poly-3-hydroxybutyrate / octanoate copolymers, poly-3-hydroxybutyrate / hexanoate / decanoate terpolymers. Additionally, aliphatic polyesters may include, for example and without limitation, the class of poly(hydroxyalkanoates), particularly poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene furanoate, and polylactic acid (PLA), as well as the corresponding polyesters modified with polycarbonate or MBS.The term "polylactic acid (PLA)" refers preferably to either homopolymers of poly-L-lactide and blends or alloys with other polymers; copolymers of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, such as glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-caproic acid and cyclic forms thereof, and the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, i.e. L-lactide, D-lactide, meso-lactide and any mixtures thereof. Preferred polyesters are PET, PET-G, PBT.

[0132] 19. Polycarbonates and polyestercarbonates. Polycarbonates are preferably prepared by reaction of bisphenol compounds with carbonic acid compounds, in particular phosgene, or with diphenyl carbonate or dimethyl carbonate in the melt transesterification process. Homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) are particularly preferred. These and further bisphenol and diol compounds that can be used for polycarbonate synthesis are disclosed, inter alia, in WO08037364 (page 7, line 21 to page 10, line 5), EP1582549 (

[0018] to

[0034] ), WO02026862 (page 2, line 23 to page 5, line 15), WO05113639 (page 2, line 1 to page 7, line 20). The polycarbonates can be linear or branched. Mixtures of branched and unbranched polycarbonates can also be used. Suitable branching agents for polycarbonates are known from the literature and are described, for example, in patent specifications US 4,185,009 and DE 2500092 (3,3-bis-(4-hydroxyaryl-oxindoles according to the invention, see the entire document in each case), DE 4240313 (see page 3, lines 33 to 55), DE 19943642 (see page 5, lines 25 to 34) and US 5,367,044 and the documents cited therein. The polycarbonates used can furthermore be essentially branched, with no branching agents being added here within the context of the preparation of the polycarbonates. An example of intrinsic branching is the Fries structure (Fries-branched polycarbonate), as disclosed for melt polycarbonate in EP 1506249. During the preparation of the polycarbonate, further chain terminators can be used. Phenols, such as phenol, alkylphenols, such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof, are preferably used as chain terminators.The polyester carbonates are obtained by the reaction of the bisphenols already mentioned, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone-dicarboxylic acid. A portion of up to 80 mol%, preferably 20 to 50 mol%, of the carbonate groups in the polycarbonate can be replaced by aromatic dicarboxylic acid ester groups.

[0133] 20. Polyketone.

[0134] 21. Polysulfone, polyethersulfone and polyetherketone.

[0135] 22. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea and melamine on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

[0136] 23. Drying and non-drying alkyd resins.

[0137] 24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and vinyl compounds as crosslinkers, and also their halogen-containing modifications which are of low flammability.

[0138] 25. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

[0139] 26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0140] 27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as the products of diglycidyl ethers of bisphenol A, bisphenol E and bisphenol F, with or without accelerators, crosslinked with customary hardeners, such as anhydrides or amines.

[0141] 28. Natural polymers, such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers, such as methylcellulose; and rosin and their derivatives.

[0142] 29. Blends (polyblends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0143] 30. Organic materials of natural origin and synthetic which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (for example phthalates, adipates, phosphates or trimellitates), and also mixtures of synthetic esters and mineral oils, in any weight ratio, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

[0144] 31. Aqueous emulsions of natural or synthetic rubber, for example, natural latex(s) of carboxylated styrene / butadiene copolymers.

[0145] 32. Adhesives, such as block copolymers, e.g. SIS, SBS, SEBS, SEPS (S stands for styrene, I stands for isoprene, B stands for polybutadiene, EB stands for ethylene / butylene block, EP stands for polyethylene / polypropylene block).

[0146] 33. Rubbers, for example polymers of conjugated dienes, such as polybutadiene or polyisoprene, copolymers of mono- and diolefins with one another or with other vinyl monomers, copolymers of styrene or methylstyrene with dienes or with acrylic derivatives, chlorinated rubber, natural rubber.

[0147] 34. Elastomers, such as natural polyisoprene (cis-1,4-polyisoprene natural rubber (NR) and trans-1,4-polyisoprene guttapercha), synthetic polyisoprene (for isoprene rubber, IR), polybutadiene (for butadiene rubber, BR), chloroprene rubber (CR), polychloroprene, Neoprene, Baypren, etc., butyl rubber (copolymer of isobutylene and isoprene, IIR), halogenated butyl rubber (chlorobutyl rubber: CIIR; bromobutyl rubber: BIIR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), Buna Nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), also known as N-rubber, hydrogenated nitrile rubber (HNBR) Therban and Zetpol, EPM (ethylene propylene rubber, copolymer of ethylene and propylene) and EPDM rubber (ethylene propylene diene rubber, terpolymer of ethylene, propylene and diene components), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomers (FKM and FEPM) Viton, Tecnoflon, Fluorel, Aflas and Dai-El, perfluoroelastomer (FFKM) Tecnoflon PFR, Kalrez, Chemraz, Perlast, Polyether Block Amides (PEBA), Chlorosulfonated Polyethylene (CSM), (Hypalon), Ethylene Vinyl Acetate (EVA), Thermoplastic Elastomers (TPE), Proteins Resilin and Elastin, Polysulfide Rubbers, Elastoolefins, Elastic Fibers used in textile production.

[0148] 35. Thermoplastic elastomers, such as styrenic block copolymers (TPE-s), thermoplastic olefins (TPE-o), elastomeric alloys (TPE-v or TPV), thermoplastic polyurethanes (TPU), thermoplastic copolyesters, thermoplastic polyamides, reactor TPO's (R-TPO's), polyolefin plastomers (POP's), polyolefin elastomers (POE's).

[0149] Most preferred are thermoplastic polymers such as polyolefins and their copolymers.

[0150] The molded artificial polymeric articles of the present invention are prepared, for example, by one of the following processing steps.

[0151] Injection blow molding, Extrusion, Blow molding, Rotational molding, Mold decoration (back injection), Slush molding, Injection molding, Co-injection molding, Blow molding, Molding, Compression molding, Resin transfer molding, Pressing, Film extrusion (cast film; blown film), Fiber spinning (woven, nonwoven), Stretching (uniaxial, biaxial), Annealing, Drawing, Calendering, Mechanical deformation, Sintering, Coextrusion, Lamination, Crosslinking (radiation, peroxide, silane), Steam cracking, Welding, Adhesives, Vulcanization, Thermoforming, Pipe extrusion, Profile extrusion, Sheet extrusion; Sheet casting, Strapping, Foaming, Recycling / rework, Visbreaking (peroxide, thermal), Fiber melt blowing, Spunbond, Surface treatment (corona discharge, flame, plasma), Sterilization (by gamma radiation, electron beam), Tape extrusion, Pultrusion, SMC processing or Plastisol.

[0152] A further embodiment of the invention is a shaped artificial polymeric article, wherein the polymer is a synthetic polymer and / or a natural or synthetic elastomer, and the polymer contains the porous metal oxide microspheres as described herein. For such articles, the definitions and preferences set forth herein apply.

[0153] The shaped man-made polymeric article is preferably an extruded, cast, spun, molded or calendered shaped man-made polymeric article.

[0154] Examples of articles according to the invention are: I-1) Plastic materials for floating devices, marine applications, pontoons, buoys, decks, piers, boats, kayaks, oars, and beach reinforcement.

[0155] I-2) Automotive applications, interior applications, exterior applications, especially trim, bumpers, dashboards, batteries, rear and front linings, under hood mouldings, hat shelves, trunk linings, interior linings, airbag covers, electronic mouldings for fittings (lights), dashboard mirror panels, headlamp glass, instrument panels, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exterior trim; door panels; gas tanks; front glazing; rear windows; seat backings, exterior panels, wire insulation, sealing pros File Extrusion, Cladding, Pillar Covers, Chassis Components, Exhaust Systems, Fuel Filters / Fillers, Fuel Pumps, Fuel Tanks, Body Side Moulding, Convertible Tops, Exterior Mirrors, Exterior Trim, Fasteners / Fixings, Front End Modules, Glass, Hinges, Locking Systems, Luggage / Roof Racks, Pressing / Stamping Parts, Seals, Side Impact Protection, Sound Deadening / Insulators and Sunroofs, Door Medallions, Consoles, Instrument Panels, Seats, Frames, Skins, Automotive Reinforcement Applications, Automotive Fiber Reinforcement Applications, Automotive Applications with Filled Polymers, Automotive Applications with Unfilled Polymers.

[0156] I-3) Road traffic equipment, in particular sign displays, road marking displays, automobile accessories, warning triangles, medical cases, helmets, tires.

[0157] I-4) Equipment for transport or public transport. Equipment for airplanes, trains, automobiles (cars, motorbikes), trucks, light trucks, buses, trams, bicycles, including fixtures.

[0158] I-5) Equipment for space applications, in particular for rockets and satellites, such as re-entry shields.

[0159] I-6) Equipment for construction and design, mining applications, sound quieting systems, street shelters, and shelters.

[0160] II-1) General appliances, cases, covers, and electrical / electronic devices (personal computers, telephones, mobile phones, printers, television sets, audio and video equipment), flower pots, satellite TV bowls, and panel units.

[0161] II-2) Coatings of other materials, such as steel or textiles.

[0162] II-3) Devices for the electronics industry, in particular insulation for plugs, in particular computer plugs, cases for electric and electronic components, printed circuit boards and also materials for electronic data storage, such as chips, check cards or credit cards.

[0163] II-4) Electrical appliances, especially washing machines, tumblers, ovens (microwaves), dishwashers, mixers, and irons.

[0164] II-5) Covers for lights (e.g. street lights, lampshades).

[0165] II-6) Applications in wire and cable (semiconductors, insulation and cable jacketing).

[0166] II-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulation of electronic devices, semiconductors, coffee makers and vacuum cleaners.

[0167] III-1) Technical articles, such as gears, sliding fits, spacers, screws, bolts, handles and knobs.

[0168] III-2) Rotating blades, ventilator and windmill blades, solar devices, closets, wardrobes, partition walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, conveyor belts.

[0169] III-3) Health care items, especially portable toilets, shower enclosures, toilet seats, covers and sinks.

[0170] III-4) Hygiene articles, especially diapers (baby and adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, bathtubs, portable toilets, toothbrushes and bedpans.

[0171] III-5) Pipes for water, wastewater and chemicals (bridged or not bridged), pipes for the protection of electric wires and cables, pipes for gas, oil and sewage, gutters, downpipes, and drainage systems.

[0172] III-6) Profiles of any shape (glazing), cladding, siding.

[0173] III-7) Glass substitutes, especially extruded plates, architectural glass (monolithic, twin or multi-wall), aircraft, schools, extruded sheets, window films for architectural glass, trains, transit and health articles.

[0174] III-8) Plates (walls, cutting boards), silos, wood substitutes, plastic materials, wood composites, walls, surfaces, furniture, decorative foils, flooring (interior and exterior use), flooring, duckboard and tiles.

[0175] III-9) Intake and exhaust manifolds.

[0176] III-10) Cement, concrete, composite uses and coverings, siding and cladding, handrails, balustrades, kitchen worktops, roofs, roofing sheets, tiles and waterproofing.

[0177] IV-1) Plates (walls and cutting boards), trays, artificial turf, astroturf, artificial covers for stadium rings (athletics), artificial floors for stadium rings (athletics), and tape.

[0178] IV-2) Long and short fibre fabrics (carpets / sanitary articles / ground sheets / monofilaments; filters; wipes / curtains (shades) / medical uses), loose fibres (uses like gowns / protective clothing), nets, ropes, cables, string, cords, threads, safety seat belts, clothing, underwear, gloves; boots; rubber boots, undergarments, apparel, swimwear, sportswear, umbrellas (parasols, sunshades), parachutes, paraglides, sails, "balloon silk", camping articles, tents, airbeds, sunbeds, bulk bags, and bags.

[0179] IV-3) Membranes, insulation, covers, seals for roofs, geomembranes, tunnels, dumps, ponds, wall roof membranes, geomembranes, swimming pools, swimming pool liners, pool liners, pond liners, curtains (shades) / sunshades, sun shades, canopies, wallpaper, food packaging and wrapping (flexible and solid), medical packaging (flexible and solid), airbags / safety belts, arm rests and head rests, carpets, center consoles, dashboards, cockpits, doors, overhead console modules, door trim, headliners, interior lighting, interior mirrors, luggage racks, rear luggage covers, seats, steering columns, steering wheels, textiles and trunk trim.

[0180] V-1) Films (packaging, rigid packaging, dump, laminate, bale wrap, swimming pools, trash bags, wallpaper, stretch film, raffia, desalination film, batteries and connectors.

[0181] V-2) Agricultural films (greenhouse covers, tunnels, mulch tunnels, microtunnels, "raspa y amagado", multispan, low walk-in tunnel, high tunnel, mulch, silage, silo bag, silo stretch, fumigation, air bubble, keder, solawrap, thermal, bale wrap, stretch bale wrap, seedbed, film tube); other agricultural applications (e.g. nonwoven soil cover, netting (made of tape, multifilament, and combinations thereof), waterproofing. Such agricultural films can be either single layer or multilayer constructions, typically made with 3, 5, or 7 layers. This can result in film structures such as ABA, ABC, ABCBA, ABCBD, ABCDCBA, AABCBAA, where A, B, C, D represent different polymers and adhesives. However, adjacent layers can also be joined so that the final film article can be made with an even number of layers, i.e., 2, 4, or 6 layers, e.g., AABA, AABB, AABAA, ABBAA, AABCB, AABCAA, etc.

[0182] V-3) Tape

[0183] V-4) Foams (sealing, insulation, barrier), sports and leisure mats.

[0184] V-5) Sealant

[0185] VI-1) Food packaging and wrapping (flexible and solid), BOPP, BOPET, bottles.

[0186] VI-2) Storage systems, such as boxes (crates), luggage, chests, household boxes, pallets, containers, shelves, trucks, screw boxes, packs and cans.

[0187] VI-3) Cartridges, syringes, medical applications, containers for any transport, trash cans and waste bins, garbage bags, containers, dust bins, bin liners, wheeled bins, containers in general, tanks for water / used water / chemicals / gas / oil / petrol / diesel; tank liners, boxes, crates, battery cases, pails, medical equipment such as pistons, ophthalmic applications, diagnostic equipment, and pharmaceutical blister packaging.

[0188] VII-1) Household items of any kind (electrical appliances, thermoses / clothes hangers, etc.), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap closures.

[0189] VII-2) Support devices and articles for leisure, such as sports and fitness equipment, gymnastics mats, ski boots, in-line skates, skis, bigfoot, athletic surfaces (e.g. tennis courts); screw caps, lids and stoppers for bottles and cans.

[0190] VII-3) Furniture in general, foam products (cushions, shock absorbing materials), foam, sponges, tableware, clothing, mats, garden chairs, outdoor stadium seats, tables, sofas, toys, building kits (boards / figures / balls), play houses, slides and play cars.

[0191] VII-4) Materials for optical and magnetic data storage.

[0192] VII-5) Utensils (eating, drinking, cooking, storing).

[0193] VII-6) Boxes for CDs, cassettes, video tapes; DVDs, electronic goods, office supplies of any kind (ballpoint pens, stamps and ink pads, mice, shelves, trucks), bottles of any quantity and content (drinks, detergents, cosmetics including perfumes), and adhesive tape.

[0194] VII-7) Footwear (shoes / soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, bottle labels, sofas, artificial joints (human), printing plates (flexo), printed circuit boards and display technology.

[0195] VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silicates, glass, asbestos).

[0196] Preferred are shaped man-made polymeric articles which are films, pipes, cables, tapes, sheets, containers, frames, fibres or filaments.

[0197] Another preferred embodiment of the present invention is a thin film, typically obtained using blown extrusion techniques. Single layer films or multilayer films with 3, 5 or 7 layers are of particular interest. The most important use of plastic thin films in agriculture is as covers for greenhouses and tunnels for growing crops in a protected environment.

[0198] A further embodiment of the invention is an extruded, cast, spun, molded or calendered polymeric composition comprising a synthetic polymer and / or a natural or synthetic elastomer and the porous metal oxide microspheres described herein, for which the definitions and preferences set forth herein apply.

[0199] The porous metal oxide spheres are preferably present in the extruded, cast, spun, molded or calendered polymer composition in an amount of 0.01 wt% to 40.0 wt%, especially 0.01 wt% to 20.0 wt%, based on the weight of the composition. Concentrations of 0.1 wt% to 20.0 wt%, especially 0.1 wt% to 10.0 wt%, are more preferred. Concentrations of 0.25 wt% to 10.0 wt%, especially 0.5 wt% to 10.0 wt%, are highly preferred.

[0200] The extruded, cast, spun, molded or calendered polymer compositions and molded artificial polymer articles may comprise at least one further additive in an amount of 0.001% to 30% by weight, preferably 0.005% to 20% by weight, in particular 0.005% to 10% by weight, based on the weight of the extruded, cast, spun, molded or calendered polymer composition or article. Examples are listed below:

[0201] 1. Antioxidants

[0202] 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4- Methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

[0203] 1.2. Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0204] 1.3. Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0205] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0206] 1.5. Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0207] 1.6. Alkylidene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl) Butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene Ene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0208] 1.7. O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0209] 1.8. Hydroxybenzylated malonates, such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0210] 1.9. Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0211] 1.10. Triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3, 5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0212] 1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salts of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0213] 1.12. Acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0214] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0215] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanate, anurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; esters with 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0216] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0217] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0218] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1 supplied by Uniroyal).

[0219] 1.18. Ascorbic Acid (Vitamin C)

[0220] 1.19. Amine antioxidants, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-disec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, Diamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p -phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-Octadecanoylaminophenol, Bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.,

[0221] 2.UV absorbers and light stabilizers

[0222] 2.1. 2-(2'-hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'- tert-Butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3' -tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole transesterification product with polyethylene glycol 300;, [ka] Wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0223] 2.2. 2-Hydroxybenzophenones, such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0224] 2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0225] 2.4. Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenylacrylate).

[0226] 2.5. Nickel compounds, such as nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethyl-butyl)phenol], for example the 1:1 or 1:2 complexes with or without further ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, such as the methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without further ligands.

[0227] 2.6. Sterically hindered amines, such as carbonic acid bis(1-undecyloxy-2,2,6,6-tetramethyl-4-piperidyl) ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert- Butyl-4-hydroxybenzylmalonate, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, linear or cyclic condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraacetate carboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy) bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, condensation products of 2-chloro-4,Condensation product of 6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 4 -Mixtures of hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation products of 1,2-bis(3-aminopropylamino)ethane with 2,4,6-trichloro-1,3,5-triazine, and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]); condensation products of 1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine, and N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin Reaction products with doline, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction products of maleic anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Registry Number 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, reaction products of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine, 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine, [ka] 1,3,5-triazine-2,4,6-triamine, N,N'''-1,6-hexanediylbis[N',N''-dibutyl-N,N',N''-tris(2,2,6,6-tetramethyl-4-piperidinyl)-reaction product, oxidized and hydrogenated, 3-bromo-1-propene, 1,3,5-triazine-2,4,6-triamine, N,N'''-1,6-hexanediylbis[N',N''-dibutyl-N,N',N''-tris(2,2 ,6,6-tetramethyl-4-piperidinyl)-, 4-piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy)-, 4,4'-carbonate, 1,3,5-triazine-2,4,6-triamine, N2,N2'-1,6-hexanediylbis[N4,N6-dibutyl-N2,N4,N6-tris(2,2,6,6-tetramethyl-4-piperidinyl)-, oxidized, hydrogenated, N-allyl derivatives and combinations thereof.

[0228] 2.7. Oxamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0229] 2.8. 2-(2-hydroxyphenyl)-1,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine , 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2 -[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyl 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-bis-biphenyl-4-yl-1,3,5-triazin-2-yl)-5-(2-ethyl-(n)-hexyloxy)phenol; dodecanedioic acid, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl] ester (CAS number 1482217-03-7). ,

[0230] 3. Metal deactivators, such as N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0231] 4. Phosphites and phosphonites, such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-t tert-butylphenyl)4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin , 2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, phosphoric acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-Dimethylpropyl)phenyl triester (CAS No. 939402-02-5), phosphoric acid, triphenyl ester, polymer with alpha-hydro-omega-hydroxypoly[oxy(methyl-1,2-ethanediyl)], C10-16 alkyl ester (CAS No. 1227937-46-3).

[0232] The following phosphites are particularly preferred: Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl)phosphite [ka] TIFF0007665523000036.tif41155

[0233] 5. Hydroxylamines, such as N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0234] 6. Nitrones, such as N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecyl nitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-ocatadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amine.

[0235] 7. Thiosynergists, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate] or distearyl disulfide.

[0236] 8. Peroxide scavengers, such as esters of β-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0237] 9. Polyamide stabilizers, such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

[0238] 10. Basic co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0239] 11. PVC heat stabilizers, such as mixed metal stabilizers (e.g., barium / zinc, calcium / zinc types), organotin stabilizers (e.g., organotin mercaptoesters, -carboxylates, -sulfides), lead stabilizers (e.g., tribasic lead sulfate, dibasic lead stearate, dibasic lead phthalate, dibasic lead phosphite, lead stearate), organic based stabilizers and combinations thereof.

[0240] 12. Nucleating agents, such as inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, preferably alkaline earth metal phosphates, carbonates or sulfates; organic compounds, such as mono- or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.

[0241] 13. Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour and other natural product powders or fibers, synthetic fibers.

[0242] 14. Plasticizers, wherein the plasticizer is selected from the group consisting of di(2-ethylhexyl)phthalate, diisononyl phthalate, diisodecyl phthalate, dipropylheptyl phthalate, trioctyl trimellitate, tri(isononyl) trimellitate, epoxidized soybean oil, di(isononyl)cyclohexane-1,2-dicarboxylate, 2,4,4-trimethyl-1,3-pentaediol diisobutyrate.

[0243] Plasticizers used according to the present invention may also include those selected from the group consisting of phthalates, trimellitates, aliphatic dibasic esters, polyesters, polymeric, epoxides, phosphates. In a preferred embodiment, the plasticizers are: butyl benzyl phthalate, butyl 2-ethylhexyl phthalate, diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisotredecyl phthalate. , diiso(C11,C12,C13)phthalate, di(n-butyl)phthalate, di(n-C7,C9)phthalate, di(n-C6,C8,C10)phthalate, diiso(n-nonyl)phthalate, di(n-C7,C9,C11)phthalate, di(n-C9,C11)phthalate, di(n-undecyl)phthalate, tri(n-C8,C10)trimellitate, tri(2-ethylhexyl)trimellitate , tri(isooctyl) trimellitate, tri(isononyl) trimellitate, di(n-C7,C9) adipate, di(2-ethylhexyl) adipate, di(isooctyl) adipate, di(isononyl) adipate, polyesters of adipic acid or glutaric acid and propylene glycol or butylene glycol or 2,2-dimethyl-1,3-propanediol, epoxidized fats and oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil, octyl epoxythalate, 2-ethylhexyl epoxythalate, isodecyl diphenyl phosphate, tri(2-ethylhexyl) phosphate, tricresyl phosphate, di(2-ethylhexyl) terephthalate, di(isononyl)cyclohexane-1,2-dicarboxylate, and combinations thereof.In one particularly preferred embodiment, the plasticizer is: diisohexyl phthalate, diisoheptyl phthalate, di(2-ethylhexyl) phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, diisotredecyl phthalate, diiso(C11,C12,C13) phthalate, di(n-butyl) phthalate, di(n-C7,C9) phthalate, di(n-C6,C8,C10) phthalate, diiso(n-nonyl) phthalate, di(n-C7,C9,C11) phthalate, di(n-C9,C11) phthalate, di(n-undecyl) phthalate,

[0033] The polyether ester is selected from the group consisting of tri(n-C8,C10)trimellitate, tri(2-ethylhexyl)trimellitate, tri(isooctyl)trimellitate, tri(isononyl)trimellitate, di(n-C7,C9)adipate, di(2-ethylhexyl)adipate, di(isooctyl)adipate, di(isononyl)adipate, polyesters of adipic acid or glutaric acid and propylene glycol or butylene glycol or 2,2-dimethyl-1,3-propanediol, epoxidized fats and oils such as epoxidized soybean oil, di(isononyl)cyclohexane-1,2-dicarboxylate, and combinations thereof.

[0244] 15. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and expansion agents.

[0245] 16. Benzofuranones and indolinones, such as those disclosed in US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[ 2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

[0246] In certain embodiments, the photonic materials with UV absorbing functionality disclosed herein can be coated or incorporated into substrates such as plastics, wood, fibers or textiles, ceramics, glass, metals, and composite products thereof.

[0247] The scope and subject matter of the present invention will be better understood based on the following examples, which are intended to be illustrative, but non-limiting, of certain specific embodiments of the invention. EXAMPLES

[0248] The UV measurements for application examples 1 to 19 are carried out as follows: Ultraviolet transmission spectra were measured using a Varian 5000 UV-Vis-NIR dual beam spectrophotometer. The plaque to be measured was placed in a sample holder and the transmitted light was measured by the receiver between 200 and 800 nm in 1 nm increments. No reference beam was used. A 0% transmission reference was determined by blocking the measurement beam to the receiver. A 100% transmission reference was determined by allowing the measurement beam to reach the receiver unobstructed.

[0249] [Synthesis Example 1] Porous Silica Microspheres Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water is added to a three-necked reaction flask equipped with a thermometer, condenser, magnetic stirring, and nitrogen atmosphere. The water is heated to 80° C. and 10 g of styrene is added with stirring, followed by 100 mg of acrylic acid dissolved in 10 mL DI water via syringe. 100 mg of ammonium persulfate is dissolved in 10 mL DI water and added to the stirred mixture via syringe. The reaction mixture is stirred at 80° C. for 24 hours. The polymer colloidal dispersion is cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0250] The aqueous polystyrene colloidal dispersion is diluted to 1 wt% with deionized water, 1 wt% silica nanoparticles are added, and the mixture is sonicated to prevent particle aggregation. The continuous oil phase contains 0.1 wt% polyethylene glycol / perfluoropolyether surfactant in fluorinated oil. The aqueous colloidal dispersion and oil are each injected by a syringe with a pump into a microfluidic device with a 50 μm drop junction. The system is allowed to equilibrate until monodisperse droplets are produced. The monodisperse droplets are collected in a reservoir.

[0251] The collected droplets are dried in an oven at 45° C. for 4 hours to obtain monodisperse polymer templated microspheres. The polymer templated microspheres are placed on a silicon wafer and calcined by heating from room temperature to 500° C. over 3 hours, holding at 500° C. for 2 hours, and recooling to room temperature over 3 hours. Monodisperse silica microspheres with an average diameter of 15 microns are obtained.

[0252] 2 and 3 are scanning electron microscope (SEM) images of polymer-templated microspheres and porous silica microspheres prepared in a similar manner.

[0253] [Synthesis Example 2] Drying method Repeating Example 1, the drying step utilizes microwave irradiation, drying under vacuum, and / or drying in the presence of a desiccant.

[0254] [Synthesis Example 3] Preparation of porous silica microspheres by spray drying. Styrene / acrylic acid copolymer was prepared as follows: 230 mL of deionized (DI) water is added to a three-necked reaction flask equipped with a thermometer, condenser, magnetic stirring, and nitrogen atmosphere. The water is heated to 80° C. and 10 g of styrene is added with stirring, followed by 100 mg of acrylic acid dissolved in 10 mL DI water, added via syringe. 100 mg of ammonium persulfate is dissolved in 10 mL DI water and added via syringe to the stirred mixture. The reaction mixture is stirred at 80° C. for 24 hours. The polymer colloidal dispersion is cooled to room temperature and purified by centrifugation to produce polystyrene nanospheres with an average particle size of 250 nm.

[0255] An aqueous polystyrene colloidal dispersion is diluted to 1 wt% with deionized water, 1 wt% silica nanoparticles are added, and the mixture is sonicated to prevent particle aggregation. The aqueous dispersion is spray-dried to obtain polymer-templated microspheres containing polymer nanospheres and silica. The microspheres are calcined by heating from room temperature to 500°C for 3 hours, holding at 500°C for 2 hours, and recooling to room temperature for 3 hours. Porous silica microspheres are obtained.

[0256] [Synthesis Example 4] Zinc oxide porous spheres A sample of porous zinc oxide microspheres was prepared according to the procedure of Example 3, substituting zinc oxide for silica, and the polystyrene nanospheres have an average particle size of 230 nm and a wt / wt ratio of polymer to zinc oxide of 1:2. A 0.5 mg sample of the porous microspheres was placed in a 6 cm 2 The sample appears a distinct blue color to the human eye.

[0257] [Synthesis Example 5] Silica / titania porous spheres A sample of porous microspheres containing silica and titania was prepared according to the method of Example 1, with a polymer to total metal oxide wt / wt ratio of 3:1, and a silica to titania wt / wt ratio of 9:1.

[0258] [Application Examples 1 to 3] Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B215) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 1 below.

[0259] [Table 1]

[0260] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0261] The results of the UV measurements of Application Examples 1 to 3 are shown in Figure 5. As can be seen, the addition of porous microspheres results in a clear decrease in transmission.

[0262] Irganox B215 is a compound of the formula [ka] It is a mixture of compounds TIFF0007665523000039.tif60147.

[0263] [Application Examples 4 to 7] Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Tinuvin® PA 328) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 2 below.

[0264] [Table 2]

[0265] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0266] The results of the UV measurements for application examples 4 to 7 are shown in Figure 6. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even reducing it to near zero for certain ranges of wavelengths.

[0267] Tinuvin® PA 328 has the formula [ka] It is a compound of the formula:

[0268] [Application Examples 8 and 9] Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Tinuvin® 326) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 3 below.

[0269] [Table 3]

[0270] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0271] The results of the UV measurements for application examples 8 to 9 are shown in Figure 7. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even reducing it to near zero for certain ranges of wavelengths.

[0272] Tinuvin 326® has the formula [ka] It is a compound of the formula:

[0273] [Application Examples 10 and 11] Polypropylene powder (Profax 6301, 12 g / 10 min melt flow rate) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Chimassorb® 81) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 4 below.

[0274] [Table 4]

[0275] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0276] The results of the UV measurements for Application Examples 10 and 11 are shown in Figure 8. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even to near zero for certain ranges of wavelengths.

[0277] Chimassorb® 81 has the formula [ka] It is a compound of the formula:

[0278] [Application Examples 12 and 13] Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Tinuvin® 1577) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 5 below.

[0279] [Table 5]

[0280] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0281] The results of the UV measurements for Application Examples 12 and 13 are shown in Figure 9. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even to near zero for certain ranges of wavelengths.

[0282] Tinuvin 1577® has the formula [ka] It is a compound of the formula:

[0283] [Application Examples 14 and 15] Polypropylene powder (Profax 6301, melt flow rate of 12 g / 10 min) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Uvinul® 3035) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 6 below.

[0284] [Table 6]

[0285] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0286] The results of the UV measurements for Application Examples 14 and 15 are shown in Figure 10. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even reducing it to near zero for certain ranges of wavelengths.

[0287] Uvinul 3035® has the formula [ka] It is a compound of the formula:

[0288] [Application Examples 16 and 17] Polyethylene powder (Microthene MN 700 LDPE, 20 g / 10 min melt flow rate) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Tinuvin® 326) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 7 below.

[0289] [Table 7]

[0290] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0291] The results of the UV measurements for Application Examples 16 and 17 are shown in Figure 11. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even to near zero for certain ranges of wavelengths.

[0292] [Application Examples 18 and 19] Polyethylene powder (Microthene MN 700 LDPE, 20 g / 10 min melt flow rate) is weighed into a 240 ml cup. Antioxidant (Irganox B215), UV absorber (Chimassorb® 81) and porous silica microspheres of Synthesis Example 3 are weighed and mixed with the powder. The weights of the components for each sample are listed in Table 8 below.

[0293] [Table 8]

[0294] The polymer mixture is placed into a preheated 210°C CW Brabender Plasti-Corder and mixed at 50 rpm for 3 minutes to obtain a homogenous molten mixture. The molten polymer is then compression molded at 218°C to a thickness of 250 μm, with 3 minutes of low pressure followed by 3 minutes of high pressure. The mold is then cooled in the compression molder for 3 minutes. Rectangles of 5 cm x 5 cm are cut from the sheet for UV-Vis measurements.

[0295] The results of the UV measurements for Application Examples 18 and 19 are shown in Figure 12. As can be seen, the use of a mixture of porous microspheres and UV absorbers significantly reduces the transmission, even to near zero for certain ranges of wavelengths.

[0296] Elongation at break Samples of the application examples can be exposed to an Atlas Weatherometer (WOM, ASTM G155, 0.35 W / m2 at 340 nm, dry cycle) for accelerated light weathering. Specimens of the film samples are removed at specified time intervals after exposure and tensile tested. To evaluate the decay of the mechanical properties of the samples as a result of post-oxidative degradation of the polymer, the residual tensile strength is measured using a Zwick® Z1.0 isokinetic tensiometer (according to modified ISO 527). For samples of application examples 2, 3, 6, 7, 9, 11, 13, 15, 17 and 19, the retention of the elongation at break (as % of the initial) after 1000 hours of WOM treatment is greater than 50%. The present invention includes the following embodiments. (Embodiment 1) 1. Use of porous metal oxide microspheres as light stabilizers for molded artificial polymeric articles, comprising: the polymer is a synthetic polymer and / or a natural or synthetic elastomer; the porous metal oxide spheres comprise a metal oxide; and forming a liquid dispersion of polymeric nanoparticles and a metal oxide; forming droplets of the dispersion; drying the droplets to obtain polymer template microspheres comprising the polymer nanospheres and the metal oxide; and Removing the polymer nanospheres from the template microspheres to obtain porous metal oxide microspheres. and preparing the product by a process comprising: The small spheres are Average diameter between 0.5 μm and 100 μm, an average porosity of 0.10 to 0.80; and Uses average pore diameters from 50 nm to 999 nm. (Embodiment 2) The use of embodiment 1, wherein the metal oxide is selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof. (Embodiment 3) 3. The use according to embodiment 1 or 2, wherein the porous metal oxide microspheres comprise 50.0 wt% to 99.9 wt% metal oxide based on the total weight of the microspheres. (Embodiment 4) 4. Use according to any one of the preceding embodiments, wherein the porous metal oxide microspheres have an average diameter of from 1 μm to 75 μm. (Embodiment 5) 5. The use according to any one of the preceding embodiments, wherein the porous metal oxide microspheres have an average porosity of from 0.45 to 0.65. (Embodiment 6) 6. The use according to any one of the preceding embodiments, wherein the porous metal oxide microspheres have an average pore size of from 50 nm to 800 nm. (Embodiment 7) The porous metal oxide spheres are Average diameter between 1 μm and 75 μm, an average porosity of 0.45 to 0.65; and Average pore size from 50nm to 800nm Use according to any one of embodiments 1 to 3, wherein (Embodiment 8) The porous metal oxide spheres are Average diameter between 4.5 μm and 9.9 μm, an average porosity of 0.45 to 0.65; and Average pore size from 220nm to 300nm Use according to any one of embodiments 1 to 3, wherein (Embodiment 9) The use according to any one of the preceding embodiments, wherein the porous metal oxide microspheres are used in a concentration of 0.01 wt % to 20.0 wt % based on the weight of the shaped artificial polymeric article. (Embodiment 10) The use according to any one of the preceding claims, wherein the porous metal oxide microspheres are used in combination with one or more UV absorbers, the UV absorbers being selected from the group consisting of 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones, oxalanilides, cinnamates and benzoates. (Embodiment 11) The use of embodiment 10, wherein the one or more UV absorbers are used at a concentration of 0.01 wt% to 20.0 wt% based on the weight of the molded artificial polymeric article. (Embodiment 12) Use according to any one of the preceding embodiments, wherein the molded artificial polymeric article comprises a sterically hindered amine light stabilizer (HALS). (Embodiment 13) Use according to any one of the preceding embodiments, wherein the shaped artificial polymeric article is an extruded, cast, spun, molded or calendered shaped artificial polymeric article. (Embodiment 14) Use according to any one of the preceding embodiments, wherein the shaped manmade polymeric article is a film, a pipe, a cable, a tape, a sheet, a container, a frame, a fibre or a monofilament. (Embodiment 15) 2. A shaped artificial polymeric article, wherein the polymer is a synthetic polymer and / or a natural or synthetic elastomer, and the polymer contains the porous metal oxide microspheres of embodiment 1. (Embodiment 16) 13. An extruded, cast, spun, molded or calendared polymer composition, wherein the polymer is a synthetic polymer and / or a natural or synthetic elastomer, and the polymer contains the porous metal oxide microspheres of embodiment 1.

Claims

1. Use of porous metal oxide microspheres as a light stabilizer for a polymeric article, comprising: the polymer is a synthetic polymer and / or a natural or synthetic elastomer; the porous metal oxide spheres comprise a metal oxide; and forming a liquid dispersion of polymer nanospheres and a metal oxide; forming droplets of the dispersion; drying the droplets to obtain polymer template microspheres comprising the polymer nanospheres and the metal oxide; and Removing the polymer nanospheres from the template microspheres to obtain porous metal oxide microspheres. and preparing the product by a process comprising: The small spheres are Average diameter between 0.5 μm and 100 μm, an average porosity of 0.10 to 0.80; and Uses average pore diameters from 50 nm to 999 nm.

2. 2. The use according to claim 1, wherein the metal oxide is selected from the group consisting of silica, titania, alumina, zirconia, ceria, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, and combinations thereof.

3. 3. The use according to claim 1 or 2, wherein the porous metal oxide microspheres comprise from 50.0 wt% to 99.9 wt% of metal oxide based on the total weight of the microspheres.

4. 4. The use according to any one of claims 1 to 3, wherein the porous metal oxide spheres have an average diameter of from 1 μm to 75 μm.

5. 5. The use according to any one of claims 1 to 4, wherein the porous metal oxide spheres have an average porosity of 0.45 to 0.

65.

6. 6. The use according to any one of claims 1 to 5, wherein the porous metal oxide microspheres have an average pore size of from 50 nm to 800 nm.

7. The porous metal oxide spheres are Average diameter between 1 μm and 75 μm, an average porosity of 0.45 to 0.65; and Average pore size from 50nm to 800nm 4. The use according to any one of claims 1 to 3, wherein

8. The porous metal oxide spheres are Average diameter between 4.5 μm and 9.9 μm, an average porosity of 0.45 to 0.65; and Average pore size from 220nm to 300nm 4. The use according to any one of claims 1 to 3, wherein

9. 9. Use according to any one of claims 1 to 8, wherein the porous metal oxide microspheres are used in a concentration of 0.01 wt% to 20.0 wt% relative to the weight of the polymer article.

10. 10. The use according to any one of claims 1 to 9, wherein the porous metal oxide microspheres are used in combination with one or more UV absorbers, the UV absorbers being selected from the group consisting of 2-hydroxyphenyltriazines, benzotriazoles, 2-hydroxybenzophenones, oxalanilides, cinnamates and benzoates.

11. 11. The use according to claim 10, wherein the one or more UV absorbers are used in a concentration of 0.01 wt% to 20.0 wt% relative to the weight of the polymer article.

12. The use according to any one of claims 1 to 11, wherein the polymer article comprises a sterically hindered amine light stabilizer (HALS).

13. The use according to any one of claims 1 to 12, wherein the polymeric article is an extruded, cast, spun, moulded or calendared polymeric article.

14. The use according to any one of claims 1 to 13, wherein the polymer article is a film, a pipe, a cable, a tape, a sheet, a container, a frame, a fibre or a monofilament.

15. The polymer is a synthetic polymer and / or a natural or synthetic elastomer, Average diameter between 1 μm and 75 μm, an average porosity of 0.45 to 0.65; and Average pore size from 50nm to 800nm A polymeric article comprising porous metal oxide globules having a

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