Compositions containing oxidized wet beaded carbon black

Abstract

The present invention relates to a composition, such as a rubber composition, comprising (a) an elastomeric polymeric material, and (b) an oxidized wet-beaded carbon black. The oxidized wet-beaded carbon black can be prepared by wet-beading carbon black and subsequently oxidizing the wet-beaded carbon black. The oxidized wet-beaded carbon black can be beneficially used in rubber compositions to enhance the properties of the resulting rubber product.

Description

[Technical field]

[0001] The present invention relates to a composition, such as a rubber composition, comprising (a) an elastomeric polymeric material, and (b) an oxidized wet-beaded carbon black. The oxidized wet-beaded carbon black can be prepared by wet-beading carbon black and subsequently oxidizing the wet-beaded carbon black. The oxidized wet-beaded carbon black can be beneficially used in rubber compositions to enhance the properties of the resulting rubber product. [Background technology]

[0002] Polymer compositions, such as rubber compositions, are widely applied to manufacture numerous industrial products, such as transmission and conveyor belts, tires or footwear. Carbon black is included in many polymer compositions to modify, for example, their color, mechanical, electrical, and / or processing properties. Carbon black, for example, is commonly added to rubber compositions used to manufacture tires or components thereof to impart electrical dissipative properties to the insulating matrix. At the same time, the carbon black additive affects mechanical and elastic properties, such as stiffness, abrasion resistance, and hysteresis, which greatly affect the performance of the resulting tire, for example, in terms of its rolling resistance and durability.

[0003] However, carbon black is a fine powder that is difficult to store, transport or process. To circumvent these difficulties, carbon black powder is often provided as pellets or beads having increased bulk density.

[0004] One method for providing these beads is known as wet beading, in which carbon black powder is stirred in water and then dried. Such a method is described in GB 839,918.

[0005] Dry beading in drums and feeding oxidizer directly in the dry beading drum are known in the prior art, but this technology is not applicable to rubber customers due to the low pellet strength of the dry beading product.

[0006] It is therefore an object of the present invention to provide a composition containing beaded carbon black having a high degree of oxidation and the same high pellet strength that does not adversely affect the properties of the rubber composition or rubber product, but improves the properties of the manufactured article. Summary of the Invention

[0007] Surprisingly, it has been found that the above objectives can be achieved by a composition comprising (a) an elastomeric polymeric material, and (b) an oxidized wet-beaded carbon black (202). The oxidized wet-beaded carbon black (202) is preferably prepared by wet-beading carbon black and then oxidizing the wet-beaded carbon black using ozone, preferably in a screw conveyor, to obtain the oxidized wet-beaded carbon black (202).

[0008] The composition is used to manufacture tires, preferably pneumatic tires, tire treads, belts, belt reinforcements, carcasses, carcass reinforcements, sidewalls, innerliners, apex, shoulders, hump strips, chafers, bead fillers, cable sheaths, tubes, drive belts, conveyor belts, roll covers, shoe soles, hoses, sealing members, profiles, damping elements, coatings, or colored or printed articles.

[0009] Additionally, an article made from the composition of the present invention is provided, which is preferably a tire. Additionally, a method of preparing the composition of the present invention is disclosed, which comprises: (a) mixing an elastomeric polymeric material with oxidized wet beaded carbon.

[0010] These and any other features and advantages of the present invention are described in more detail in the following description, figures, embodiments and claims. [Brief description of the drawings]

[0011] [Figure 1] A method (100) for producing oxidized wet beaded carbon black (202). [Diagram 2] The inner part of a screw conveyor (200, 300) for producing oxidized wet beaded carbon black. [Diagram 3] The outer portion of a screw conveyor (200, 300) for producing oxidized wet beaded carbon black. [Figure 4] Part of the conveyor screw (400). [Diagram 5] A portion of a conveyor screw (500) having a second helical conveyor blade (501) forming a circumferential clearance (503). [Figure 6] A portion of a conveyor screw (600) having sections (601, 602, 603) of different helical conveyor blades (501, 502). [Figure 7] A portion of the conveyor screw (700) having a second helical conveyor blade (501) and turners (702, 703) forming a circumferential clearance (503). [Figure 8] A portion of a conveyor screw (700) having a second helical conveyor blade (501) and turners (702, 703) that form a circumferential clearance (503), including the angle and direction of rotation. [Figure 9] Image of oxidized wet beaded carbon black (202). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A composition is provided that includes (a) an elastomeric polymeric material, and (b) an oxidized wet-beaded carbon black. It is particularly preferred that the composition includes the oxidized wet-beaded carbon black prepared according to the method of the present invention. Further disclosed is the manufacture of the oxidized wet-beaded carbon black according to the present invention, and the preparation of the aforementioned composition, including the addition of the oxidized wet-beaded carbon black to a composition that includes an elastomeric polymeric material. Thus, a composition, such as a rubber composition, is provided as described herein. The rubber composition is widely applied to manufacture numerous industrial products, such as transmission and conveyor belts, tires or footwear.

[0013] "Carbon black" as referred to herein means carbon produced by thermal oxidative pyrolysis or thermal splitting of a carbon feedstock, and which is substantially composed of carbon, for example, more than 80%, more than 90% or more than 95% by weight based on the total amount. Various industrial methods are known for producing carbon black, such as the furnace process, the gas black process, the acetylene black process, the thermal black process or the lamp black process. The production of carbon black is well known per se in the art and is reviewed, for example, in J.-B. Donet et al., "Carbon Black: Science and Technology", 2nd Edition, and will not be described in further detail here. Carbon black refers to carbon black in powder form, unless otherwise stated. Wet carbon black refers to carbon black powder comprising water and optionally a binder. Beaded carbon black refers to either dry or wet beaded carbon black. Oxidized wet beaded carbon black refers to carbon black produced according to the present invention, where, unless otherwise stated, the carbon black is first beaded and then oxidized. The terms beads and pellets are used synonymously. Oxidized carbon black generally has significant oxygen content and oxygen-containing functional groups, including, but not limited to, quinone, carboxy, phenol, lactol, lactone, anhydride and ketone groups. The screw conveyor according to the present invention is a screw conveyor designed for the oxidation of carbon black beads. Diameter always refers to the inside diameter unless otherwise specified.

[0014] Carbon black is included in many polymer compositions to modify, for example, their color, mechanical, electrical, and / or processing properties. Carbon black, for example, is commonly added to rubber compositions used to manufacture tires or components thereof to impart electrical dissipative properties to the insulating matrix. At the same time, carbon black additives affect mechanical and elastic properties such as stiffness, abrasion resistance, and hysteresis, which greatly affect the performance of the resulting tire, for example, in terms of its rolling resistance and durability.

[0015] The term "composition" as used herein refers to a material composed of multiple constituent chemical species or components. An "elastomeric polymeric material" is understood as a material consisting essentially of an elastomeric polymer. The term "polymer" is used herein in its general sense in the art to refer to a polymeric compound, i.e., a compound having a relatively high molecular weight (e.g., 500 Da or more), the structure of which includes multiple repeat units (also called "mers") that are actually or conceptually derived from a relatively low molecular weight chemical species. The term "elastomeric polymer" is used herein in its general sense in the art to refer to a polymer that is elastic.

[0016] Particularly useful as elastomeric polymeric materials (or elastomeric polymeric materials) for the implementation of the present invention are elastomers, such as rubber materials. The elastomeric polymeric material (a) of the composition according to the present invention may comprise one or more rubbers. The terms "rubber", "rubber material" and "elastomer" may be used interchangeably throughout the present specification, unless otherwise specified. Rubbers that may be used according to the present invention include those containing olefinic unsaturation, i.e., diene-based rubber materials, as well as non-diene-based rubber materials. The term "diene-based rubber material" is intended to include both natural and synthetic rubbers, or mixtures thereof. The elastomeric polymeric material (a) may consist of synthetic rubber.

[0017] The elastomeric polymer material (a) of the composition according to the invention may comprise natural and / or synthetic rubber.

[0018] Natural rubber can be used in its raw form and in various processed forms conventionally known in the art of rubber processing. Natural rubber can be obtained, for example, from the rubber tree (Herbia brasiliensis), guayule, and dandelion. Thus, the elastomeric polymer material (a) can comprise or consist of natural rubber.

[0019] Synthetic rubbers can include styrene-butadiene rubbers, such as emulsion-styrene-butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber, or a mixture of any of the above in combination. According to the present invention, synthetic rubbers can also be obtained from renewable materials. For example, polybutadiene can be produced from alcohol obtained by fermentation of plant biomass.

[0020] Suitable rubbers may also include functionalized rubbers and rubbers bonded to silicon or tin. For example, the rubber may be functionalized with functional groups such as amine, alkoxy, silyl, thiol, thioester, thioether, sulfanyl, mercapto, sulfide, or combinations thereof. The one or more functional groups may be primary, secondary, or tertiary, and may be located at one or both chain ends (e.g., alpha, omega functionalization), pendant from the polymer backbone, and / or provided within the chain of the polymer backbone. The rubber according to the present invention may also be partially crosslinked. Thus, prior to use in the composition of the present invention, a portion of the polymer chains of the rubber material may be crosslinked by means of a coupling agent or without a coupling agent.

[0021] The composition according to the invention may in particular be a curable composition, for example a vulcanizable rubber composition. The term "vulcanizable rubber composition" refers to a composition of rubber components, optionally including various additional components conventionally used in the art of rubber compounding, that can be cured by vulcanization under the formation of a vulcanizate. The terms "curable" and "vulcanizable" are used interchangeably throughout the present specification, unless otherwise stated, and refer to a chemical reaction that links polymer chains together by a crosslinking or vulcanizing agent. The curing reaction can be induced by any means known in the art, such as the addition of light, moisture, heat and / or a crosslinking agent.

[0022] The elastomeric polymeric material (a) according to the present invention may comprise natural rubber. According to the present invention, the natural rubber may comprise natural rubber obtained from rubber trees (Herbia brasiliensis), guayule, dandelion, or a mixture of any combination of the above. The natural rubber may comprise natural rubber obtained from guayule and / or dandelion. The elastomeric polymeric material (a) may comprise 5 phr or more, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more of natural rubber. As used herein, the term "phr" refers to the parts by weight of the listed individual material per 100 parts by weight of rubber or elastomer. The elastomeric polymer material (a) may contain natural rubber at 100 phr or less, for example 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr or less, or 70 phr or less, or 65 phr or less, or 60 phr or less. The elastomeric polymer material (a) may contain natural rubber in a range between any of the above lower and upper limits. For example, the elastomeric polymer material (a) may contain natural rubber in a range of 5 to 95 phr, for example 10 to 90 phr, or 20 to 80 phr, or 30 to 70 phr, or 40 to 60 phr. According to the present invention, the elastomeric polymer material (a) may consist of natural rubber.

[0023] The elastomeric polymer material (a) according to the present invention may comprise synthetic rubber. According to the present invention, the synthetic rubber may comprise synthetic rubber obtained from renewable materials. The renewable material according to the present invention may be alcohol obtained by fermentation of plant biomass. For example, the synthetic rubber may comprise polybutadiene obtained from alcohol obtained by fermentation of plant biomass. The elastomeric polymer material (a) may comprise 5 phr or more, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more of synthetic rubber. As used herein, the term "phr" refers to the parts by weight of the listed individual material per 100 parts by weight of rubber or elastomer. The elastomeric polymer material (a) may comprise synthetic rubber in an amount of 100 phr or less, for example 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr or less, or 70 phr or less, or 65 phr or less, or 60 phr or less. The elastomeric polymer material (a) may comprise synthetic rubber in a range between any of the above lower and upper limits. For example, the elastomeric polymer material (a) may comprise synthetic rubber in a range of 5 to 95 phr, for example 10 to 90 phr, or 20 to 80 phr, or 30 to 70 phr, or 40 to 60 phr. According to the present invention, the elastomeric polymer material (a) may comprise synthetic rubber.

[0024] According to the present invention, the elastomeric polymer material (a) may comprise a mixture of natural and synthetic rubber. The elastomeric polymer material (a) may comprise 5-100 phr of natural rubber and 5-100 phr of synthetic rubber, for example 10-90 phr of natural rubber and 10-90 phr of synthetic rubber, or 20-80 phr of natural rubber and 20-80 phr of synthetic rubber, or 30-70 phr of natural rubber and 30-70 phr of synthetic rubber, or 40-60 phr of natural rubber and 40-60 phr of synthetic rubber, or 40-100 phr of natural rubber and 5-60 phr of synthetic rubber, or 50-95 phr of natural rubber and 5-50 phr of synthetic rubber, or 60-90 phr of natural rubber and 10-50 phr of synthetic rubber, or 5-40 phr of natural rubber and 60-100 phr of synthetic rubber, or 10-20 phr of natural rubber and 80-90 phr of synthetic rubber. For example, the elastomeric polymeric material (a) may comprise 50 phr of natural rubber and 50 phr of synthetic rubber, or the elastomeric polymeric material (a) may comprise 5 phr of natural rubber and 95 phr of synthetic rubber.

[0025] The synthetic rubber according to the present invention preferably comprises emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, more preferably polyisoprene and / or polybutadiene, even more preferably polybutadiene. The synthetic rubber according to the present invention preferably comprises emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, more preferably polyisoprene and / or polybutadiene, even more preferably polybutadiene. The synthetic rubber may comprise emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene. The synthetic rubber may comprise or consist of polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.The synthetic rubber may comprise or consist of polybutadiene, polyisoprene, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0026] The oxidized wet beaded carbon black can be or be derived from plasma black, gas black, channel black, thermal black, lamp black or furnace black, preferably furnace black.

[0027] The oxidized wet beaded carbon black can also be ground before being added to the composition. Thus, the composition can include ground oxidized wet beaded carbon black.

[0028] Additionally, the composition can include a mixture of oxidized wet-beaded carbon black and additional carbon black, such as oxidized dry-beaded carbon black, beaded carbon black, carbon black powder, and oxidized carbon black powder. For example, the composition can include 1 to 100% by weight of oxidized wet-beaded carbon black and 1 to 99% by weight of additional carbon black, based on the total weight of carbon black in the composition.

[0029] The composition may comprise 3 to 200 phr of the oxidized wet beaded carbon black (b), preferably 5 to 190 phr of the oxidized wet beaded carbon black (b), more preferably 10 to 150 phr, even more preferably 20 to 130 phr of the oxidized wet beaded carbon black (b), and most preferably 30 to 100 phr of the oxidized wet beaded carbon black (b).

[0030] The composition may include one or more additives selected from vulcanizing agents, curing aids such as primary and secondary vulcanization accelerators, activators and pre-vulcanization inhibitors, processing additives such as oils, waxes, resins, plasticizers, softeners, rheology modifiers, pigments, peptizers, coupling agents, surfactants, biocides, and anti-degradants such as heat or light stabilizers, antioxidants and antiozonants, metal oxides, metal hydroxides, and filler materials such as silica, organosilica, carbon nanotubes, carbon fibers, graphite, and metal fibers.

[0031] The composition of the present invention can be obtained and processed by common elastomer processing techniques. The composition according to the present invention can be obtained, for example, by mixing the oxidized wet-beaded carbon black (b) of the present invention and optional ingredients (if used) with the elastomeric polymer material (a) and dispersing, for example, the oxidized wet-beaded carbon black (b) and optional ingredients (if used) in the elastomeric polymer material (a). Dispersion can be achieved by any means known in the art, such as mixing, stirring, grinding, kneading, ultrasonic, dissolver, shaker mixer, rotor stirring dispersion assembly or high pressure homogenizer or combinations thereof. For example, a lab mixer with intermeshing rotor geometry can be used. Dispersion can be carried out, for example, until the oxidized wet-beaded carbon black (b) is homogeneously dispersed in the elastomeric polymer material (a) with a dispersion index of 95% or more, preferably 97% or more, or 99% or more, as classified according to ASTM D2663-88 test method B.

[0032] The preparation of the composition according to the invention can be carried out, for example, in a multi-step process. First, the oxidized wet-beaded carbon black (b) and optionally non-curable additives (if used) can be added simultaneously or successively to the elastomeric polymer material (a). The elastomeric polymer material (a), the oxidized wet-beaded carbon black (b) and additives (if used) can then be mixed at a temperature typically ranging from 40°C to 160°C for a total mixing time of less than 10 minutes, for example in the range of 2 to 8 minutes. The resulting mixture can then be blended with one or more curable additives at a temperature of less than 115°C for less than 5 minutes, typically less than 3 minutes, preferably about 2.5 minutes.

[0033] The method may include further steps such as extruding the product or cooling it to room temperature and storing it for further processing. The method may further include a curing step, which may be carried out, for example, by subjecting the composition to thermal curing conditions, for example, a temperature of 120-200° C. for 5 minutes to 3 hours. Curing may be carried out, for example, in a curing press, at a temperature of, for example, 140-180° C. for 5-60 minutes and a pressure of 100-150 bar.

[0034] As can be seen, the compositions according to the invention can be utilized in various technical applications requiring polymer-based materials containing carbon black fillers, for example to impart antistatic or conductive properties, color, mechanical reinforcement and / or low hysteresis properties. Mechanical properties of interest, particularly in the manufacture of tires, include tear resistance, rebound and hysteresis. The compositions according to the invention provide cured compositions with good and beneficial mechanical properties, particularly for the manufacture of tires. Beneficial mechanical properties according to the invention are, for example, high tensile strength, high rebound and low hysteresis. The compositions according to the invention provide cured compositions with mechanical properties comparable to those of conventional rubber compositions containing carbon black.

[0035] Therefore, the present invention also relates to articles, particularly tires, made from or containing the aforementioned compositions according to the present invention. Tires according to the present invention can include treads, carcasses, sidewalls, innerliners, apex, shoulders, hump strips, chafers, and / or bead fillers, at least one of which is made from or contains the compositions according to the present invention. Such tires include, for example, but are not limited to, truck tires, passenger tires, off-the-road tires, aircraft tires, agricultural tires, and earthmoving tires.

[0036] The tire may include a sidewall, the sidewall being made from a composition according to the present invention, the composition preferably comprising (a) 40 to 60 phr of natural rubber and 40 to 60 phr of synthetic rubber, preferably 50 to 60 phr of natural rubber and 40 to 50 phr of synthetic rubber, more preferably 55 phr of natural rubber and 45 phr of synthetic rubber, and (b) 30 to 70 phr of oxidized wet beaded carbon black, preferably 40 to 60 phr of oxidized wet beaded carbon black, preferably 50 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene.

[0037] The tire may comprise a carcass, the carcass being made from a composition according to the present invention, the composition preferably comprising (a) 40-80 phr of natural rubber and 20-60 phr of synthetic rubber, preferably 50-70 phr of natural rubber and 30-50 phr of synthetic rubber, more preferably 60 phr of natural rubber and 40 phr of synthetic rubber, and (b) 5-70 phr of oxidized wet beaded carbon black, preferably 40-60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises polybutadiene and emulsion styrene-butadiene rubber (ESBR), more preferably 20 phr of polybutadiene and 20 phr of emulsion styrene-butadiene rubber (ESBR).

[0038] The tire comprises a chafer, the chafer being made from a composition according to the present invention, the composition preferably comprising (a) 30-70 phr of natural rubber and 30-70 phr of synthetic rubber, preferably 40-60 phr of natural rubber and 40-60 phr of synthetic rubber, more preferably 50 phr of natural rubber and 50 phr of synthetic rubber, and (b) 55-95 phr of oxidized wet beaded carbon black, preferably 65-85 phr of oxidized wet beaded carbon black, preferably 75 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises emulsion styrene-butadiene rubber (ESBR), more preferably emulsion styrene-butadiene rubber (ESBR).

[0039] The tire may comprise a bead filler and / or apex, the bead filler and / or apex being made from a composition according to the present invention, the composition preferably comprising (a) 80 to 100 phr of natural rubber, preferably 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber, and (b) 35 to 75 phr of oxidized wet beaded carbon black, preferably 45 to 65 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black.

[0040] The tire may include an innerliner, the innerliner being made from a composition according to the present invention, the composition preferably comprising (a) 80 to 100 phr of synthetic rubber, preferably 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, and (b) 40 to 80 phr of oxidized wet beaded carbon black, preferably 50 to 70 phr of oxidized wet beaded carbon black, more preferably 60 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises, more preferably consists of, a halogenated butyl rubber.

[0041] The tire may include a tread, preferably a truck tire, the tread being made from a composition according to the present invention, the composition preferably comprising (a) 60-95 phr of natural rubber and 5-40 phr of synthetic rubber, preferably 70-85 phr of natural rubber and 15-30 phr of synthetic rubber, more preferably 80 phr of natural rubber and 20 phr of synthetic rubber, and (b) 30-70 phr of oxidized wet beaded carbon black, preferably 40-60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene.

[0042] The tire may comprise a tread, preferably a passenger tire, the tread being made from a composition according to the present invention, the composition preferably comprising (a) 80-100 phr of synthetic rubber, preferably 90-100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, and (b) 35-75 phr of oxidized wet beaded carbon black, preferably 45-65 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene.

[0043] The tire may comprise a tread, preferably a passenger tire, the tread being made from a composition according to the present invention, the composition preferably comprising: (a) 80-100 phr of synthetic rubber, preferably 90-100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber; (b) 35-75 phr of oxidized wet beaded carbon black, preferably 45-65 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black; and (c) 60-100 phr of silica, preferably 70-90 phr of silica, more preferably 80 phr of silica, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene.

[0044] The tire may comprise a tread, preferably an off-the-road (OTR) tire, the tread being made from a composition according to the present invention, the composition preferably comprising (a) 80 to 100 phr of natural rubber, preferably 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber, and (b) 35 to 75 phr of oxidized wet beaded carbon black, preferably 45 to 75 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black.

[0045] The article may be a cable sheath, a tube, a drive belt, a conveyor belt, a roll cover, a shoe sole, a hose, a seal, a profile, a damping element, a coating, or a coloured or printed article.

[0046] Further, the article may be a conveyor belt, the conveyor belt being made from a composition according to the present invention, the composition preferably comprising (a) 60-95 phr of natural rubber and 5-40 phr of synthetic rubber, preferably 70-85 phr of natural rubber and 15-30 phr of synthetic rubber, more preferably 80 phr of natural rubber and 20 phr of synthetic rubber, and (b) 30-70 phr of oxidized wet beaded carbon black, preferably 40-60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene.

[0047] Furthermore, the present invention relates to the use of the above-mentioned composition according to the invention for producing a tire, preferably a pneumatic tire, a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, an inner liner, an apex, a shoulder, a hump strip, a chafer, a bead filler, a cable sheath, a tube, a drive belt, a conveyor belt, a roll cover, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating or a colored or printed article.

[0048] Further disclosed is a method for preparing a composition, preferably a composition according to the present invention, comprising mixing an elastomeric polymeric material with oxidized wet beaded carbon. Further disclosed is the use of oxidized wet beaded carbon to prepare a rubber composition.

[0049] Oxidized wet-beaded carbon black preferably refers to carbon black that has been wet-beaded and subsequently oxidized, as described below.

[0050] 1. A method for producing oxidized wet-beaded carbon black, comprising the steps of: (a) providing carbon black; (b) wet-beading the carbon black obtained in step (a) to obtain wet-beaded carbon black; and (c) oxidizing the wet-beaded carbon black obtained in step (b) in a reaction chamber to obtain oxidized wet-beaded carbon black.

[0051] Thus, a process is provided in which carbon black beads (provided by wet-beading), such as dry carbon black beads, are subsequently oxidized. The carbon black beads obtained after wet-beading generally refer to dried beads. Drying means that the wet beads are subjected to a drying step. The moisture content of the dry beads after wet-beading can be up to 5% by weight, such as 4% by weight, for example 0.001-5% by weight, 0.01-4% by weight, 0.1-3% by weight. Preferably, the wet-beaded carbon black has a moisture content of 0.01-2% by weight. The weight % refers to the total weight of the wet-beaded carbon black. The obtained oxidized wet-beaded carbon black can be used in the composition of the present invention.

[0052] Oxidized wet-beaded carbon black has, among other things, high pellet crush strength and low pellet attrition. At the same time, the volatile content can be controlled during production without the risk of losing volatile content (i.e., reducing the degree of oxidation) during the drying or beading process. In other words, the oxidation products are not exposed to high temperatures because the oxidation occurs after wet-beading (including drying) of the carbon black, and therefore the oxidation can be controlled more efficiently. Furthermore, the properties of rubber products can be improved by using oxidized wet-beaded carbon black.

[0053] In addition, the wet beading of carbon black depends on the specific carbon black powder material, and therefore the drying process varies depending on the carbon black powder material. Thus, methods that require a higher amount of energy for drying result in a higher loss of volatiles on the surface of the oxidized wet beaded carbon black. The novel and inventive method overcomes such limitations, thereby providing a more versatile method.

[0054] The oxidation in step (c) can be carried out in a screw conveyor comprising a reaction chamber as mentioned in step (c) and at least one ozone inlet for supplying ozone to the reaction chamber. The wet beaded carbon black obtained in step (a) can be fed to the reaction chamber of a screw conveyor, in particular a screw conveyor. The screw conveyor is further described below. However, the method of the present invention is not limited to a screw conveyor and can be carried out in any reactor, in particular a reactor that can prevent the destruction of beads during oxidation. Nevertheless, a screw conveyor is particularly preferred for wet beaded carbon black.

[0055] The speed of the screw (screw of the screw conveyor) is desirably 0.01 to 10 rpm, preferably 0.1 to 5 rpm, more preferably 0.2 to 3 rpm, even more preferably 0.3 to 2.5 rpm, and most preferably 0.4 to 1 rpm. In general, the screw rotation speed is not limited to a specific value. The screw rotation speed may have an effect on the properties of the oxidized wet beaded carbon black produced. For example, a lower screw rotation speed results in a higher volatile content of the oxidized wet beaded carbon black produced, since the wet beaded carbon black resides longer in the reaction chamber. Thus, if the desired volatile content is to be constant, a lower screw rotation speed may require a lower supply of ozone (or ozone flow rate, such as a set ozone flow rate). The screw rotation speed is desirably set to a value at which no or only minimal bead destruction is observed. The optimal rotation speed may depend on the particular wet beaded carbon black material to be oxidized. Therefore, it is recommended to measure the optimal rotation speed of the screw of the particular screw conveyor as well as the wet beaded carbon black. The measurements are the rotation speed n(t) and the motor current I required for the rotation speed n(t). set The set rotation speed n(t) can be stored in a lookup table as screw rotation speed n(t). As mentioned above, the set rotation speed n(t) should be the rotation speed at which no or only minimal bead breakage is observed. Additionally, the required flow of oxidizing agent (such as ozone) can be determined and stored in the lookup for the desired oxidized wet beaded carbon black. The user can increase or decrease the screw rotation speed or ozone flow rate as needed during the process.

[0056] The screw rotation speed has an effect on pellet crushing strength, pellet wear, and fines content, as well as bead breakage. A high screw rotation speed results in a higher throughput of the process. During the oxidation step (c), at least 80%, preferably 90%, more preferably 95% of the pellets should not be crushed.

[0057] The carbon black in step (a) is generally provided as a powder. Any type of carbon black powder material, such as acetylene black, channel black, furnace black, lamp black and thermal black, can be used according to the present invention. Furnace black is particularly preferred. A crusher can further pulverize the carbon black powder before wet beading.

[0058] The statistical thickness surface area (STSA) of the carbon black from step (a), as measured in accordance with ASTM D6556-17, is between 30 and 190 m 2 / g, preferably 50 to 160m 2 / g, more preferably 100 to 140m 2 / g, most preferably 110-120m 2 / g, and the compressed oil absorption (COAN) measured according to ASTM D3493-18 may be in the range of 55 to 150 mL / 100 g, preferably 80 to 120 mL / 100 g, and more preferably 90 to 115 mL / 100 g.

[0059] The carbon black from step (a) has a BET surface area, measured in accordance with ASTM D6556-17, of between 30 and 200 m 2 / g, preferably 50 to 170m 2 / g, more preferably 100 to 150m 2 / g, and the oil absorption (OAN) measured according to ASTM D2414-18 may be in the range of 60 to 180 mL / 100 g, preferably 85 to 140 mL / 100 g, more preferably 100 to 130 mL / 100 g.

[0060] Generally, the BET surface area can be measured by nitrogen adsorption according to ASTM D6556-17.

[0061] The carbon black from step (a) has a BET surface area, measured in accordance with ASTM D6556-17, of between 40 and 100 m 2 / g, preferably 50 to 80m2 / g, more preferably 55 to 70m 2 / g, and the oil absorption (OAN) measured according to ASTM D2414-18 may be in the range of 150 to 450 mL / 100 g, preferably 200 to 320 mL / 100 g, more preferably 240 to 300 mL / 100 g.

[0062] The carbon black from step (a) has a BET surface area, measured in accordance with ASTM D6556-17, of between 10 and 100 m 2 / g, preferably 20 to 90m 2 / g, more preferably 25 to 80m 2 / g, and the oil absorption (OAN) measured according to ASTM D2414-18 may be in the range of 20 to 180 mL / 100 g, preferably 30 to 160 mL / 100 g, more preferably 40 to 150 mL / 100 g.

[0063] The carbon black from step (a) has a BET surface area, measured in accordance with ASTM D6556-17, of between 200 and 600 m 2 / g, preferably 250 to 500m 2 / g, more preferably 300 to 450m 2 / g, and the oil absorption (OAN) measured according to ASTM D2414-18 may be in the range of 50 to 200 mL / 100 g, preferably 60 to 120 mL / 100 g, more preferably 70 to 100 mL / 100 g.

[0064] The carbon black from step (a) has a BET surface area, as measured in accordance with ASTM D6556-17, of between 15 and 500 m 2 / g, preferably 30 to 300m 2 / g, more preferably 40 to 250m 2 / g, and even more preferably 50 to 200 m 2 / g, and most preferably in the range of 70 to 150 m / g.

[0065] The oil absorption number (OAN) of the carbon black according to step (a), measured according to ASTM D2414-18, may be in the range of 30-350 mL / 100 g, preferably 40-300 mL / 100 g, more preferably 50-150 mL / 100 g, even more preferably 100-290 mL / 100 g, and most preferably 40-150 mL / 100 g.

[0066] For oxidation, any oxidizing agent can be used. The method according to the invention is not limited to a specific oxidizing agent. In step (c), ozone, H2O2 and / or NOx (such as HNO3) can be used for oxidation. Ozone is particularly preferred since it can be easily obtained from an ozone generator using air. Furthermore, a reduction in oxidation / corrosion of the equipment is observed by using ozone instead of NOx, which is particularly useful for screw conveyors that include moving parts such as screws. However, if a specific functional group is desired on the surface of the carbon black, a different oxidizing agent such as NOx can be used.

[0067] High concentrations of ozone can be used in the reaction chamber for oxidation. The concentration or amount of ozone in the reaction chamber depends on the degree of oxidation (amount of volatiles) desired. The concentration of ozone should be highest at the ozone inlet and decrease towards the outlet of the produced oxidized wet beaded carbon black. It is desirable that the ozone reacts completely with the wet beaded carbon black. Therefore, it is desirable that there is substantially no ozone at the outlet of the reaction chamber, or that the amount of ozone is less than 0.1% by weight of the gas present at the outlet of the reaction chamber. The ozone concentration or amount of ozone can be adjusted by the ozone flow rate into the reaction chamber. It is desirable that 0.1 to 95% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, even more preferably 1.5 to 15% by weight, and most preferably 2 to 10% by weight of the gas present in the reaction chamber is ozone, and / or the gas provided to the reaction chamber via the ozone inlet is ozone. Usually, 0.5 to 5% by weight of the gas present in the reaction chamber is ozone. In particular, ozone-enriched air is used for the oxidation step containing the amounts or concentrations referred to herein. The concentration of ozone in the reaction chamber or provided to the reaction chamber via the ozone inlet is between 1 and 300 g / m 3 , for example 1 to 200 g / m 3 , 1~50g / m 3 , 1~60g / m 3 , 15~60g / m 3 , 15~60g / m 3 , or 15 to 50 g / m 3The ozone concentration or amount of ozone in the reaction chamber can take into account the concentration gradient in the reaction chamber. Thus, the overall ozone concentration or amount of ozone in the entire reaction chamber is generally taken into account. Thus, as long as the overall concentration complies with the above range, the ozone concentration at the ozone inlet can be above the above maximum value or below the above minimum value at the outlet. The ozone flow rate can be 100-50000 g / h, for example, 300-5000 g / h, 300-30000 g / h, 500-10000 g / h, 800-5000 g / h, 5000-30000 g / h, or 1000-30000 g / h. The ozone flow rate can be adjusted as desired depending on the degree of oxidation. Furthermore, the ozone flow rate depends on the size of the screw conveyor. When a large screw conveyor is used, a higher ozone flow rate should be utilized. The ozone provided to the reaction chamber via the ozone inlet can be derived from air or liquid oxygen.

[0068] Typically, the ozone concentration is adjusted / controlled to provide a volatile content of 1-25 wt%, e.g., 1.5-20 wt%, 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%, measured at 950° C. Thus, the ozone concentration in the reaction chamber should be adjusted / controlled to achieve the desired volatile content.

[0069] For example, the ozone flow rate to the reactor can be adjusted / controlled to adjust / control the ozone concentration. Ozone concentration refers to the ozone concentration as the wet beaded carbon black is processed, e.g., the ozone concentration in the reactor or reactor chamber.

[0070] The volatile content at 950°C can also be adjusted / controlled by the air flow rate and residence time of the wet beaded carbon black. The residence time of the wet beaded carbon black can be adjusted by the feed rate of the wet beaded carbon black and / or the screw rotation speed.

[0071] Typically, the air flow rate is adjusted / controlled such that the volatile content measured at 950° C. is 1-25 wt%, e.g., 1.5-20 wt%, 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 5-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%. For example, air flows into the reaction chamber.

[0072] Typically, the residence time of the wet beaded carbon black is adjusted / controlled such that the volatile content measured at 950° C. is 1-25 wt%, e.g., 1.5-20 wt%, 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 5-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%. e.g., residence time of the wet beaded carbon black in the reaction chamber.

[0073] Typically, the screw rotation speed is adjusted / controlled such that the volatile content measured at 950° C. is 1-25 wt%, e.g., 1.5-20 wt%, 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 5-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%, e.g., the screw rotation speed of a screw conveyor.

[0074] The ozone concentration, air flow rate, residence time of the wet beaded carbon black, and / or screw rotation speed can be adjusted / controlled such that the volatile content measured at 950° C. is 1-25 wt%, e.g., 1.5-20 wt%, 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 5-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%.

[0075] The volatile content at 950 °C can be measured using a thermogravimetric analyzer (TGA-701) manufactured by Fa.LECO Instruments according to the following procedure. The sample pan is dried at 650 °C for 30 min. The carbon black material is stored in a desiccator with desiccant prior to measurement. The baked-out sample pan is loaded into the instrument, tared, and filled with 0.5 g to 10 g of carbon black material. The oven of the TGA instrument loaded with the sample-loaded pan is then gradually heated to 105 °C by automated software control to dry the sample until a constant mass is achieved. The pan is then closed with a lid, the oven is purged with nitrogen (99.9 vol.% grade), and heated to 950 °C. The oven temperature is maintained at 950 °C for 7 min. The volatile content at 950 °C is calculated using the following formula:

number

[0076] The weight ratio of the wet beaded carbon black (e.g., dry weight of carbon black) to the ozone for oxidation in step (c) should be greater than 1, preferably greater than or equal to 3, more preferably greater than or equal to 4. In particular, the weight ratio of the wet beaded carbon black (e.g., dry weight of carbon black) to the ozone for oxidation in step (c) should be 1:1 to 15:1, preferably 1.1:1 to 13:1, more preferably 1.5:1 to 10:1, even more preferably 2:1 to 8:1, and most preferably 3:1 to 6:1.

[0077] The temperature of the oxidation in step (c) is 10-60°C, preferably 20-50°C, more preferably 30-45°C. In particular, the temperature in the reaction chamber is 10-60°C, preferably 20-50°C, more preferably 30-45°C. The temperature in the screw conveyor can be controlled by a liquid or fluid, e.g. water, attached to the screw conveyor or the barrel of the screw conveyor. Thus, the screw conveyor can include a temperature control unit for cooling or heating. It is desirable that the temperature for the reaction chamber or oxidation is controlled so that no loss of volatiles occurs during the oxidation. In general, the oxidation of wet beaded carbon black is an exothermic reaction and heat should be dissipated. This may be particularly relevant for processes in which highly oxidized carbon black or highly oxidized wet beaded carbon black is obtained. However, in processes in which less oxidized carbon black is obtained, it may be beneficial to transfer additional heat to the reaction chamber for the oxidation step.

[0078] Wet beading (b) generally includes the steps of (b1) treating carbon black with water to obtain wet carbon black, (b2) beading the wet carbon black to obtain beaded carbon black containing water, and (b3) drying the beaded carbon black to obtain wet beaded carbon black (201).

[0079] The moisture content of the wet beaded carbon black should be less than 10% by weight, more preferably less than 5% by weight, even more preferably 0.001-4% by weight, and most preferably 0.01-1% by weight. This means that after the aforementioned drying step, most of the moisture content is removed, so that the oxidation is carried out using an already dried wet beaded carbon black. Therefore, it is preferred that the oxidation is carried out using a dried wet beaded carbon black.

[0080] Wet beading is usually carried out in a "wet beading box" equipped with a number of agitating pins that extend longitudinally through the body and are attached to a shaft that rotates at speeds up to about 240 rpm depending on the type of carbon black powder. The action of the pins causes the wet carbon black to form into beads or pellets, which are then dried in a dryer. However, any type of wet beading equipment can be used for wet beading.

[0081] The weight of water used for beading is usually equal to the weight of the carbon black powder to be beaded. The range can be 5% to 1000% by weight based on the total weight of the carbon black. Preferably, it is 20 to 200% by weight, more preferably 50 to 150% by weight, based on the total weight of the carbon black.

[0082] The water for wet beading usually contains a binder, preferably the binder contains molasses and / or lignosulfonate. Such binder is uniformly dispersed throughout the beads. The binder can increase the crush strength and packing point of the carbon black beads. The binder can be present in an amount of 0.01-1.00% by weight, preferably 0.05-0.9% by weight, more preferably 0.1-0.80% by weight, based on the total weight of the carbon black, especially the carbon black for wet beading. The weight ratio of the binder to the carbon black for wet beading is 1 / 10000-1 / 100, preferably 1-1 / 2000-1 / 110, more preferably 1 / 1000-1 / 125.

[0083] The pellet size (or bead size) of the wet beaded carbon black and / or oxidized wet beaded carbon black (used in the present invention) can be 10 mm or less, preferably 5 mm or less, more preferably 3 mm or less. At least 90% by weight of the wet beaded carbon black and / or oxidized wet beaded carbon black, based on the total weight of the wet beaded carbon black and / or oxidized wet beaded carbon black, can have a pellet size of 0.1 to 20 mm, preferably 0.1 to 15 mm, more preferably 0.1 to 10 mm, and most preferably 0.5 to 10 mm. In other words, (a) 10 to 90% by weight oxidized wet beaded carbon black can have a pellet size of 0.1 to 10 mm, preferably 0.5 to 6 mm, more preferably 0.5 to 5 mm, (b) 30 to 90% by weight oxidized wet beaded carbon black can have a pellet size of 0.1 to 10 mm, preferably 0.5 to 6 mm, more preferably 0.5 to 5 mm, (c) 50 to 90% by weight oxidized wet beaded carbon black can have a pellet size of 0.1 to 10 mm, preferably 0.5 to 6 mm, more preferably 0.5 to 5 mm, or (d) 70 to 90% by weight oxidized wet beaded carbon black can have a pellet size of 0.1 to 10 mm, preferably 0.5 to 6 mm, more preferably 0.5 to 5 mm.

[0084] The bulk density of the wet beaded carbon black is usually more than 150 g / L, preferably 150 to 600 g / L, more preferably 300 to 500 g / L. The bulk density can be measured according to ASTM D1513-05.

[0085] Air flow rate to reaction chamber is 5~1000Nm 3 / h, e.g. 5-200Nm 3 / h, 10~150Nm 3 / h, 15~100Nm 3 / h, 20~50Nm 3 / h, 10~600Nm 3 / h, 15~300Nm 3 / h, 10~600Nm 3 / h, 100~800Nm 3 / h, or 200-600Nm 3 / h. The air flow rate generally depends on the set ozone flow rate. In addition, the air flow rate depends on the size of the reaction chamber. Larger reaction chambers usually require higher air flow rates. The wet beaded carbon black feed to the reaction chamber can be 0.01-1000g / s, e.g., 1-500g / s, 100-600g / s, 0.05-50g / s, 0.08-20g / s, or 0.08-5g / s.

[0086] For the oxidized wet beaded carbon black used in the composition of the present invention, the volatile content measured at 950°C should be 1-25 wt%, and the average pellet crush strength of pellets with diameters of 0.71-1.0 mm should be 4-80 cN, preferably 5-50 cN, more preferably 10-40 cN. The pellet crush strength, e.g., the average pellet crush strength, can be measured according to ASTM D5230-19. In particular, the volatile content of the oxidized wet beaded carbon black measured at 950°C is 1.5-20 wt%, e.g., 1-10 wt%, 1.5-10 wt%, 1.5-20 wt%, 2-10 wt%, 2-15 wt%, 2.5-10 wt%, 3-7 wt%, or 3.5-7 wt%. The volatile content of the wet beaded carbon black according to the present invention measured at 950°C is preferably 2.2-25% by weight, preferably 2.2-20% by weight, more preferably 2.2-15% by weight, even more preferably 3-15% by weight, and most preferably 3-10% by weight. Surprisingly, it has been found that oxidized wet beaded carbon black can be produced having a high volatile content measured at 950°C and at the same time a high pellet crushing strength, especially when the wet beaded carbon black is produced by subsequent oxidation, by using a screw conveyor as the oxidation unit. Furthermore, the oxidized wet beaded carbon black can be beneficially used in rubber compositions to enhance the properties of the resulting rubber products.

[0087] The average pellet crushing strength of the oxidized wet beaded carbon black pellets having a diameter of 1.0 to 1.4 mm may be 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN. The average pellet crushing strength of the oxidized wet beaded carbon black pellets having a diameter of 1.4 to 1.7 mm may be 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN.

[0088] It is particularly desirable that the average pellet crushing strength of pellets having a diameter of 0.71 to 1.0 mm is 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN, the average pellet crushing strength of pellets having a diameter of 1.0 to 1.4 mm is 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN, and the average pellet crushing strength of pellets having a diameter of 1.4 to 1.7 mm is 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN.

[0089] It is particularly desirable that the average pellet crushing strength of the five hardest pellets having a diameter of 0.71 to 1.0 mm is 5 to 110 cN, preferably 10 to 80 cN, more preferably 15 to 50 cN. The pellet crushing strength of the hardest pellets having a diameter of 0.71 to 1.0 mm should be 5 to 110 cN, preferably 10 to 80 cN, more preferably 15 to 50 cN. The average pellet crushing strength of the five hardest pellets having a diameter of 1.0 to 1.4 mm should be 5 to 110 cN, preferably 10 to 80 cN, more preferably 15 to 50 cN. The pellet crushing strength of the hardest pellets having a diameter of 1.0 to 1.4 mm should be 5 to 110 cN, preferably 10 to 80 cN, more preferably 15 to 50 cN.

[0090] The iodine adsorption amount of the oxidized wet beaded carbon black should be 30 to 80 mg / g, preferably 40 to 70 mg / g, more preferably 45 to 65 mg / g. The iodine adsorption amount can be measured according to ASTM D1510-17.

[0091] The statistical thickness surface area (STSA) of oxidized wet beaded carbon black, measured in accordance with ASTM D6556-17, ranges from 15 to 500 m 2 / g, preferably 20 to 400m 2 / g, more preferably 30 to 300m 2 / g, and even more preferably 40 to 200 m 2 / g, most preferably 50 to 150m 2 / g range. 39.

[0092] The fines content of the oxidized wet beaded carbon black may be 0.1-50%, preferably 1-10%, more preferably 1-5%. The fines content can be measured according to ASTM D1508-02. Low fines content is an indicator to avoid the destruction of beads / pellets during the oxidation process.

[0093] The pH value of the oxidized wet beaded carbon black should be less than 7, for example, 2-6, 2-5, 2-4, 2-3, preferably 2.4-2.9, more preferably 2.7-2.9. The pH value can be measured according to ASTM D1512-15b, Test Method B - Sonic Slurry.

[0094] Pellet attrition should be less than 6.5%, preferably 0.1-5%, more preferably 0.2-3%, and most preferably 0.5-2%. Pellet attrition can be measured according to ASTM D1508-02. Low pellet attrition is desirable so that transportation and mixing of the beads is improved. In addition, low pellet attrition prevents breakage of the pellets during transportation or handling.

[0095] The method for producing oxidized wet-beaded carbon black can be carried out in a screw conveyor that includes a reaction chamber and at least one ozone inlet for supplying ozone to the reaction chamber. In this way, the screw conveyor can be used for producing oxidized wet-beaded carbon black. It has been found that the destruction of carbon black beads can be advantageously avoided by using a screw conveyor for oxidation.

[0096] Furthermore, the screw conveyor may include means for generating ozone. The means for generating ozone should be connected to at least one ozone inlet.

[0097] The screw conveyor is typically a cylinder containing a "helical blade" coiled around a shaft. The screw conveyor is further modified to allow for oxidation of the wet beaded carbon black. Thus, the screw conveyor includes at least one ozone inlet for supplying ozone to the chamber of the screw conveyor. In this manner, the chamber of the screw conveyor is a reaction chamber where an oxidizing agent, such as ozone, can oxidize the wet beaded carbon black.

[0098] The screw conveyor may include at least one temperature control unit for cooling or heating the reaction chamber. During the oxidation of the wet beaded carbon black, the temperature may increase. The temperature of the reaction chamber may be controlled by the temperature control unit to avoid the risk of losing volatiles (which would reduce the degree of oxidation). However, in processes that result in less oxidized carbon black, it may be beneficial to transfer additional heat to the reaction chamber for the oxidation step. The temperature control unit is preferably attached to the outer surface of the reaction chamber or barrel.

[0099] The screw of the screw conveyor (conveyor screw) may be a conventional helical screw blade. The screw of the screw conveyor has a screw thread (or a helical screw blade), and the screw thread may have 2 to 100 turns, preferably 5 to 50 turns. The screw thread may have a continuous or a constant increasing / decreasing pitch. Generally, the screw comprises a shaft and a helical conveyor blade thereon. However, it is also possible that the screw is a shaftless helical conveyor blade. Thus, the blade may be directly driven by a motor. The screw conveyor may comprise a helical conveyor blade. The screw generally has at least one screw flight extending radially and helically from and along the shaft.

[0100] The screw may be configured at least partially as a flight, preferably at least partially as a single flight, more preferably at least partially as a double flight, and the screw includes at least one second helical conveyor blade (second flight), and when the screw is configured at least partially as a double flight ribbon, it further includes at least one first helical conveyor blade (first flight).

[0101] The screw conveyor or helical conveyor blade may include at least one first helical conveyor blade and / or at least one second helical conveyor blade. The first and second helical conveyor blades may be arranged in sequence, thus forming a single thread. It may also be desirable for the first and second helical conveyor blades to form a double-start thread (or a double-start thread, or a double flight). For example, the first and second helical conveyor blades may form a high-low thread, the first helical conveyor blade being a low thread and the second helical conveyor blade being a high thread. Each revolution of the first conveyor blade may extend over at least a portion of the length of the shaft between each subsequent revolution of the second conveyor blade. If a double-start thread is present, it is not necessary for both threads to start at the same time.

[0102] The second spiral conveyor blade may extend over at least a portion of the length of the shaft, with a radial distance to the shaft, thereby forming a circumferential clearance between the shaft and the second spiral conveyor blade. A spiral conveyor blade having such a clearance is commonly referred to as a flight ribbon. Thus, the screw may be configured at least partially as a flight ribbon, preferably at least partially as a single flight ribbon, more preferably at least partially as a double flight ribbon.

[0103] The screw may be configured at least partially as a flighted ribbon, preferably at least partially as a single-flighted ribbon, more preferably at least partially as a double-flighted ribbon, and the screw includes at least one second helical conveyor blade (second flight), and when the screw is configured at least partially as a double-flighted ribbon, further includes at least one first helical conveyor blade (first flight).

[0104] The screw may be configured as a flight ribbon, preferably a single flight ribbon, more preferably a double flight, where one flight at least partially comprises the flight ribbon, and the screw comprises at least one second helical conveyor blade (second flight), and when the screw is configured as a double ribbon, it further comprises at least one first helical conveyor blade (first flight), where the at least one second helical conveyor blade (second flight) is at least partially configured as a flight ribbon.

[0105] The screw may be configured as a double flight, the screw comprising at least one second helical conveyor blade (second flight) and at least one first helical conveyor blade (first flight), the at least one second helical conveyor blade (second flight) being particularly preferably configured at least partially as a flight ribbon (preferably a second section), the flight ribbon being preferably adjacent to the ozone inlet.

[0106] It is also preferred that the screw can be configured as one flight, the screw includes at least one second spiral conveyor blade (second flight), the at least one second spiral conveyor blade (second flight) is at least partially configured as a flight ribbon (preferably as a second section), preferably the at least one second spiral conveyor blade (second flight) has three sections, the first section being a flight directly and continuously attached to the shaft, the second section being a flight ribbon, and the third section being a flight directly and continuously attached to the shaft. It is preferred that the flight ribbon is adjacent to the ozone inlet. The second section should be located between the first section and the second section.

[0107] It is particularly preferred that the screw can be configured as a double flight, the screw comprising at least one second spiral conveyor blade (second flight) and at least one first spiral conveyor blade (first flight), the at least one second spiral conveyor blade (second flight) being at least partially configured as a flight ribbon (preferably as a second section), preferably the at least one second spiral conveyor blade (second flight) having three sections, the first section being a flight directly and continuously attached to the shaft, the second section being a flight ribbon, the third section being a flight directly and continuously attached to the shaft, preferably the at least one first spiral conveyor blade (first flight) being a flight directly and continuously attached to the shaft. It is preferred that the flight ribbon is adjacent to the ozone inlet. The second section should be located between the first section and the second section.

[0108] The clearance between the shaft and the helical conveyor blade in a conventional screw conveyor has the drawback of reducing the ability to transport material. In other words, the main purpose of a conventional screw conveyor is the transportation of material, for example to overcome an incline. However, the screw conveyor according to the present invention is not only used to transport material, but also to oxidize the feed material. Such blades with clearance between the shaft and the helical conveyor blade can be beneficially used for oxidation. The oxidizing agent can be better distributed through the reaction chamber and the wet beaded carbon black can be mixed uniformly. The uniform mixing during oxidation allows for improved and uniform oxidation of the wet beaded carbon black.

[0109] It is particularly preferred that the second spiral conveyor blade, having a radial distance to the shaft thereby forming a circumferential clearance between the shaft and the second spiral conveyor blade, extends over at least a portion of the length of the shaft in which the ozone inlet is located.

[0110] The second spiral conveyor blade may include a first section including a spiral conveyor blade attached directly to the shaft, and a second section including a spiral conveyor blade extending over at least a portion of the length of the shaft (preferably where the ozone inlet is located) with a radial distance to the shaft, thereby forming a circumferential clearance between the shaft and the second spiral conveyor blade. Furthermore, the second spiral conveyor blade desirably includes a first section including a spiral conveyor blade attached directly to the shaft, a second section including a spiral conveyor blade extending over at least a portion of the length of the shaft (preferably where the ozone inlet is located) with a radial distance to the shaft, thereby forming a circumferential clearance between the shaft and the second spiral conveyor blade, and a third section including a spiral conveyor blade attached directly to the shaft. The second spiral conveyor blade preferably includes sections in the following order: a first section, a second section and a third section. The first helical conveyor blade may form a second thread of the screw, the diameter (or outer diameter) of the first helical conveyor blade being smaller than the diameter (or outer diameter) of the second helical conveyor blade.

[0111] The second conveyor blade can be attached to the shaft over at least a part of the length of the shaft via spacer bars extending radially from the shaft, preferably via three or more bars. In particular, if the second conveyor blade has a radial distance to the shaft, thereby forming a circumferential clearance between the shaft and the second spiral conveyor blade, it can be attached to the shaft over at least a part of the length of the shaft via spacer bars extending radially from the shaft, preferably via three or more bars. This means that the part of the second conveyor blade having said clearance should be attached to the shaft over at least a part of the length of the shaft via spacer bars extending radially from the shaft, preferably via three or more bars.

[0112] The radial distance to the shaft forming a circumferential clearance between the shaft and the second spiral conveyor blade should be between 10 and 200 mm, preferably between 20 and 150 mm, more preferably between 30 and 100 mm, even more preferably between 40 and 80 mm, and most preferably between 45 and 70 mm.

[0113] In conventional screw conveyors, the formation of a circumferential clearance between the shaft and the helical conveyor blades due to the radial distance to the shaft is a drawback in that it reduces the ability to convey material. In other words, the main purpose of conventional screw conveyors is the transportation of materials, for example overcoming inclines. However, the screw conveyor according to the present invention is not only used to convey materials, but also to oxidize the feed material. Such blades with clearance can be beneficially used for oxidation. The oxidizing agent can be better distributed through the reaction chamber and the wet beaded carbon black can be mixed uniformly. The uniform mixing during oxidation allows for an improved and uniform oxidation of the wet beaded carbon black.

[0114] The first conveyor blade has a first outer diameter and the second conveyor blade has a second outer diameter, preferably the first and second outer diameters being different from each other. In particular, the first outer diameter is smaller than the second outer diameter. The spacing (lead) of the second conveyor blade over at least a portion of the length of the shaft should be smaller than the spacing (lead) of the first conveyor blade.

[0115] The screw conveyor can include a drive and a driven screw extending into a barrel forming a reaction chamber, the screw including a shaft and at least one first helical conveyor blade. The drive should be configured to drive the driven screw.

[0116] Typically, the screw of the screw conveyor comprises a shaft and at least one first helical conveyor blade. Alternatively or additionally, the screw of the screw conveyor comprises a shaft and at least one second helical conveyor blade.

[0117] The screw of the screw conveyor and / or reaction chamber can have a length of 0.1-100 m, e.g., 1-20 m, 5-15 m, 2-4 m, 10-90 m, or 20-80 m. The volume of the reaction chamber can be 1-10000 L, e.g., 10-1000 L, 20-100 L, 2-50 L, 100-9000 L, or 500-5000 L. The volume of the reaction chamber can be selected as required for the process. A higher input of wet beaded carbon black feed requires a larger reaction chamber. The screw conveyor can include a drive and a driven screw that extends into a barrel that forms the reaction chamber. The screw conveyor typically includes an inlet for the wet beaded carbon black to the reaction chamber. Similarly, the screw conveyor typically includes an outlet for the produced oxidized wet beaded carbon black, the outlet being located on the opposite side of the reaction chamber relative to the inlet. The inlet is located at the top of the screw conveyor and the outlet is located at the bottom of the screw conveyor.

[0118] The diameter of the screw may be 50-300 mm, preferably 60-250 mm, more preferably 70-200 mm, even more preferably 80-150 mm, most preferably 90-130 mm. The diameter of the at least one first and / or at least one second spiral conveyor blade may be 50-1000 mm, preferably 100-800 mm, more preferably 150-700 mm, even more preferably 200-600 mm, most preferably 250-400 mm. The diameter of the at least one first spiral conveyor blade may be 25-500 mm, preferably 50-400 mm, more preferably 75-350 mm, even more preferably 100-300 mm, most preferably 150-300 mm. The inner diameter of the barrel may be 50-3000 mm, for example 100-800 mm, 150-700 mm, 200-600 mm, 250-400 mm, 100-2000 mm, or 150-1000 mm, preferably the inner diameter of the barrel is larger than the diameter of the at least one first and / or at least one second spiral conveyor blade. The inner diameter of the at least one second spiral conveyor blade may be 40-900 mm, preferably 80-750 mm, more preferably 130-650 mm, even more preferably 180-550 mm, most preferably 230-350 mm. The outer diameter of the at least one second spiral conveyor blade should be between 50 and 1000 mm, preferably between 100 and 800 mm, more preferably between 150 and 700 mm, even more preferably between 200 and 600 mm, and most preferably between 250 and 400 mm.

[0119] In general, the size of each of the components of the screw conveyor should be selected relative to the size of the screw conveyor. Large screw conveyors usually include larger components and larger dimensions of the components. Therefore, the size and dimensions of a particular component or part of the screw conveyor usually match.

[0120] The gap between the spiral conveyor blade and the inner surface of the reactor chamber can be from 0 mm (or more than 0 mm) to 200 mm, preferably from 1 mm to 100 mm, more preferably from 2 mm to 80 mm, even more preferably from 5 to 50 mm, and most preferably from 10 to 40 mm.

[0121] The at least one first and / or at least one second spiral conveyor blade may include at least one turner attached to a surface opposite to the conveying direction. The turner should be capable of lifting a portion of the wet beaded carbon black material so that mixing of the material is improved. This allows for uniform mixing of the material so that oxidation is promoted.

[0122] The at least one first and / or at least one second spiral conveyor blade may include at least one first turner and at least one second turner. The at least one first and at least one second turner may be alternately attached to the at least one first and / or at least one second spiral conveyor blade. The angle of the at least one first turner must be greater than the angle of the at least one second turner, the turner extending at an angle to the tangent of the circumference of the second conveyor blade (as shown in FIG. 8). The angle of the at least one first turner may be 30-100°, preferably 35-90°, more preferably 40-80°, even more preferably 50-70°, and most preferably 55-65°. The angle of the at least one second turner is between 10 and 60°, preferably between 15 and 55°, more preferably between 20 and 50°, even more preferably between 25 and 45°, and most preferably between 35 and 45°, and the turner extends at an angle to a tangent to the circumference of the second conveyor blade.

[0123] The present invention will now be described with reference to the accompanying drawings, which do not limit the scope and area of ​​the present invention. The description provided is purely for the purposes of example and illustration. However, certain features illustrated in the drawings may be used to further limit the scope of the present invention and the claims.

[0124] FIG. 1 relates to a method for producing oxidized wet-beaded carbon black (202). First, carbon black is provided (101), preferably as a powder. As mentioned above, the carbon black powder is preferably furnace black. However, any type of carbon black material can be used according to the invention, including mixtures of carbon black materials. In a second step, the carbon black is wet-beaded. Wet-beading can include treating the carbon black powder with water and optionally a binder. The mixture is subsequently beaded and dried to obtain the wet-beaded carbon black (102). The beads are then subjected to an oxidation step (103) to obtain the oxidized wet-beaded carbon black (202). The oxidation step is preferably carried out in a screw conveyor (200, 300) according to the invention. However, the specific means for oxidation is not limited to a screw conveyor. Preferably, ozone is used as the oxidizing agent. The produced oxidized wet-beaded carbon black can be used in the compositions of the invention.

[0125] Referring to FIG. 2, an inner portion of a screw conveyor (200) is shown. The screw conveyor (200) includes at least one first spiral conveyor blade (214, 502) attached to a shaft (213) connected to an electric motor (215) that drives the screw. Alternatively, the spiral conveyor blade shown in FIG. 2 is at least one second spiral conveyor blade (501). The screw conveyor (200) further includes a barrel (211) that defines a reaction chamber (218) or provides a barrier that defines the reaction chamber (218). The screw conveyor (200) includes an inlet (210) for the wet beaded carbon black (201) and an outlet (212) for the produced oxidized wet beaded carbon black (202). At the bottom of the screw conveyor (200) are attached several ozone inlets (216) which feed ozone (217) into the reaction chamber (218). The screw includes at least one first spiral conveyor blade (214) to transport the feed material in a direction from the inlet towards the outlet. If there is a second spiral conveyor blade (501) extending over at least a portion of the length of the shaft and having a radial distance to the shaft (213) thereby forming a circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501), it is desirable that the clearance (i.e. the radial distance to the shaft (213) which forms the circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501)) is located over the length of the portion of the shaft where the ozone inlet is located. The longitudinal direction of the screw (220) is shown in FIG.

[0126] Referring to FIG. 3, an outer portion of the screw conveyor (300) is shown. In this view, three temperature control units (301) are visible, which are attached to the outer wall of the screw conveyor (300), i.e., the outer wall of the barrel (211). The temperature control units extend on the opposite side of the screw conveyor (300), which is not shown in this view. Each temperature control unit (301) includes an inlet (302) for a fluid, such as water, and an outlet (303) for a fluid, such as water. The inlets (301) and outlets (302) can be interchanged. Furthermore, the barriers (304) are shown as dashed lines indicating the flow path of the fluid. Thus, each barrier has at least one opening to define a flow path so that the fluid can be transported from the inlet (302) to the outlet (303). Some openings are not shown in the figure, since they exist on the opposite side of the temperature control units 301.

[0127] FIG. 4 shows a section of a screw (400) including at least one first helical conveyor blade (214, 502) attached to a shaft (213). In this figure, a screw configured as a single flight (at least partially) is shown. The at least one first helical conveyor blade (214, 502) is attached directly to the shaft (213) without a radial distance to the shaft (213) and thus without forming a circumferential clearance (503) between the shaft (213) and the first helical conveyor blade (214, 502). Alternatively, the helical conveyor blade shown in FIG. 2 is at least one second helical conveyor blade (501). The spacing of the first conveyor blades (214, 502) is shown in the figure. The spacing of the first conveyor blades is the lead. The spacing of a particular conveyor blade or the lead of a particular conveyor blade is the distance along the axis of the screw that is covered by one complete revolution of the conveyor blade. If the screw contains only one conveyor blade, the lead and pitch are the same (single start thread). In Figure 4, the flights are attached directly and continuously to the shaft (no clearance, not a flight ribbon).

[0128] Figure 5 shows a section of a screw (500) comprising a shaft (213), at least one first helical conveyor blade (502) and at least one second helical conveyor blade (501), which second helical conveyor blade extends over at least a partial length of the shaft, with a radial distance to the shaft (213), thereby forming a circumferential clearance (503) between the shaft (213) and the second helical conveyor blade (501). The screw is therefore designed as a double-thread (or double-start thread), the first helical conveyor (502) being a low thread and the second helical conveyor being a high thread (501). This means that each revolution of the first conveyor blades (214, 502) extends between each subsequent revolution of the second conveyor blade (501) over at least a partial length of the shaft. This configuration is preferably present where the ozone inlet is located. Thus, the described screw (500) is preferably located in the central part of the screw, where the inlet for ozone (216) is preferably located. Thus, the ozone (217) provided through the inlet (216) can be easily distributed in the reaction chamber (218) and an improved uniform oxidation is achieved. It should be noted that the at least one second helical conveyor blade (501) extends over at least a part of the length of the shaft (213) while having a radial distance to the shaft (213), thereby forming a circumferential clearance (503) between the shaft (213) and the second helical conveyor blade (501), and can be attached to the screw via a bar (spacer bar) not shown in the figure. The bar (spacer bar) can support the structure. However, any conceivable means for attaching the at least one second helical conveyor blade (501) to the screw can be used. The spacing (504) or lead (504) of the at least one first helical conveyor blade (502) is shown in Figure 5. The spacing (505) or lead (505) of the at least one second helical conveyor blade (501) is shown in Figure 5.In this figure, the screw is shown configured as a double flight (at least partially) with a ribbon flight, which is at least one second helical conveyor (501).

[0129] Referring to Fig. 6, a screw (600) with different sections of helical conveyor blades (601, 602, 603) is shown. In this configuration, the screw includes a shaft (213), at least one first helical conveyor blade (502) and at least one second helical conveyor blade (501), which has a radial distance to the shaft (213), thereby extending over at least a portion of the length of the shaft while forming a circumferential clearance (503) between the shaft (213) and the second helical conveyor blade (501). The screw is designed as a double-thread (or double-start thread), with the first helical conveyor (502) being a low thread and the second helical conveyor being a high thread (501). Thus, the second spiral conveyor blade (501) extends only partially over the length of the shaft while having a radial distance to the shaft (213), thereby forming a circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501). This portion is shown as section (602). Thus, the second spiral conveyor blade (501) in sections (601) and (603) is directly attached to the shaft (213). A smooth transition is generally made from the section of the second spiral conveyor blade (501) to which the shaft (213) is directly connected, to the section that extends over at least a portion of the length of the shaft while having a radial distance to the shaft (213), thereby forming a circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501).

[0130] 7 and 8 show a cross section of a screw including a shaft (213), at least one first helical conveyor blade (502), at least one second helical conveyor blade (501) and further turners (702, 703), the second helical conveyor blade extending over at least a portion of the length of the shaft with a radial distance to the shaft (213) thereby forming a circumferential clearance (503) between the shaft (213) and the second helical conveyor blade (501). The at least one second helical conveyor blade (501) extending over at least a portion of the length of the shaft with a radial distance to the shaft (213) thereby forming a circumferential clearance (503) between the shaft (213) and the second helical conveyor blade (501) is attached to the screw (213) via a spacer bar (701). Reference numeral 502 indicates that at least one first spiral conveyor blade (502) has a smaller diameter. In Fig. 8, the respective diameters and clearances (503) of the respective spiral conveyor blades are shown. The inner diameter (804) of at least one second spiral conveyor blade (501) extending over at least a portion of the length of the shaft while having a radial distance to the shaft (213) thereby forming a circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501) simultaneously defines the clearance (503) between the second spiral conveyor blade (501) and the shaft (213). It should be noted that the diameters mentioned in this specification refer to the diameters of the spiral conveyor blades, taking into account a cross section, for example as shown in Fig. 7.Further shown in Figure 8 is the outer diameter (803) of the at least one second spiral conveyor blade (501) extending over at least a portion of the length of the shaft (213) while having a radial distance to the shaft (213) and thereby forming a circumferential clearance (503) between the shaft (213) and the second spiral conveyor blade (501), the distance (807) between the at least one first spiral conveyor blade (502) and the at least one second spiral conveyor blade (501), the diameter (806) of the at least one first spiral conveyor blade (502), and the distance (805) between the inner and outer diameters of the at least one second spiral conveyor blade (501). As can be seen in Figure 8, the turners (702, 703) are attached to the at least one second spiral conveyor blade (501) at specific angles (801, 802). Each angle is such that the turner extends at an angle relative to a tangent to the circumference of the second conveyor blade, as shown in particular in Figure 8. As mentioned above, the turner (702, 703) may also be attached to at least one of the first helical conveyor blades (214, 502).

[0131] Figure 9 shows an oxidized wet-beaded carbon black prepared according to the present invention. As can be seen from the image, it is possible to oxidize the wet-beaded carbon black without destroying the beads. EXAMPLES

[0132] Example 1: Preparation of oxidized wet-beaded carbon black according to the present invention The carbon black powder used to prepare the oxidized wet beaded carbon black in Examples AI (Examples AI) is N234.

[0133] In Examples AH, the carbon black powder is converted into wet beads by applying water to the carbon black powder to convert the wet carbon black powder into beads, and then drying the resulting wet-beaded carbon black.

[0134] The wet beaded carbon black is then subjected to a screw conveyor for oxidation. Ozone is fed into the reaction chamber of the screw conveyor to oxidize the wet beaded carbon black. The setup and results of the production of oxidized wet beaded carbon black are shown in Table 1. The ozone flow rate indicates the target ozone flow rate in the reaction chamber. The reaction chamber of the screw conveyor is cooled with water.

[0135] In Comparative Example I (Comparative Example I), the carbon black powder is first oxidized and then dry beaded to avoid devolatilization of the carbon black beads.

[0136] Table 1: Preparation of oxidized wet-beaded carbon black. [Table 1] 1 Pellet crush strength is measured according to ASTM D5230-19. 2 Fines content is measured according to ASTM D1508-02. 3 Volatiles are measured at 950° C. for 7 minutes as described below. 4 BET surface area is measured according to ASTM D6556-17. 5 STSA surface area is measured according to ASTM D6556-17. 6 Iodine adsorption is measured according to ASTM D1510-17. 7 Pellet attrition is measured according to ASTM D1508-02. 8 The pH value is measured according to ASTM D1512-15b, Test Method B - Sonic Slurry. 9 Oil absorption is measured according to ASTM D2414-18. 10 Weight ratio of carbon black to ozone.

[0137] The volatile content at 950 °C was measured using a thermogravimetric analyzer (TGA-701) manufactured by Fa.LECO Instruments according to the following procedure. The sample pan was dried at 650 °C for 30 min. The carbon black material was stored in a desiccator equipped with a desiccant prior to measurement. The baked-out sample pan was loaded into the instrument, tared, and filled with 0.5 g to 10 g of carbon black material. The oven of the TGA instrument loaded with the sample-filled pan was then gradually heated to 105 °C by automated software control to dry the sample until a constant mass was achieved. The pan was then closed with a lid, and the oven was purged with nitrogen (99.9 vol.% grade) and heated to 950 °C. The oven temperature was maintained at 950 °C for 7 min. The volatile content at 950 °C was calculated using the following formula:

number

[0138] The produced oxidized wet-beaded carbon black has a remarkable pellet crush strength compared to the beads obtained in Comparative Example I. This indicated that the beads were not destroyed during the oxidation treatment in the screw conveyor. The pellet crush strength is particularly high by using a low screw rotation speed, such as 0.5 rpm instead of 3 rpm. Meanwhile, by using a higher screw rotation speed, the fines content is lower. The BET, STSA and CTAB surface areas of the produced oxidized wet-beaded carbon black are larger compared to the palletized carbon black according to Comparative Example I. Furthermore, the pellet wear and OAN are improved compared to the palletized carbon black according to Comparative Example I. Figure 11 shows the oxidized wet-beaded carbon black produced according to Example A.

[0139] The oxidized wet beaded carbon black produced can be used in compositions according to the present invention.

[0140] Example 2: Performance of Oxidized Wet Beaded Carbon Black in Rubber Compositions The performance of oxidized wet beaded carbon black in compositions containing elastomeric polymeric materials for the production of rubber products is compared to beaded carbon black powder and oxidized carbon black powder. In Examples J and K, the properties of the rubber products produced from the compositions were measured several times and the values ​​shown in each table refer to the average of the measurements.

[0141] As can be seen from the table below, the loss factor tan δ is lower and therefore improved by using oxidized wet beaded carbon black. Furthermore, the dynamic modulus is higher compared to carbon black that is first oxidized and then dry beaded. Thus, oxidized wet beaded carbon black can be beneficially used in rubber compositions to enhance the properties of the resulting rubber products. The preparation of the compositions and the articles produced can be seen below.

[0142] [Table 2] Table: Test formulation 1 Accelerators, commercially available from Rhein Chemie Additives 2 Accelerators, commercially available from Rhein Chemie Additives

[0143] The compositions were prepared according to standard rubber mixing procedures by applying three mixing steps, each consisting of mixing in an internal mixer GK1.5E with intermeshing rotor geometry, followed by mixing on an open two-roll mill.

[0144] In the first step, the natural rubber was milled in an internal mixer for 30 seconds. Half of the CB, ZnO and stearic acid were then added and mixed for 1:15 minutes. The ram was then lifted and washed, and the remaining half of the carbon black was added and mixed for 1:15 minutes while the ram was lifted and washed again. After a total of 4 minutes of mixing, the compound was transferred to an open mill. The chamber temperature was 60°C and the rotor speed was 45 rpm during the entire first mixing step. It was ensured that the batch temperature did not exceed 160°C.

[0145] After storing the composite for more than 16 hours, the composite was mixed for 6 minutes without adding any chemicals, during which the mixing chamber had a temperature of 60°C and the rotor speed was 48 rpm. The composite was then transferred to an open mill, ensuring that the batch temperature did not exceed 160°C.

[0146] After another storage time of a minimum of 16 hours, sulfur, TBBS-80 and DPG-80 were added to the above composition while the internal mixer was operated at a chamber temperature of 40° C. and a rotor speed of 33 rpm. The drop temperature was 80° C. to 110° C. Again, in the final stage of mixing, the mixture was mixed on an open mill and a sheet was formed.

[0147] The specimens or articles for dynamic-mechanical analysis were cured at 150° C. for 13 minutes.

[0148] Example J [Table 3]

[0149] Example K [Table 4]

[0150] The above values ​​and the loss factor tan(d) were measured according to DIN 53 513 using cylindrical specimens (height 10 mm, diameter 10 mm) in strain-controlled mode (1 ± 0.5 mm) or force-controlled mode (50 N ± 25 N) at 60 °C and a frequency of 16 Hz.

[0151] Aspects of the invention 1. (a) an elastomeric polymeric material, and (b) Oxidized wet beaded carbon black (202) A composition comprising:

[0152] 2. 2. The composition of embodiment 1, wherein the elastomeric polymer material (a) comprises a rubber.

[0153] 3. 3. The composition of claim 1 or 2, wherein the elastomeric polymeric material (a) comprises natural rubber and / or synthetic rubber, wherein the synthetic rubber comprises styrene-butadiene rubber, such as emulsion-styrene-butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber, or a mixture of any combination of the above.

[0154] 4. 2. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises natural rubber and / or synthetic rubber, wherein the synthetic rubber comprises solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber, or a mixture of any of the foregoing in combination.

[0155] 5. 2. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises natural rubber and / or synthetic rubber, wherein the synthetic rubber comprises solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorocarbon rubber, or a mixture of any of the foregoing in combination.

[0156] 6. 2. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises natural rubber.

[0157] 7. 2. The composition of any one of the preceding embodiments, wherein the natural rubber comprises natural rubber obtained from rubber trees (Herbia braziliensis), guayule, dandelion, or a mixture of any combination of the foregoing.

[0158] 8. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises, based on parts by weight per 100 parts by weight of rubber, 40 to 100 phr of natural rubber and 5 to 60 phr of synthetic rubber, preferably 40 to 60 phr of natural rubber and 40 to 60 phr of synthetic rubber, more preferably 50 phr of natural rubber and 50 phr of synthetic rubber.

[0159] 9. The composition of embodiment 8, wherein the synthetic rubber comprises emulsion styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0160] 10. The composition of embodiment 8, wherein the synthetic rubber comprises polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0161] 11. The composition of embodiment 8, wherein the synthetic rubber comprises polybutadiene, polyisoprene, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0162] 12. The composition of embodiment 8, wherein the synthetic rubber comprises emulsion styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0163] 13. The composition of embodiment 8, wherein the synthetic rubber comprises polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber, or a mixture of any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0164] 14. The composition of embodiment 8, wherein the synthetic rubber comprises a mixture of polybutadiene, polyisoprene, halogenated butyl rubber, or any combination thereof, preferably polyisoprene or polybutadiene, more preferably polybutadiene.

[0165] 15. 5. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises natural rubber.

[0166] 16. 15. The composition of any one of the preceding embodiments, wherein the elastomeric polymer material (a) comprises a synthetic rubber.

[0167] 17. 17. The composition of any one of embodiments 1-14 and 16, wherein the synthetic rubber comprises a synthetic rubber obtained from renewable sources.

[0168] 18. 18. The composition of any one of aspects 1-14, 16 and 17, wherein the synthetic rubber comprises polybutadiene obtained from alcohol obtained by fermentation of plant biomass.

[0169] 19. The composition of any one of aspects 1-14 and 16-18, wherein the elastomeric polymer material (a) comprises, based on parts by weight per hundred parts of rubber (phr), from 5 to 40 phr of natural rubber and 60 to 100 phr of synthetic rubber, preferably from 10 to 20 phr of natural rubber and 80 to 90 phr of synthetic rubber, more preferably from 5 phr of natural rubber and 95 phr of synthetic rubber.

[0170] 20. The composition of any one of embodiments 1-5 and 16-18, wherein the elastomeric polymer material (a) comprises a synthetic rubber.

[0171] twenty one. 5. The composition of any one of the preceding embodiments, wherein the oxidized wet beaded carbon black (202) is or is derived from plasma black, gas black, channel black, thermal black, lamp black or furnace black, preferably furnace black.

[0172] twenty two. The statistical thickness surface area (STSA) of oxidized wet beaded carbon black (202), measured according to ASTM D6556-17, is between 15 and 500 m 2 / g, preferably 20 to 400m 2 / g, more preferably 30 to 300m 2 / g, and even more preferably 40 to 200 m 2 / g, most preferably 50 to 150m 2 39. The composition of any one of the preceding embodiments, wherein the .alpha.-to-.alpha.

[0173] twenty three. The composition according to any one of the preceding embodiments, comprising from 3 to 200 phr of the oxidized wet beaded carbon black (202)(b), preferably from 5 to 190 phr of the oxidized wet beaded carbon black (b), more preferably from 10 to 150 phr, even more preferably from 20 to 130 phr of the oxidized wet beaded carbon black (202)(b), and most preferably from 30 to 100 phr of the oxidized wet beaded carbon black (202)(b).

[0174] twenty four.

[0023] The composition of any one of the preceding embodiments, wherein the oxidized wet-beaded carbon black (202) is prepared by wet-beading carbon black and then oxidizing the wet-beaded carbon black using ozone, preferably in a screw conveyor, to obtain the oxidized wet-beaded carbon black (202).

[0175] twenty five. The composition of any one of the preceding embodiments, further comprising one or more additives selected from vulcanizing agents, curing aids such as primary and secondary vulcanization accelerators, activators and pre-vulcanization inhibitors, processing additives such as oils, waxes, resins, plasticizers, softeners, rheology modifiers, pigments, peptizers, coupling agents, surfactants, biocides, and anti-degradants such as heat or light stabilizers, antioxidants and antiozonants, metal oxides, metal hydroxides, and filler materials such as silica, organosilica, carbon nanotubes, carbon fibers, graphite, and metal fibers.

[0176] twenty five. 5. The composition of any one of the preceding embodiments, wherein the oxidized wet beaded carbon black (202) has a volatile content measured at 950° C. of 1 to 2 wt. %.

[0177] 26. The composition of any one of the preceding embodiments, wherein the oxidized wet beaded carbon black (202) has an average pellet crush strength of 4 to 80 cN, preferably 5 to 50 cN, and more preferably 10 to 40 cN, for pellets having a diameter of 0.71 to 1.0 mm.

[0178] 27. 10. The composition of any one of the preceding embodiments, wherein the oxidized wet beaded carbon black (202) has an average pellet crush strength of 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN for pellets having a diameter of 1.0 to 1.4 mm, and / or the oxidized wet beaded carbon black (202) has an average pellet crush strength of 4 to 80 cN, preferably 5 to 50 cN, more preferably 10 to 40 cN for pellets having a diameter of 1.4 to 1.7 mm.

[0179] 28. The composition of any one of the preceding embodiments, wherein the volatile content of the oxidized wet beaded carbon black (202), measured at 950° C., is from 1 to 25% by weight, e.g., from 1.5 to 20% by weight, from 1 to 10% by weight, from 1.5 to 10% by weight, from 1.5 to 20% by weight, from 2 to 10% by weight, from 2 to 15% by weight, from 2.5 to 10% by weight, from 3 to 7% by weight, or from 3.5 to 7% by weight.

[0180] 29. The composition according to any one of the preceding aspects, wherein the iodine adsorption amount of the oxidized wet beaded carbon black (202) is 30 to 80 mg / g, preferably 40 to 70 mg / g, and more preferably 45 to 65 mg / g.

[0181] 30. The statistical thickness surface area (STSA) of oxidized wet beaded carbon black (202), measured according to ASTM D6556-17, is between 15 and 500 m 2 / g, preferably 20 to 400m 2 / g, more preferably 30 to 300m 2 / g, and even more preferably 40 to 200 m 2 / g, most preferably 50 to 150m 2 39. The composition of any one of the preceding embodiments, wherein the .alpha.-to-.alpha.

[0182] 31. 5. The composition of any one of the preceding embodiments, wherein the oxidized wet beaded carbon black (202) has a volatile content measured at 950° C. of 5 to 15 wt. %.

[0183] 32. 10. The composition according to any one of the preceding embodiments, wherein the fines content of the oxidized wet beaded carbon black (202) is from 0.1 to 50%, preferably from 1 to 10%, more preferably from 1 to 5%.

[0184] 33. 10. The composition according to any one of the preceding embodiments, wherein the pH value of the oxidized wet beaded carbon black (202) is less than 7, such as from 2 to 6, preferably from 2 to 5, more preferably from 2 to 3, even more preferably from 2.4 to 2.9, and most preferably from 2.7 to 2.9.

[0185] 34. An article made from the composition according to any one of the preceding embodiments.

[0186] 35. 35. The article of embodiment 34, wherein the article is a tire.

[0187] 36.

[0041] Example 35. The tire of Example 35, wherein the tire comprises a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, an innerliner, an apex, a shoulder, a hump strip, a chafer, and a bead filler, at least one of which is made from the composition of any one of Examples 1-33.

[0188] 37.

[0046] A tire as described in any one of embodiments 35-36, wherein the tire has a circumferential tread in a cap / base configuration including a peripheral tread cap rubber layer that includes the running surface of the tire and a tread base rubber layer underlying at least a portion of the tread cap rubber layer, and at least one of the tread cap rubber layer and the tread base rubber layer is made from the composition as described in any one of embodiments 1-33.

[0189] 38. 38. The tire of any one of embodiments 35-37, wherein the tire includes a sidewall, the sidewall being made from the composition of any one of embodiments 1-33, the composition preferably including components (a) and (b): (a) 40-60 phr of natural rubber and 40-60 phr of synthetic rubber, preferably 50-60 phr of natural rubber and 40-50 phr of synthetic rubber, more preferably 55 phr of natural rubber and 45 phr of synthetic rubber, preferably comprising polybutadiene, more preferably consisting of polybutadiene; (b) 30 to 70 phr of oxidized wet beaded carbon black, preferably 40 to 60 phr of oxidized wet beaded carbon black, preferably 50 phr of oxidized wet beaded carbon black.

[0190] 39. The tire of any one of embodiments 35-38, wherein the tire includes a carcass, the carcass being made from the composition of any one of embodiments 1-40, the composition preferably including components (a) and (b): (a) 40-80 phr natural rubber and 20-60 phr synthetic rubber, preferably 50-70 phr natural rubber and 30-50 phr synthetic rubber, more preferably 60 phr natural rubber and 40 phr synthetic rubber, preferably comprising polybutadiene and emulsion styrene-butadiene rubber (ESBR), more preferably 20 phr polybutadiene and 20 phr emulsion styrene-butadiene rubber (ESBR); (b) 30 to 70 phr of oxidized wet beaded carbon black, preferably 40 to 60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black.

[0191] 40. The tire of any one of embodiments 35-39, comprising a chafer, the chafer being made from the composition of any one of embodiments 1-40, the composition preferably comprising components (a) and (b): (a) 30-70 phr of natural rubber and 30-70 phr of synthetic rubber, preferably 40-60 phr of natural rubber and 40-60 phr of synthetic rubber, more preferably 50 phr of natural rubber and 50 phr of synthetic rubber, preferably comprising emulsion styrene-butadiene rubber (ESBR), more preferably consisting of emulsion styrene-butadiene rubber (ESBR); (b) 55 to 95 phr of oxidized wet beaded carbon black, preferably 65 to 85 phr of oxidized wet beaded carbon black, preferably 75 phr of oxidized wet beaded carbon black.

[0192] 41. 41. The tire of any one of aspects 35-40, wherein the tire comprises a bead filler and / or an apex, the bead filler and / or the apex being made from the composition of any one of aspects 1-33, the composition preferably comprising components (a) and (b): (a) 80 to 100 phr of natural rubber, preferably 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; (b) 35 to 75 phr of oxidized wet beaded carbon black, preferably 45 to 65 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black.

[0193] 42. 42. The tire of any one of embodiments 35-41, the tire including an innerliner, the innerliner being made from the composition of any one of embodiments 1-33, the composition preferably including components (a) and (b): (a) 80 to 100 phr of synthetic rubber, preferably 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, preferably comprising, more preferably consisting of, a halogenated butyl rubber; (b) 40 to 80 phr of oxidized wet beaded carbon black, preferably 50 to 70 phr of oxidized wet beaded carbon black, more preferably 60 phr of oxidized wet beaded carbon black.

[0194] 43. 43. The tire of any one of embodiments 35-42, wherein the tire includes a tread, preferably a truck tread, the tread being made from the composition of any one of embodiments 1-33, the composition preferably including components (a) and (b): (a) 60-95 phr natural rubber and 5-40 phr synthetic rubber, preferably 70-85 phr natural rubber and 15-30 phr synthetic rubber, more preferably 80 phr natural rubber and 20 phr synthetic rubber, preferably comprising polybutadiene, more preferably consisting of polybutadiene; (b) 30 to 70 phr of oxidized wet beaded carbon black, preferably 40 to 60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black.

[0195] 44. 44. The tire of any one of embodiments 35-43, wherein the tire includes a tread, preferably a passenger tire tread, the tread being made from the composition of any one of embodiments 1-33, the composition preferably including components (a) and (b): (a) 80-100 phr of synthetic rubber, preferably 90-100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, preferably comprising solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprising 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; (b) 35 to 75 phr of oxidized wet beaded carbon black, preferably 45 to 65 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black.

[0196] 45. 45. The tire of any one of aspects 35-44, wherein the tire includes a tread, preferably a passenger tire tread, the tread being made from the composition of any one of aspects 1-33, the composition preferably including components (a)-(c): (a) 80-100 phr of synthetic rubber, preferably 90-100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, preferably comprising solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprising 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; (b) 3 to 25 phr of oxidized wet beaded carbon black, preferably 5 to 15 phr of oxidized wet beaded carbon black, more preferably 5 phr of oxidized wet beaded carbon black; (c) 60 to 100 phr of silica, preferably 70 to 90 phr of silica, more preferably 80 phr of silica.

[0197] 46. 46. ​​The tire of any one of embodiments 35-45, wherein the tire includes a tread, preferably an off-the-road (OTR) tire tread, the tread being made from the composition of any one of embodiments 1-33, the composition preferably including components (a) and (b): (a) 80 to 100 phr of natural rubber, preferably 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; (b) 35 to 75 phr of oxidized wet beaded carbon black, preferably 45 to 75 phr of oxidized wet beaded carbon black, more preferably 55 phr of oxidized wet beaded carbon black.

[0198] 47. 35. The article of embodiment 34, which is a cable sheath, a tube, a drive belt, a conveyor belt, a roll cover, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating, or a colored or printed article.

[0199] 48. 48. The article of any one of claims 34 to 47, wherein the article is a conveyor belt, the conveyor belt being comprised of the composition of any one of claims 1-3, the composition preferably comprising components (a) and (b): (a) 60-95 phr natural rubber and 5-40 phr synthetic rubber, preferably 70-85 phr natural rubber and 15-30 phr synthetic rubber, more preferably 80 phr natural rubber and 20 phr synthetic rubber, preferably comprising polybutadiene, more preferably consisting of polybutadiene; (b) 30 to 70 phr of oxidized wet beaded carbon black, preferably 40 to 60 phr of oxidized wet beaded carbon black, more preferably 50 phr of oxidized wet beaded carbon black.

[0200] 49. Use of a composition according to any one of aspects 1 to 33 for producing a tire, preferably a pneumatic tire, a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, an inner liner, an apex, a shoulder, a hump strip, a chafer, a bead filler, a cable sheath, a tube, a drive belt, a conveyor belt, a roll cover, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating, or a coloured or printed article, preferably an article according to any one of aspects 34 to 48.

[0201] 50. A process for preparing a composition, preferably a composition according to any one of claims 1 to 33, comprising: (a) mixing an elastomeric polymeric material with an oxidized wet beaded carbon black, the composition thus prepared being preferably used to make an article according to any one of claims 34 to 48.

[0202] 51. 51. The method of claim 50, wherein the oxidized wet-beaded carbon black (202) is prepared by wet-beading carbon black and then oxidizing the wet-beaded carbon black using ozone, preferably in a screw conveyor, to obtain the oxidized wet-beaded carbon black (202). [Explanation of symbols]

[0203] 200 Screw Conveyor 201 Wet bead carbon black 202 Oxidized wet bead carbon black 210 Entrance 211 barrels 212 Exit 213 Shaft 214 First spiral conveyor blade 215 Electric Motor 216 Ozone inlet 217 Ozone 218 Reaction Chamber 501 Second Spiral Conveyor Blade 502 First spiral conveyor blade 503 Circumferential clearance 504 First spiral conveyor blade spacing 505 Second Spiral Conveyor Blade Spacing 702, 703 Turner 801, 802 Turner's angle

Claims

1. (a) an elastomeric polymer material, and (b) Oxidized wet beaded carbon black (202) A composition comprising:

2. The composition of claim 1 , wherein the elastomeric polymeric material (a) comprises a rubber.

3. 3. The composition of claim 1 or 2, wherein the elastomeric polymer material (a) comprises natural rubber and / or synthetic rubber, and the synthetic rubber comprises styrene-butadiene rubber, polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinyl acetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber, or a mixture of any combination of the foregoing.

4. 3. The composition of claim 1 or 2, wherein the elastomeric polymeric material (a) comprises, based on parts by weight per 100 parts by weight of rubber, 40 to 100 phr of natural rubber and 5 to 60 phr of synthetic rubber.

5. 3. The composition of claim 1 or 2, wherein the oxidized wet-beaded carbon black (202) is prepared by wet-beading carbon black and then oxidizing the wet-beaded carbon black using ozone to obtain the oxidized wet-beaded carbon black (202).

6. 3. The composition according to claim 1, wherein the volatile content of the oxidized wet-beaded carbon black (202) measured at 950°C is 1 to 25% by weight.

7. 3. The composition according to claim 1, wherein the oxidized wet-beaded carbon black (202) has an average pellet crushing strength of pellets having a diameter of 1.0 to 1.4 mm of 4 to 80 cN.

8. 3. The composition according to claim 1, wherein the volatile content of the oxidized wet-beaded carbon black (202) measured at 950°C is 1.5 to 20% by weight.

9. 3. The composition according to claim 1, wherein the fines content of the oxidized wet beaded carbon black (202) is 0.1 to 50%.

10. 3. An article made from the composition of claim 1 or 2.

11. The article of claim 10, wherein the article is a tire.

12. 12. The article of claim 11, which is a cable sheath, a tube, a drive belt, a conveyor belt, a roll cover, a shoe sole, a hose, a seal, a profile, a damping element, a coating, or a colored or printed article.

13. 3. Use of the composition according to claim 1 or 2 for the manufacture of a tire, tire tread, belt, belt reinforcement, carcass, carcass reinforcement, sidewall, inner liner, apex, shoulder, hump strip, chafer, bead filler, cable sheath, tube, drive belt, conveyor belt, roll cover, shoe sole, hose, sealing element, profile, damping element, coating or colored or printed article.

14. (A) A method for preparing a composition comprising mixing an elastomeric polymer material with oxidized wet beaded carbon.

15. 15. The method of claim 14, wherein the oxidized wet-beaded carbon black (202) is prepared by wet-beading carbon black and then oxidizing the wet-beaded carbon black using ozone to obtain the oxidized wet-beaded carbon black (202).

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