• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    rubber formulation; and method of manufacturing a rubber formulation. described are rubber formulations comprising a base rubber composition, graphene carbon particles and non-conductive filler particles such as silica. the formulations have favorable properties, such as relatively low surface resistivities, and are useful in various applications, such as tire treads.
    公开号:BR112014025860B1
    申请号:R112014025860-0
    申请日:2013-04-15
    公开日:2021-07-20
    发明作者:Justin J Martin；Noel R Vanier；Brian K Rearick；Raphael O Kollah；Timothy A Okel；David Asay；Charles F Kahle；Cheng-Hung Hung
    申请人:Ppg Industries Ohio, Inc.；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to rubber formulas that comprise graphene carbon particles. BACKGROUND OF THE INVENTION
    [002] Several fillers were added to rubber compositions. Soot, for example, has been used on various parts of tires, including the tread, to reduce electrical charge build-up. Additionally, silica has been used in tire treads to reduce rolling resistance. While it is desirable to add significant amounts of silica to improve the performance characteristics of tire tread formulas, the maximum amount that can be added is limited by the relatively large amount of soot that is added to adequately reduce electrical charge buildup. SUMMARY OF THE INVENTION
    [003] One aspect of the present invention provides a rubber formula comprising a base rubber composition, from 0.1 to 20% by weight of graphene carbon particles and from 1 to 50% by weight of filler particles, wherein the tire tread formula has surface resistivity of less than 1010Q/m2.
    [004] Another aspect of the present invention provides a method of manufacturing a rubber formula comprising mixing graphene carbon particles and filler particles with a base rubber composition and curing the mixture, wherein the cured mixture has resistivity of surface less than 1010Q/sq. DETAILED DESCRIPTION OF THE ACHIEVEMENTS OF THE PRESENT INVENTION
    [005] Rubber formulas in accordance with the embodiments of the present invention are useful in various applications that include tire components such as vehicle tire treads, under-treads, tire casings, tire sidewalls, tire belt wedge, tire rim and tire wire coating film, wire and cable coating, hoses, washers and seals, industrial and automotive steering belts, engine mounts, V-belts, drive belts, coatings bearings, shoe sole materials, packing rings, damping elements and the like. Although tire tread formulations are described herein as a specific embodiment of the present invention, it is to be understood that rubber formulations in accordance with the present invention are not limited to such uses and can be used in a variety of other applications.
    [006] The rubber formulations according to the present invention comprise a base rubber composition to which graphene carbon particles are added. As used herein, the term "graphenic carbon particles" means carbon particles that have structures comprising one or more layers of flat sheets of an atom thick of carbon atoms bonded to sp2 that are densely packed in a lattice of honeycomb-shaped crystal. The average number of stacked layers may be less than 100, for example, less than 50. In certain embodiments, the average number of stacked layers is 30 or less, such as 20 or less, 10 or less, or, in some cases, 5 or less. The graphene carbon particles can be substantially flat, but at least a portion of the flat sheets can be substantially curved, curled, folded, or crumpled. Particles generally do not have spheroidal or equal-axis morphology.
    [007] In certain embodiments, the graphene carbon particles present in the compositions according to the present invention have a thickness, measured in a direction perpendicular to the layers of carbon atoms, of not more than 10 nanometers, not more than 5 nanometers or, in certain embodiments, no more than 4, 3, 2, or 1 nanometer, such as no more than 3.6 nanometer. In certain embodiments, the graphene carbon particles can be from 1 atom layers to layers 3, 6, 9, 12, 20, or 30 atoms thick or more. In certain embodiments, the graphene carbon particles present in the compositions according to the present invention have a thickness and length, measured in a direction parallel to the layers of carbon atoms, of at least 50 nanometers, such as more than 100 nanometers, in some cases more than 100 nanometers up to 500 nanometers or more than 100 nanometers up to 200 nanometers. Graphene carbon particles can be supplied in the form of ultra-thin flakes, platelets or sheets that have relatively high aspect ratios (where the aspect ratio is defined as the ratio of the longest dimension of a particle to the shortest dimension of a particle. a particle) of more than 3:1, such as more than 10:1.
    [008] In certain embodiments, the carbon graphene particles used in the compositions according to the present invention have relatively low oxygen content. For example, the graphene carbon particles used in certain embodiments of the compositions according to the present invention may, even when they have a thickness of no more than 5 or no more than 2 nanometers, have an oxygen content of no more than 2% by weight atomic, such as not more than 1.5 or 1% by atomic weight or not more than 0.6 atomic weight, such as about 0.5% by atomic weight. The oxygen content of graphene carbon particles can be determined using X-Ray Photoelectron Spectroscopy, as described in D.R. Dreyer et al, Chem. Soc. Rev. 39, 228-240 (2010).
    [009] In certain embodiments, the carbon graphene particles used in the compositions according to the present invention have specific B.E.T. at least 50 square meters per gram, such as 70 to 1000 square meters per gram, or in some cases 200 to 1000 square meters per gram, or 200 to 400 square meters per gram. As used herein, the expression "B.E.T specific extension." designates specific extent determined by nitrogen adsorption according to the ASTMD 3663-78 standard based on the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, 60, 309 (1938).
    [010] In certain embodiments, the carbon graphene particles used in the compositions according to the present invention have 2D/G Raman spectroscopy peak ratio of at least 1.1, for example, at least 1.2 or 1.3 . As used herein, the term "2D/G peak ratio" means the ratio of the intensity of the 2D peak at 2692 cm-1 to the intensity of the G peak at 1580 cm-1.
    [011] In certain embodiments, graphene carbon particles used in the compositions according to the present invention have relatively low bulk density. The carbon graphene particles used in certain embodiments of the present invention are characterized by having a bulk density (tapped density) of less than 0.2 g/cm3, such as not more than 0.1 g/cm3. For the purposes of the present invention, the bulk density of the graphemic carbon particles is determined by placing 0.4 grams of the graphemic and carbon particles in a glass measuring cylinder having a readable scale. The cylinder is raised to about 1.54 cm and tapped 100 times by tapping the base of the cylinder on a hard surface to allow the graphene carbon particles to settle inside the cylinder. The volume of the particles is then measured and the bulk density is calculated by dividing 0.4 grams by the measured volume, where the bulk density is expressed in terms of g/cm3.
    [012] In certain embodiments, the carbon graphite particles used in the compositions according to the present invention have compressed density and densification percentage that is less than the compressed density and densification percentage of graphite powder and certain types of graphene particles of carbon substantially flat. It is currently believed that lower tapped density and lower densification percentage contribute, separately from each other, to better dispersion and/or rheological properties than graphene carbon particles that exhibit higher tapped density and higher densification percentage. In certain embodiments, the compressed density of the carbon graphene particles is 0.9 or less, such as less than 0.8, less than 0.7, such as 0.6 to 0.7. In certain embodiments, the percentage densification of the carbon graphemic particles is less than 40%, such as less than 30%, such as 25 to 30%.
    [013] For the purposes of the present invention, the compressed density of carbon particles is calculated from a measured thickness of a given mass of particles after compression. Specifically, the measured thickness is determined by submitting 0.1 grams of graphene carbon particles to cold compression under 6800 kg of force in a 1.3 centimeter mold for 45 minutes, where the contact pressure is 500 MPa. The compressed density of graphene carbon particles is then calculated from this measured thickness according to the following equation:

    [014] The percentage densification of the graphene carbon particles is then determined as the calculated compressed density ratio of the graphene carbon particles, as determined above for 2.2g/cm3, which is the density of graphite.
    [015] In certain embodiments, graphene carbon particles have measured apparent net conductivity of at least 100 microSiemens, such as at least 120 microSiemens, such as at least 140 microSiemens immediately after mixing and at later times, such as within 10 minutes , 20 minutes, 30 minutes or 40 minutes. For the purposes of the present invention, the apparent net conductivity of graphene carbon particles is determined as follows. First, a sample comprising a 0.5% solution of graphene carbon particles in butyl cellosolve is sonicated for 30 minutes with a bath sonicator. Immediately after sonication, the sample is placed in a standard calibrated electrolyte conductivity cell (K=1). A Fisher Scientific AB 30 conductivity meter is introduced into the sample to measure the sample's conductivity. Conductivity is set over about 40 minutes.
    [016] According to certain embodiments, percolation, defined as long-range interconnectivity, occurs between the conductive carbon graphene particles. This percolation can reduce the resistivity of formulations. The conductive graphene particles can occupy a minimal volume within the composite matrix, such that the particles form a continuous or nearly continuous network. In this case, the aspect ratios of graphene carbon particles can affect the minimum volume needed for percolation. In addition, the surface energy of graphene carbon particles can be identical or similar to the surface energy of elastomeric rubber. Otherwise, particles may tend to flocculate or separate as they are processed.
    [017] The graphene carbon particles used in the compositions according to the present invention can be prepared, for example, by means of thermal processes. According to embodiments of the present invention, graphene carbon particles are produced from carbon-containing raw materials that are heated to high temperatures in a thermal zone. Graphene carbon particles can be produced, for example, by the systems and methods described in U.S. Patent Applications Serial Numbers 13/249,315 and 13/309,894.
    [018] In certain embodiments, graphene carbon particles can be obtained using the apparatus and method described in U.S. Patent Application Serial Number 13/249,315 at [0022] to [0048], the part of which is cited. is incorporated herein by reference, wherein (i) one or more hydrocarbon feedstocks capable of forming a substance with two carbon fragments (such as n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2- dichloroethane, allyl alcohol, propionaldehyde and/or vinyl bromide) are introduced into a thermal zone (such as plasma); and (ii) the hydrocarbon is heated in the thermal zone to a temperature of at least 1000°C to form the graphene carbon particles. In other embodiments, graphene carbon particles can be made using the apparatus and method described in U.S. Patent Application Serial Number 13/309,894 at [0015] to [0042], the cited portion of which is incorporated herein by reference. , wherein (i) a methane feedstock (such as a material comprising at least 50% methane or, in some cases, liquid or gaseous methane of at least 95 or 99% or more purity) is introduced into a thermal zone (such as plasma); and (ii) the methane precursor is heated in the thermal zone to form graphene carbon particles. These methods can produce graphene carbon particles that have at least some of the characteristics described above, and in some cases all of them.
    [019] DURING THE PRODUCTION OF GRAPHIC CARBON PARTICLES BY THE METHODS DESCRIBED ABOVE, A PRECURSOR THAT CONTAINS CARBON IS SUPPLIED AS A RAW MATERIAL THAT CAN BE PLACED IN CONTACT WITH AN INERT CONDUCTING GAS. CARBON-CONTAINING PRECURSOR MATERIAL CAN BE HEATED IN A THERMAL ZONE, FOR EXAMPLE THROUGH A PLASMA SYSTEM. IN CERTAIN EMBODIMENTS, THE PRECURSOR MATERIAL IS HEATED TO A TEMPERATURE IN THE RANGE OF 1,000 °c TO 20,000 °c, SUCH AS 1,200 °c TO 10,000 °c. FOR EXAMPLE, THE THERMAL ZONE TEMPERATURE CAN BE IN THE RANGE OF 1,500 TO 8,000 °C AS WELL AS 2,000 TO 5,000 °C. ALTHOUGH THE THERMAL ZONE MAY BE GENERATED BY A PLASMA SYSTEM, IT SHOULD BE UNDERSTOOD THAT ANY OTHER SUITABLE HEATING SYSTEM CAN BE USED TO CREATE THE THERMAL ZONE SUCH AS VARIOUS TYPES OF FURNACES INCLUDING ELECTRICALLY TUBE AND SIMPLE FURNACES.
    [020] The gaseous stream can be brought into contact with one or more cooling streams that are injected into the plasma chamber through at least one quench stream injection port. The coolant stream can cool the gaseous stream to facilitate formation or control particle size or morphology of graphene carbon particles. In certain embodiments of the present invention, after contacting the gaseous product stream with the cooling streams, ultrafine particles may pass through a converging member. After the carbon graphenic particles leave the plasma system, they can be collected. Any suitable means can be used to separate the graphene carbon particles from the gas stream, such as, for example, a bag filter, cyclone separator or deposition onto a substrate.
    [021] Without restriction to any theory, it is currently believed that the above methods of fabrication of graphene carbon particles are specifically suited to the production of graphene carbon particles that have relatively low thickness and relatively high aspect ratio in combination with content of relatively low oxygen, as described above. In addition, these methods are currently believed to produce a substantial amount of graphene carbon particles that have substantially curved, curled, folded, or crumpled morphology (herein referred to as "3D" morphology), as opposed to the predominant production of particles that have morphology substantially two-dimensional (or flat). This characteristic is believed to be reflected in the compressed density characteristics described above and is believed to be beneficial to the present invention because, as is currently believed, when a significant portion of graphene carbon particles have 3D morphology, the "edge contact" the edge" and "edge to face" between graphene carbon particles within the composition can be promoted. This is believed to be because particles that have 3D morphology are less likely to be aggregated into the composition (due to smaller Van der Waals forces) than particles that have two-dimensional morphology. Furthermore, it is currently believed that even in the case of "face-to-face" contact between particles that have 3D morphology, as particles may have more than one face plane, not the entire surface of the particle is placed in a single interaction "face-to-face" with another isolated particle, but can participate in interactions with other particles, including other "face-to-face" interactions on other planes. As a result, graphene carbon particles that have 3D morphology are currently believed to provide the best conductive path in present compositions and are currently believed to be useful in achieving the electrical conductivity characteristics sought by the present invention, particularly when particles carbon graphenes are present in the composition in the relatively low amounts described below.
    [022] In certain embodiments, graphene carbon particles are present in rubber formulas in amounts of at least 0.1% by weight, such as at least 0.5% by weight or, in some cases, at least 1% by weight. In certain embodiments, the carbon graphene particles are present in the composition in amounts of not more than 15% by weight, such as not more than 10% by weight or, in some cases, not more than 5% by weight, based on the weight of all non-volatile components of the composition.
    [023] In certain embodiments, the tire tread base rubber composition or other formulas comprise synthetic rubber, natural rubber, mixtures thereof, and the like. In certain embodiments, the base rubber composition comprises copolymer of styrene butadiene, polybutadiene, halobutyl and/or natural rubber (polyisoprenes). For use in tire treads, the base rubber composition generally comprises from 30 to 70% by weight of the overall tire tread formulation, for example from 34 to 54% by weight.
    [024] In certain embodiments, the rubber formulation comprises a curable rubber. As used herein, the term "curable rubber" denotes both natural rubber and its various raw and claimed forms, as well as various synthetic rubbers. For example, the curable rubber can include styrene/butadiene rubber (SBR), butadiene rubber (BR), natural rubber, any other known type of organic rubber and combinations thereof. As used herein, the terms "rubber", "elastomer" and "rubberized elastomer" may be used interchangeably, unless otherwise indicated. The terms "rubber compound", "rubber compound" and "rubber compound" can be used interchangeably to refer to rubbers that have been combined or blended with various ingredients and materials and these expressions are well known to those skilled in the art. of rubber mixture or rubber compound.
    [025] In addition to graphene carbon particles in the amounts described above, tire tread formulations in certain embodiments still comprise filler particles. Suitable fillers for use in the rubber formulations in accordance with the present invention can include a wide variety of materials known to those of ordinary skill in the art. Non-limiting examples may include inorganic oxides such as, but not limited to, inorganic particles or solid amorphous materials that contain oxygen (chemically absorbed or covalently bonded) or hydroxyl (bound or free) on an exposed surface such as, but not limited to, oxides of the metals of Periods 2, 3, 4, 5, and 6 of Groups Ib, IIb, IIIa, IIIb, IVa, IVb (except carbon), Va, VIa, VIIa, and VIII of the Periodic Table of Elements in Advanced Inorganic Chemistry: A Comprehensive Text by F. Albert Cotton et al, Fourth Edition, John Wiley and Sons, 1980. Non-limiting examples of inorganic oxides for use in the present invention may include precipitated silica, colloidal silica, silica gel, aluminum silicates, alumina and mixtures thereof. Suitable metallic silicates can include a wide variety of materials known in the art. Non-limiting examples can include, but are not limited to, alumina, lithium, sodium, potassium silicate and mixtures thereof.
    [026] In certain embodiments, the filler particles comprise silica in typical amounts of 1 to 50% by weight, for example from 28 to 44% by weight. In certain embodiments, it is desirable to maximize the amount of silica present in the formulation to increase traction and fuel efficiency performance. For example, it may be desirable to add silica in amounts greater than 30% by weight, for example greater than 40% by weight.
    [027] In certain embodiments, silica can be precipitated silica, colloidal silica and mixtures thereof. Silica can have a final mean particle size of less than 0.1 micron, 0.01 to 0.05 micron, or 0.015 to 0.02 micron as measured using an electron microscope. In additional alternative non-limiting embodiments, the silica may span from 25 to 1000, 75 to 250, or 100 to 200 square meters per gram. Extension can be measured using conventional methods known in the art. As used herein, extension is determined by the method of Brunauer, Emmett and Teller (BET) according to ASTM D1993-91. BET extension can be determined by fitting five points of relative pressure from a nitrogen sorption isotherm measurement performed with a Micromeritics TriStar 3000® instrument. A FlowPrep-060® station provides heat and continuous gas flow to prepare sample for analysis. Prior to nitrogen sorption, silica samples are dried by heating at a temperature of 160 °C in nitrogen flow (grade P5) for at least 1 (one) hour.
    [028] The silica filler for use in the present invention can be prepared using a number of methods known to those of ordinary skill in the art. For example, silica can be produced by the methods described in U.S. Patent Application Serial Number 11/103,123, which is incorporated herein by reference. In a non-limiting embodiment, silica for use as an untreated filler can be prepared by combining an aqueous solution of acid-soluble metal silicate to form a silica slurry. The silica slurry can be filtered, optionally washed and dried using conventional methods known to those skilled in the art.
    [029] According to certain embodiments of the present invention, the relative amounts of graphemic carbon and silica particles are controlled in such a way that the amount of silica is maximized for improved performance characteristics, while the amount of graphemic carbon particles is minimized in an amount that provides sufficient static dissipation. For example, the amount of silica may be greater than 30% by weight or greater than 40% by weight, while the amount of graphene carbon particles may be less than 10 or 5% by weight or less than 2 or 1% by weight . In certain embodiments, the weight ratio of silica particles to graphene carbon particles is greater than 2:1 or 3:1, for example, greater than 4:1, 5:1 or 6:1. In specific embodiments, the weight ratio may be greater than 8:1 or 10:1.
    [030] In a complex system according to the present invention in which both graphene carbon particles and silica particles are present in the elastomeric rubber matrix, the conductive carbon graphenic particles can form a continuous or nearly continuous network, despite the presence of insulating silica particles in the relatively large amounts described above.
    [031] According to certain embodiments, rubber formulations have surface resistivities of less than 1010Q/m2, for example less than 109Q/m2 or less than 107Q/m2.
    [032] The formulations according to the present invention can be prepared by combining graphene carbon particles and/or filler particles with emulsion and/or solution polymers, for example, organic rubber comprising styrene/butadiene solution (SBR), polybutadiene rubber or one of its mixtures, to form a master batch. Curable rubbers for use in the master batch can vary widely, are well known to those skilled in the art, and can include vulcanizable and sulfur-curable rubbers. In a non-limiting embodiment, curable rubbers can include those used for tires and mechanical rubber products. A non-limiting example of a master batch may comprise a combination of organic rubber, water immiscible solvent, treated load and, optionally, processing oil. This product can be supplied by a rubber producer to a tire manufacturer. A benefit of using master batch by a tire manufacturer may be the fact that graphene carbon particles and/or silica particles are substantially uniformly dispersed in the rubber, which can result in substantial reduction or minimization of time. of mixing to produce the composite rubber. In a non-limiting embodiment, the master batch may contain from 10 to 150 parts of graphene carbon particles and/or silica particles per 100 parts of rubber (PHR).
    [033] The graphene carbon particles and/or silica particles can be mixed with an uncured rubberized elastomer used to prepare the vulcanizable rubber composition by a conventional means such as in a Banburry mixer or in rubber mills at temperatures of 38° C to 200°C. Non-limiting examples of other conventional rubber additives present in the rubber composition may include conventional peroxide or sulfur curing systems. In alternative non-limiting embodiments, the sulfur curing system may include 0.5 to 5 parts sulfur, 2 to 5 parts zinc oxide and 0.5 to 5 parts accelerator. In additional alternative non-limiting embodiments, the peroxide curing system may include from 1 to 4 parts of a peroxide such as dicumyl peroxide.
    [034] Non-limiting examples of conventional rubber additives may include clays, talc, soot and the like, oils, plasticizers, accelerators, antioxidants, heat stabilizers, light stabilizers, zone stabilizers, organic acids such as, for example, stearic acid, benzoic acid or salicylic acid, other activators, extenders and color pigments. The selected compost recipe will vary with the specific vulcanized preparation. These recipes are well known to those skilled in the art of rubber compounds. In a non-limiting embodiment, a benefit of using silica particles in accordance with the present invention when the coupling material is a mercapto-organometallic compound may be the elevated temperature stability of a rubber compound containing these silica particles and essentially the absence of curing of a rubber compound at temperatures up to at least 200 °C when mixed for at least half a minute or up to 60 minutes.
    [035] In alternative non-limiting embodiments, the compounding process can be carried out continuously or in batches. In a further non-limiting embodiment, the rubber composition and at least a portion of the carbon graphemic particles and/or silica particles can be continuously supplied to an initial part of a mixing process to produce a mixture and mixing can be continuously mixed. supplied for a second part of the mixing process.
    [036] The following examples are intended to illustrate certain aspects of the present invention and are not intended to limit the scope of the present invention. EXAMPLES
    [037] Various tire tread compounds that contain varying amounts of conductive additives have been manufactured and evaluated to determine surface resistivity. A high-dispersion silica reinforcing mesh was present in amounts ranging from 47 to 70 parts per 100 rubber (PHR). Conductive particle additives included graphene carbon particles produced in accordance with embodiments of the present invention, commercially available graphene through XG Sciences, graphite, exfoliated graphite, tin oxide and antimony, nickel-coated graphite, and polypyrrole-coated silica. The carbon graphene particles were produced by the method described in U.S. Patent Application Serial Number 13/309,894. The components listed in Table 1 were blended and cured using equipment and methods well known in the tire tread formulation art. Styrene butadiene rubbers and polybutadiene rubbers were blended with the conductive additives, fillers, processing aids, antioxidants and part of the curing package in the first step to form a master batch. The components were mixed for 7 minutes or until the compound reached 160 °C. In the second step, the master batch was fed back to the blender and processed for a further 10 minutes at 160°C. In the third and final mixing step, the remaining dressings and accelerators are added to the master batch and blended for 2.5 minutes at 108°C. TABLE 1 TIRE TIRE BANDS COMPOSITIONS

    A - Graphene Carbon Particles B - Nickel Coated Graphite C - Tin Oxide and Antimony D - Polypyrrole Coated Silica E - Asbury Carbon Graphites (3725, M850, 4014, 3775, 4821, 230U) F - Graphene Sciences XG ( C-750, C-300, M-25, M-5) 1 Polybutadiene rubber available through The Goodyear Tire and Rubber Company 2 Styrene butadiene rubber available through Lanxess 3 Bis(triethoxysilylpropyl) polysulfide available through from Evonik 4 Sulfur manufacturers of commercially available rubber 5 N-cyclohexylbenzothiazol-2-sulfenamide available through Flexsys
    [038] The surface resistivities of the cured and finished rubber materials were measured according to the following procedure: Dr. Thiedig's Milli-To Ohm meter turned on and kept in equilibrium for 0.5 hours before experimental sampling; the rubber sample is placed on the insulating plastic plate; 2.27 kg concentric circle ground electrode positioned over the rubber sample with gentle pressure to ensure homogeneous contact; electrode voltage is applied, surface resistivity is measured using the smallest possible setting of 10,100 or 500 volts; and surface resistivity is determined by 10x the screen reading with units of Q or Q/m2.
    [039] Surface resistivity results are shown in Table 2. Materials in which the surface resistivity is in the range of 106 to 109 or 1010 are said to be static dissipators. For tread compounds filled with silica, it may be desirable for the percolation limit of the conductive charge to be at a minimum, both in percent by weight and by volume. Of the materials tested, the graphene carbon particles according to the present invention were the only particles that exhibited static dissipative properties at low loads (5% by volume) in the presence of silica. In addition to the electrical properties of the finished rubber products, the graphene carbon particles exhibited uniquely improved blending properties. TABLE 2 SURFACE RESISTIVITIES OF RUBBER FORMULATIONS

    [040] In certain embodiments, it is desirable to improve the dispersion of silica in the rubber mixture by breaking up large silica agglomerates that may be present in smaller or submicron particles. The quality of the silica dispersion can be determined using equipment called a Dispergrader®. When examining rubber samples using this device, the amount of white area should be minimal. Silica dispersion can be important for consistent performance, wear, good reinforcement, and for limiting failures such as crack propagation. Therefore, fillers that significantly reduce silica dispersion at low loadings may not be acceptable. Standardized silica dispersions for tread compounds prepared using highly dispersible silica and various types of particles and conductive silica are shown in Table 3. TABLE 3 CONDUCTIVE PARTICLE DISPERSION (STANDARDIZED FOR HDS)

    [041] In certain embodiments, graphene carbon particles can provide improved reinforcing properties due to their high specific extensions with respect to the volume they occupy. Tire tread compounds manufactured with graphene carbon particles and silica particles can exhibit improved tensile strength and traction improvements as defined by tan δ at 0 °C. Rolling resistance is increased although abrasive wear may remain the same. These properties are shown in Table 4. TABLE 4 SCROLL BAND PROPERTIES


    [042] The combination of low percolation limit, increased tensile strength and excellent silica dispersion obtained by using graphene carbon particles according to the present invention makes the formulations very useful in tire treads.
    [043] In certain embodiments, by pre-dispersing the carbon graphemic particles in a compatible resin, the resistivity of a tread compound can be reduced at lower carbon graphemic particle loadings, as shown in Table 5 In this example, the graphene carbon particles are pre-dispersed in a sulfur-containing resin commercially known as Thiplast. TABLE 5 SURFACE RESISTIVITIES OF TREAD TREADS DESIGNED WITH PRE-DISPER GRAPH

    [044] A criterion for evaluating the performance of conductive filler particles in systems with non-conductive fillers can be evaluating the resistivity of a rubber sample at different ratios between insulating charge and conductive charge, such as the volume or weight between silica and graphene carbon particles. As the ratio of the non-conductive charge to the conductive charge drops, percolation can be seen at lower charges of the conductive charge. Table 6 illustrates the increased surface resistivity of a sample according to the present invention that contains graphene carbon particles in relatively high volume ratio between silica and graphene carbon particles, compared to another sample having the same volume ratio but different conductive particles. TABLE 6

    [045] For purposes of this detailed description, it is to be understood that the present invention may consider several alternative variations and sequences of steps, unless expressly specified otherwise. In addition, unless otherwise indicated, all numbers expressing quantities used in the specification and claims are to be understood as modified in all cases by the expression "about". Consequently, unless otherwise indicated, the numerical parameters described in the above descriptive report and in the appended claims are approximate and may vary depending on the properties that are desired to be obtained by means of the present invention. At the very least, and not as an attempt to limit the application of the equivalents doctrine to the scope of the claims, each numerical parameter should at least be interpreted in light of the range of significant digits reported and through the application of common rounding techniques.
    [046] Although the numerical ranges and parameters that define the broad scope of the present invention are approximate, the numerical values defined in the specific examples are reported as accurately as possible. Any numerical values, however, inherently contain certain errors that necessarily result from the standard variation found in their corresponding test measurements.
    [047] In addition, it should be understood that any numerical range indicated herein is intended to include all sub-ranges included therein. For example, a range from "1 to 10" is intended to include all sub-ranges between the indicated minimum value of 1 and the indicated maximum value of 10, inclusive, that is, it has a minimum value greater than or equal to 1 and a maximum value less than or equal to 10.
    [048] In this patent application, the use of the singular includes the plural and the plural includes the singular, unless specifically indicated otherwise. Furthermore, in this patent application, the use of "or" indicates "and/or", unless specifically indicated otherwise, even though "and/or" may be explicitly used in certain cases.
    权利要求:
    Claims (19)
    [0001]
    1. RUBBER FORMULATION, characterized in that it comprises: - a base rubber composition; - 0.1 to 20% by weight of graphene carbon particles; and - 1 to 50% by weight of filler particles, wherein the graphene carbon particles have an oxygen content of less than 2% by atomic weight and the rubber formulation has surface resistivity of less than 1010Q/m2.
    [0002]
    RUBBER FORMULATION according to claim 1, characterized in that the rubber formulation comprises a tire tread formulation.
    [0003]
    3. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles comprise less than 10% by weight of the formulation.
    [0004]
    4. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles comprise less than 5% by weight of the formulation.
    [0005]
    5. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles have apparent net conductivity of at least 100 microSiemens.
    [0006]
    6. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles have a bulk density of less than 0.2 g/cm3.
    [0007]
    7. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles have a compressed density of less than 0.9.
    [0008]
    8. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles comprise silica.
    [0009]
    9. RUBBER FORMULATION, according to claim 8, characterized in that the silica comprises from 28 to 44% by weight of the formulation.
    [0010]
    10. RUBBER FORMULATION according to claim 8, characterized in that the silica comprises precipitated silica.
    [0011]
    11. RUBBER FORMULATION according to claim 1, characterized in that the base rubber composition comprises styrene/butadiene rubber, butadiene rubber, natural rubber and/or functionalized derivatives thereof.
    [0012]
    12. RUBBER FORMULATION according to claim 11, characterized in that the base rubber composition further comprises at least one additive selected from processing oils, antioxidants, curatives and metal oxides.
    [0013]
    RUBBER FORMULATION, according to claim 1, characterized in that the formula comprises less than 10% by weight of soot.
    [0014]
    RUBBER FORMULATION, according to claim 1, characterized in that the formula is substantially free of soot.
    [0015]
    15. RUBBER FORMULATION, according to claim 1, characterized in that graphene carbon particles comprise less than 10% by weight of the formulation and the filler particles comprise silica in an amount greater than 28% by weight of the formulation.
    [0016]
    16. RUBBER FORMULATION, according to claim 8, characterized in that silica and graphene carbon particles are present in the formulation in a weight ratio of more than 4:1.
    [0017]
    17. METHOD OF MANUFACTURING A RUBBER FORMULATION, characterized in that it comprises: - mixing graphene carbon particles and filler particles with a base rubber composition; and - mixture curing, in which graphene carbon particles have oxygen content of less than 2% by atomic weight and the cured mixture has surface resistivity of less than 1010Q/m2.
    [0018]
    18. METHOD, according to claim 17, characterized in that graphene carbon particles comprise less than 10% by weight of the formulation and the filler particles comprise silica in an amount greater than 28% by weight of the formulation.
    [0019]
    19. METHOD according to claim 18, characterized in that silica and graphene carbon particles are present in the formula in a weight ratio of more than 4:1.
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    同族专利:
    公开号 | 公开日
    EP2844694B1|2017-08-09|
    SG11201407123RA|2014-12-30|
    MX2014012414A|2015-06-03|
    SI2844694T1|2017-10-30|
    JP6087424B2|2017-03-01|
    MY185879A|2021-06-14|
    KR101668776B1|2016-10-26|
    HK1201285A1|2015-08-28|
    CN104334628A|2015-02-04|
    US20130296479A1|2013-11-07|
    RU2602142C2|2016-11-10|
    AU2013256788B2|2015-08-06|
    JP2015517583A|2015-06-22|
    PH12014502428B1|2015-01-12|
    HUE037079T2|2018-08-28|
    MX361693B|2018-12-10|
    EP2844694A1|2015-03-11|
    CA2871739C|2017-10-10|
    PT2844694T|2017-10-04|
    PH12014502428A1|2015-01-12|
    WO2013165677A1|2013-11-07|
    KR20150003374A|2015-01-08|
    CA2871739A1|2013-11-07|
    CN104334628B|2016-11-16|
    ES2642016T3|2017-11-14|
    IL234995A|2017-05-29|
    PL2844694T3|2018-01-31|
    AU2013256788A1|2014-10-16|
    RU2014148680A|2016-06-27|
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    法律状态:
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C08L 7/00 (2006.01), C08L 9/00 (2006.01), C08L 21/ |
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/462,955|US20130296479A1|2012-05-03|2012-05-03|Rubber formulations including graphenic carbon particles|
    US13/462,955|2012-05-03|
    PCT/US2013/036565|WO2013165677A1|2012-05-03|2013-04-15|Rubber formulations including graphenic carbon particles|
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