Elastomeric composites produced from sustainable fillers and methods of making and using the same

Abstract

The present invention relates to elastomeric composites produced from sustainable fillers and methods of making and using the same. Methods of producing elastomeric composites in a sustainable manner are embodied and broadly described herein in accordance with one or more objects of the present disclosure. In one aspect, the elastomeric composites include carbon materials derived from carbon oxide compounds homogenously dispersed in an elastomer. The elastomeric composites described herein, once vulcanized, have comparable or improved performance properties compared to elastomers prepared from traditional fillers and methods. The unvulcanized elastomeric composites described herein can be vulcanized to produce various components for the production of tires and other articles.

Description

Technical Field

[0001] This invention relates to elastomeric composite materials produced from sustainable fillers and methods for their manufacture and use. Background Technology

[0002] Fillers such as carbon black are widely used in the production of rubber compositions for manufacturing tires and other products. In large-scale production, it is always desirable to use environmentally sustainable materials with minimal long-term environmental impact. However, the selection of such materials must not compromise the chemical and physical properties of the rubber composition. Therefore, sustainable processes for producing rubber compositions with satisfactory performance properties are needed. Summary of the Invention

[0003] For one or more purposes of this disclosure, methods for sustainably producing elastomeric composite materials are specifically embodied and broadly described herein. In one aspect, the elastomeric composite material comprises a carbon material derived from a carbon oxide compound uniformly dispersed within an elastomer. The elastomeric composite materials described herein, upon vulcanization, possess performance properties comparable to or improved upon those of elastomers prepared by conventional fillers and methods. The vulcanized elastomeric composite materials described herein can be components used in the production of tires and other articles.

[0004] Upon review of the specific embodiments, other compositions, methods, features, and advantages of this disclosure will be or will become apparent to those skilled in the art. All such additional compositions, methods, features, and advantages are intended to be included within the scope of this specification and disclosure, and are protected by the appended claims. Furthermore, all optional and preferred features and modifications of the described embodiments may be used in all aspects of the disclosure taught herein.

[0005] The present invention discloses the following solutions: Option 1. An elastomer composite material comprising a carbon material derived from a carbon oxide compound uniformly dispersed in an elastomer.

[0006] Option 2. The elastomeric composite material according to Option 1, wherein the carbon oxide compound comprises carbon dioxide, carbon monoxide, or a combination thereof.

[0007] Option 3. The elastomeric composite material according to Option 1 or 2, wherein the carbon material derived from the carbon oxide compound contains reduced carbon oxide gas.

[0008] Option 4. The elastomeric composite material according to any one of Options 1-3, wherein the carbon material derived from carbon oxide compounds is generated by contacting the carbon oxide gas with a reducing agent gas stream in the presence of a catalyst.

[0009] Option 5. The elastomeric composite material according to Option 4, wherein the reducing agent gas stream comprises hydrogen or hydrocarbon gas.

[0010] Option 6. The elastomeric composite material according to Option 5, wherein the hydrocarbon gas comprises natural gas or syngas.

[0011] Option 7. The elastomeric composite material according to Option 5, wherein the hydrocarbon gas comprises methane.

[0012] Scheme 8. The elastomeric composite material according to any one of Schemes 4-7, wherein the catalyst comprises transition metal atoms selected from Group VI metals, Group VII metals and mixtures thereof.

[0013] Scheme 9. The elastomeric composite material according to any one of Schemes 4-7, wherein the catalyst comprises a metal oxide compound selected from beryllium oxide, magnesium oxide, calcium oxide, strontium oxide and barium oxide.

[0014] Scheme 10. The elastomeric composite material according to Scheme 1, wherein the carbon material derived from carbon oxide gas is produced by a method comprising the steps of: (a) mixing the carbon oxide gas and a reducing gas stream to form a reactive gas mixture, and (b) injecting the reactive gas mixture into a reaction zone in the presence of a catalyst, wherein the catalyst reacts with the reaction mixture to form the carbon material derived from carbon oxide gas.

[0015] Option 11. An elastomeric composite material according to any one of Options 1-10, wherein the method of producing the elastomeric composite material comprises reacting a continuous flow of a first fluid containing the elastomeric material with a continuous flow of a second fluid containing the carbon material derived from carbon oxides to form a mixture with the elastomeric material and produce the elastomeric composite material.

[0016] Option 12. The elastomeric composite material according to any one of Options 1-10, wherein the elastomeric composite material is produced by a method comprising the following steps: (a) A continuous flow of a first fluid containing the elastomer is fed into a reactor comprising a mixing zone and a discharge end; (b) A continuous flow of a second fluid comprising the carbon material derived from carbon oxides is fed into the mixing zone of the reactor to form an elastomeric composite material, wherein the elastomeric composite material is conveyed as a continuous flow to the discharge end; and (c) Discharge the elastomer composite material from the outlet end of the reactor.

[0017] Option 13. The elastomeric composite material according to Option 11 or 12, wherein the carbon material derived from carbon oxide is milled before being mixed with the elastomeric material.

[0018] Scheme 14. The elastomeric composite material according to any one of Schemes 1-13, wherein the elastomeric material comprises natural rubber, a chlorinated derivative of natural rubber, or butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene wherein the alkyl group is a C1 to C3 alkyl group, acrylonitrile, a homopolymer, copolymer or terpolymer of ethylene or propylene.

[0019] Option 15. An elastomeric composite material according to any one of Options 1-14, wherein the method does not include mixing the additive with the elastomeric material and the carbon material derived from carbon oxides.

[0020] Scheme 16. The elastomeric composite material according to any one of Schemes 1-14, wherein the method further comprises mixing at least one additive with the elastomeric material and the carbon material derived from carbon oxides.

[0021] Scheme 17. The elastomeric composite material according to Scheme 16, wherein the at least one additive is selected from anti-ozone agents, antioxidants, plasticizers, processing aids, resins, flame retardants, bulking oils, lubricants, and any combination thereof.

[0022] Scheme 18. The elastomeric composite material according to any one of Schemes 1-17, wherein the carbon material derived from carbon oxide is approximately 20 phr to approximately 120 phr of the elastomeric composite material.

[0023] Scheme 19. A vulcanized elastomer composite material comprising a vulcanized elastomer composite material according to any one of Schemes 1-18.

[0024] Option 20. The vulcanized elastomer composite material according to Option 19, wherein the vulcanized elastomer composite material exhibits one or more performance characteristics similar to furnace black, wherein the surface area ratio of the furnace black, as defined by ASTM D6556, exhibits at least 15% higher performance characteristics than furnace black using dry-blended equivalent complexes of carbon black derived from the same carbon oxide as the elastomer composite material.

[0025] Option 21. The vulcanized elastomer composite material according to Option 19, wherein when the elastomer composite material is produced by a liquid method, the Z-value of the elastomer composite material is at least 15% higher than the Z-value of an elastomer composite material produced by a dry-mixing method using the same amount of carbon material derived from carbon oxide compounds.

[0026] Scheme 22. An article comprising the vulcanized elastomer composite material according to Scheme 19.

[0027] Option 23. The article of claim 22, wherein the article of claim 22 comprises a tire or a tire assembly.

[0028] Option 24. The article of claim 23, wherein the tire assembly comprises a tire tread, a tire sub-tread, a tire wire-skim, a tire sidewall, or a cushion gum for retreading the tire.

[0029] Scheme 25. A method for producing an elastomeric composite material comprising a carbon material derived from carbon oxides, the method comprising mixing an elastomer with the carbon material derived from carbon oxides, wherein the carbon material derived from carbon oxides is uniformly dispersed in the elastomer. Detailed Implementation

[0030] With the help of the teachings given in the foregoing specification, those skilled in the art will conceive of many modifications and other embodiments of the disclosed compositions and methods. Therefore, it is to be understood that this disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Those skilled in the art will recognize many variations and modifications to the aspects described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0031] Although specific terms are used in this document, they are used only in a general and descriptive sense, not for the purpose of limitation.

[0032] As will be apparent to those skilled in the art upon reading this disclosure, each embodiment described and illustrated herein has discrete components and features that can be readily separated from or combined with features of any of the other plurality of embodiments without departing from the scope or spirit of this disclosure.

[0033] Any enumerated method may be performed in the order of the enumerated events or in any other logically possible order. That is, unless expressly stated otherwise, there is absolutely no intention to interpret any method or aspect set forth herein as requiring its steps to be performed in a particular order. Therefore, if a method claim does not specifically specify in the claims or specification that the steps are limited to a particular order, there is absolutely no intention to infer the order in any way. This applies to any possible non-express basis of interpretation, including the logical content of the arrangement of steps or procedures, the general meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0034] Before describing various aspects of this disclosure, the following definitions are provided and shall be used unless otherwise specified. Other terms may be defined elsewhere in this disclosure.

[0035] definition As used herein, “comprising” should be interpreted as specifying the presence of the mentioned feature, integer, step, or component, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Furthermore, the terms “through,” “comprising,” “comprises,” “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such” are each used in their open, non-restrictive sense and are interchangeable. Additionally, the term “comprising” is intended to include instances and aspects covered by the terms “consisting of” and “basically composed of.” Similarly, the term “basically composed of” is intended to include instances covered by the term “consisting of.”

[0036] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly specifies otherwise. Thus, for example, reference to “a plasticizer” includes, but is not limited to, mixtures or combinations of two or more such plasticizers, and so on.

[0037] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in range format herein. It should be further understood that each endpoint of a range is meaningful both relative to and independent of another endpoint. It should also be understood that many numerical values ​​are disclosed herein, and each numerical value is also disclosed herein as “approximately” that particular value, in addition to being the value itself. For example, if the value “10” is disclosed, then “approximately 10” is also disclosed. A range may be expressed herein as from “approximately” one particular value, and / or to “approximately” another particular value. Similarly, when a numerical value is expressed as an approximation using the antecedent “approximately”, it should be understood that the particular value constitutes another aspect. For example, if the value “approximately 10” is disclosed, then “10” is also disclosed.

[0038] When expressing a range, another aspect includes from one specific numerical value and / or to another specific numerical value. For example, when a specified range includes one or two boundaries, the range excluding any one or both of these included boundaries is also included in this disclosure; for example, the phrase "x to y" includes the range from "x" to "y" as well as the range greater than "x" and less than "y". The range can also be expressed as an upper limit, such as "approximately x, y, z or less", and should be interpreted as including the specific ranges of "approximately x", "approximately y", and "approximately z" as well as the ranges of "less than x", "less than y", and "less than z". Similarly, the phrase "approximately x, y, z or greater" should be interpreted as including the specific ranges of "approximately x", "approximately y", and "approximately z" as well as the ranges of "greater than x", "greater than y", and "greater than z". Furthermore, the phrase "approximately 'x' to 'y'" (where 'x' and 'y' are numerical values) includes "approximately 'x' to approximately 'y'".

[0039] It should be understood that this range format is used for convenience and brevity, and therefore should be interpreted flexibly as including not only the explicitly listed values ​​that form the boundaries of the range, but also all individual values ​​or subranges contained within that range, as if each value and subrange were explicitly listed. For example, the range of values ​​“approximately 0.1% to 5%” should be interpreted as including not only the explicitly listed values ​​of approximately 0.1% to approximately 5%, but also individual values ​​within the indicated range (e.g., approximately 1%, approximately 2%, approximately 3%, and approximately 4%) and subranges (e.g., approximately 0.5% to approximately 1.1%; approximately 5% to approximately 2.4%; approximately 0.5% to approximately 3.2%, and approximately 0.5% to approximately 4.4%, and other possible subranges).

[0040] As used herein, the terms “approximately,” “about,” “at or about,” and “basically” mean that the quantity or value in question may be an exact value or a value that provides an equivalent result or effect as described in the claims or taught herein. That is, it is to be understood that quantities, dimensions, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller as needed to reflect tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art in order to obtain an equivalent result or effect. In some cases, it is not reasonable to determine a value that provides an equivalent result or effect. In such cases, it is generally understood that, as used herein, “approximately” and “at or about” refer to a nominal value indicated within ±10% of its value, unless otherwise stated or inferred. Generally, quantities, dimensions, formulations, parameters, or other quantities or characteristics are “approximately,” “about,” and “at or about,” whether or not explicitly stated so. It is to be understood that, unless otherwise specifically stated, when “approximately,” “about,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself.

[0041] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes both the possibility that such an event or situation occurs and the possibility that it does not occur.

[0042] As used herein, the term "phr" refers to the number of parts by weight of the respective material relative to 100 parts by weight of rubber or elastomer. Generally, using this convention, an elastomer composition comprises 100 parts by weight of rubber / elastomer. The claimed composition may contain other rubber / elastomers not expressly mentioned in the claims, provided that the phr value of the claimed rubber / elastomer is within the claimed phr range and the total amount of all rubber / elastomers in the composition yields a total of 100 parts of rubber.

[0043] Unless otherwise stated, the terms “rubber” and “elastomer” are used interchangeably in this document.

[0044] As used herein, the term "uncured elastomeric composite" refers to a composition comprising at least one natural or synthetic rubber component and optionally one or more fillers, processing aids, or additives that has not yet been vulcanized. Uncured rubber is sensitive to temperature changes and tends to undergo "cold flow" (slow movement or deformation under stress) over time. In some respects, uncured rubber compositions are masterbatches.

[0045] As used herein, the term "vulcanized elastomer composite" refers to a rubber composition obtained by taking an uncured composition as described herein and curing or vulcanizing it, typically using sulfur compounds and / or other vulcanizing additives and in the presence of heat. Vulcanized or cured rubber, compared to uncured rubber, does not experience a cold flow and is less sensitive to temperature changes. Alternatively, the rubber composition can be cured in a mold to form finished products, including but not limited to tires.

[0046] Unless otherwise specified, the pressure mentioned in this article is based on atmospheric pressure (i.e., one atmosphere).

[0047] Elastomer composite materials and their production methods This article describes an elastomeric composite material made from sustainable materials. In one aspect, this elastomeric composite material includes carbon materials made from carbon oxides abundant in nature.

[0048] In one respect, carbon materials are derived from carbon oxides, such as carbon monoxide and carbon dioxide. Carbon oxides are abundant gases that can be extracted from point source emissions, such as exhaust from hydrocarbon combustion, and from some process exhausts. Carbon dioxide can also be extracted from the air. Because point source emissions have much higher concentrations of carbon dioxide than air, they are often the economical source from which to harvest carbon dioxide. However, the immediate availability of air can provide a cost offset by eliminating transportation costs through the local production of solid carbon products from carbon dioxide in the air.

[0049] In one aspect, carbon materials are produced through the catalytic conversion of carbon oxides. In another aspect, carbon materials derived from carbon oxide compounds are reduced carbon oxide gases. For example, carbon oxide gases can be contacted with a reducing agent gas stream in the presence of a catalyst to produce carbon materials. In one aspect, the reducing agent is a hydrocarbon gas (e.g., natural gas, methane, etc.), hydrogen (H2), or a mixture thereof. Without being bound by theory, hydrocarbon gases have the dual function of serving as an additional carbon source and as a reducing agent for carbon oxides. In another aspect, the reducing agent is syngas. Syngas primarily consists of carbon monoxide (CO) and hydrogen (H2), thus giving the gas a mixture of carbon oxides and reducing gases.

[0050] In one aspect, carbon materials derived from carbon oxide gases are produced by a method comprising the steps of: (a) mixing carbon oxide gas and reducing gas streams to form a reactant gas mixture, and (b) injecting the reactant gas mixture into a reaction zone in the presence of a catalyst, wherein the catalyst reacts with the reaction mixture to form a carbon material derived from the carbon oxide gas. The type, purity, and homogeneity of the solid carbon product are controlled by reaction conditions (time, temperature, pressure, partial pressure of reactants) and catalysts (including size, formation method, and form of catalyst). An exemplary method for producing the carbon materials described herein is disclosed in U.S. Patent No. 9,556,031, the teachings of which are incorporated herein by reference.

[0051] In one aspect, the catalyst comprises transition metal atoms selected from Group VI metals, Group VII metals, and mixtures thereof. In another aspect, the catalyst comprises metal oxide compounds selected from beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide.

[0052] In another aspect, the catalyst is formed from catalyst precursors. Catalyst precursors are compounds containing metals considered effective catalysts. For example, some metals considered effective catalysts exist as metallocenes (e.g., ferrocene), carbonyl compounds (e.g., cobalt carbonyl), oxides (e.g., iron oxides, also known as rust), etc., which decompose at temperatures below the reaction temperature. Those skilled in the art will conceive of a wide range of suitable compounds when selecting catalyst precursors and preparing mixtures of catalyst precursors that yield the desired catalyst upon decomposition.

[0053] Sustainable carbon materials used in the production of the elastomeric composites described herein can exist in several forms. For example, carbon materials may include, but are not limited to, graphite, including pyrolytic graphite, graphene, carbon black, fibrous carbon, buckminister fullerenes, including buckyballs, single-walled carbon nanotubes, and multi-walled carbon nanotubes. In one aspect, the carbon material is carbon black manufactured by Seerstone Development LLC.

[0054] In one aspect, elastomeric composites are produced by mixing a slurry of elastomer with a slurry of carbon material. This method is referred to herein as "liquid processing." This method differs from dry mixing, in which the elastomer and carbon material are mixed together in a dry form. Liquid processing ensures that the carbon material is uniformly dispersed throughout the elastomer, so that the carbon concentration is equal throughout the elastomeric composite (i.e., ±5%).

[0055] In one aspect, an elastomeric composite material is produced by reacting a continuous flow of a first fluid containing an elastomer with a continuous flow of a second fluid containing a carbon material derived from carbon oxides to form a mixture with the elastomer and produce an elastomeric composite material. In another aspect, the elastomeric composite material is produced by a method comprising the following steps: (a) A continuous flow of a first fluid containing an elastomer is fed into a reactor comprising a mixing zone and a discharge end; (b) A continuous flow of a second fluid comprising a carbon material derived from carbon oxides is fed into the mixing zone of the reactor to form an elastomeric composite material, wherein the elastomeric composite material is conveyed as a continuous flow to the discharge end; and (c) Discharge the elastomer composite material from the outlet end of the reactor.

[0056] U.S. Patent No. 6,048,923 provides an exemplary method for producing elastomeric composite materials, the entire contents of which are incorporated herein by reference. In one aspect, the elastomeric composite material is produced by simultaneously feeding a carbon material and an elastomeric latex fluid into a mixing zone of a coagulation reactor. The coagulation zone extends from the mixing zone and, preferably, its cross-sectional area gradually increases downstream from the inlet end to the outlet end. The particulate filler fluid is preferably fed into the mixing zone as a continuous, high-speed jet of injection fluid, while the latex fluid is fed at a low speed. The velocity, flow rate, and particulate concentration of the particulate filler fluid are sufficient to form a mixture within at least the upstream portion of the coagulation zone under high shear of the latex fluid and turbulent flow of the mixture, so that the elastomeric latex and particulate filler are substantially completely coagulated before the outlet end.

[0057] Suitable elastomeric latex fluids include natural and synthetic elastomeric latexes and latex blends. Exemplary elastomers include, but are not limited to, polymers (e.g., homopolymers, copolymers, and / or terpolymers) of rubber, 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, and propylene. The elastomer may have a glass transition temperature (Tg) of approximately -120°C to approximately 0°C, as measured by differential scanning calorimetry (DSC). Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber and its derivatives such as chlorinated rubber, polybutadiene, polyisoprene, poly(styrene-co-butadiene), and oil-extended derivatives of any of these. Blends of any of the foregoing substances may also be used.

[0058] Latex can be in an aqueous carrier liquid. Alternatively, the liquid carrier can be a hydrocarbon solvent. In either case, the elastomeric latex fluid must be suitable for continuous feeding into the mixing zone at a controlled rate, pressure, and concentration. Particularly suitable synthetic rubbers include: copolymers of styrene and butadiene; polymers and copolymers of conjugated dienes, such as polybutadiene, polyisoprene, polychloroprene, etc., and such conjugated dienes with olefinically-containing monomers that can copolymerize with them, such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl-substituted acrylates, vinyl ketones, methyl isopropenyl ketones, methyl vinyl ethers, α-methylene carboxylic acids and their esters and amides, such as copolymers of acrylic acid and dialkylacrylamide. Also suitable for this application are copolymers of ethylene and other high-α olefins such as propylene, butene-1, and pentene-1.

[0059] When the elastomer is natural rubber latex, the natural rubber latex may include fresh latex or latex concentrate (e.g., produced by evaporation, centrifugation, or emulsification). The latex is typically provided in an aqueous carrier liquid. Alternatively, the liquid carrier may be a hydrocarbon solvent.

[0060] The amount of carbon material mixed with the elastomer can vary depending on the intended use of the elastomer composite. In one aspect, the carbon material is approximately 20 phr to approximately 120 phr in the elastomer composite. In another aspect, the carbon material is approximately 20 phr, 30 phr, 40 phr, 50 phr, 60 phr, 70 phr, 80 phr, 90 phr, 100 phr, 110 phr, or 120 phr in the elastomer composite, where any value can be the lower or upper end of the range (e.g., 50 phr to 80 phr).

[0061] Elastomer composites may include one or more additives commonly used in the production of rubber compositions. In one aspect, the additive may be added to the slurry of the elastomer before mixing with the slurry of the carbon material. In another aspect, the additive may be added to the slurry of the carbon material before mixing with the slurry of the elastomer. In yet another aspect, the additive may be added to a slurry containing both the elastomer and the carbon material.

[0062] In one aspect, the additive can be silica. In another aspect, the silica can be obtained by acidification of a soluble silicate, such as sodium silicate. In one embodiment, the unsulfurized composition comprises about 85 to 95 phr or about 90 phr of precipitated silica. Conventional silica can be characterized by the Brunauer-Emmett-Teller (BET) surface area, as measured using nitrogen. In one aspect, the BET surface area can be about 150 m². 2 / g to approximately 165 m 2 / g or approximately 160 m 2 / g. The BET method for measuring surface area is described in the Journal of the American Chemical Society, Vol. 60, p. 304 (1930). In one embodiment, conventional silica may have an average final particle size of about 0.01 µm to about 0.05 µm, as determined by electron microscopy. In other embodiments, the silica particles are less than 0.01 µm. In still other aspects, the silica particles are greater than 0.05 µm.

[0063] Exemplary untreated precipitated silica can be obtained from PPG Industries as Hi-Sil™, for example under the names 210, 243, 315, EZ 160G-D, EZ 150G, 190G, 200G-D, HDP-320G, and 255CG-D; and as Zeosil™, under the names 115GR, 125GR, 165GR, 175GR, 185GR, 195GR, 1085GR, 1165MP, 1115MP, HRS 1200MP, and Premium. MP, Premium200MP, and 195HR are obtained from Solvay; as Ultrasil™, VN2, VN3, VN3GR, 5000GR, 7000GR, and 9000GR are obtained from Evonik; as Zeopol™, 8755LS, and 8745 are obtained from Evonik; as Newsil™, 115GR and 2000MP are obtained from Wuxi Quechen Silicon Chemical Co., Ltd.; as Tokusil™ 315 is obtained from Maruo Calcium Co., Ltd.; and silica derived from rice husk ash is from Yihai Food and Oil Industry, China. Any precipitated silica can be used in this method. In some other embodiments, untreated precipitated silica is prepared as a wet filter material shortly before use.

[0064] In another aspect, the silica can be pre-hydrophobic (or pre-silanized) precipitated silica. Pre-hydrophobication refers to the pretreatment of silica, i.e., the pre-hydrophobicated precipitated silica is hydrophobized by treatment with at least one silane before its addition to the rubber composition. Suitable silanes include, but are not limited to, alkylsilanes, alkoxysilanes, organoalkoxysilyl polysulfides, and organothiolalkoxysilanes. In an alternative embodiment, the pre-hydrophobicated precipitated silica may be pretreated with a silica coupling agent composed of, for example, an alkoxy-organothiolalkoxysilane or a combination of alkoxysilanes and organothiolalkoxysilanes, before blending the pretreated silica with the rubber, rather than allowing the precipitated silica to react in situ with the silica coupling agent within the rubber. See, for example, U.S. Patent No. 7,214,731. The pre-hydrophobicated precipitated silica may optionally be treated with a silica dispersing agent. Such silica dispersants may include glycols, such as fatty acids, diethylene glycol, polyethylene glycol, fatty acid esters of hydrogenated or non-hydrogenated C5 or C6 sugars, and polyoxyethylene derivatives of fatty acid esters of hydrogenated or non-hydrogenated C5 or C6 sugars. Exemplary fatty acids include stearic acid, palmitic acid, and oleic acid. Exemplary fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars (e.g., sorbitol, mannose, and arabinose) include, but are not limited to, sorbitan oleates, such as sorbitan monooleate, dioleate, trioleate, and sesquioleate, as well as laurate, palmitate, and stearate fatty acids of sorbitan. Exemplary polyoxyethylene derivatives of fatty acid esters of hydrogenated and non-hydrogenated C5 and C6 sugars include, but are not limited to, polysorbates and polyoxyethylene sorbitan esters, which are similar to the fatty acid esters of the aforementioned hydrogenated and non-hydrogenated sugars, except that an ethylene oxide group is added to each hydroxyl group. If used, the optional silica dispersant is present in an amount of about 0.1 wt% to about 25 wt% based on the weight of silica, with about 0.5 wt% to about 20 wt% being suitable, and about 1 wt% to about 15 wt% based on the weight of silica also being suitable. For various pretreated precipitated silica, see, for example, U.S. Patent Nos. 4,704,414, 6,123,762, and 6,573,324.

[0065] In one aspect, the additive is a plasticizer. In another aspect, the plasticizer is a T-type plasticizer having a temperature greater than 30°C, preferably greater than 50°C, more preferably greater than 60°C and lower than 100°C. g Hydrocarbon resins, such as those described by R. Mildenberger, M. Zander, and G. Collin in "Hydrocarbon Resins" (New York, VCH, 1997, ISBN-3-527-28617-9). Representative hydrocarbon resins include, for example, coumarone-indene resins, petroleum resins, terpene resins, α-methylstyrene resins, and mixtures thereof.

[0066] Coumarin-indene resins are available in many forms and have melting points ranging from 10°C to 160°C, preferably from 30°C to 100°C (as determined by the ring and ball method). Coumarin-indene resins are well known in themselves. Various analyses indicate that such resins are largely polyindene; however, they typically contain random polymeric units derived from methylindene, coumarone, methylcoumarone, styrene, and methylstyrene.

[0067] Petroleum resins are available with softening points ranging from 10°C to 120°C, preferably from 30°C to 100°C. Suitable petroleum resins include aromatic and non-aromatic types. Several types of petroleum resins are available. Some resins have low unsaturation and high aromatic content, while others are highly unsaturated, and still others contain no aromatic structures at all. The differences in the resins are mainly attributed to the olefins in the feedstock from which the resin is produced. Common derivatives of such resins include dicyclopentadiene, cyclopentadiene, their dimers, and dienes such as isoprene and isoprene. In one aspect, the hydrocarbon resin is Optera manufactured by Exxon Mobil. TM PR383, which has a temperature of approximately 54°C. g Hydrogenated C9 modified dicyclopentadiene.

[0068] In one respect, terpene resins can be used as hydrocarbon resins. Terpene polymers (or resins) are generally commercially available by polymerizing α- or β-pinene. In particular, α-pinene-based resins can be used. Terpene resins are available with various melting points from 10°C to 135°C. Terpene resins can, for example, have a molecular weight M of less than 1000 g / mol, preferably less than 950 g / mol, or between 200 g / mol and 950 g / mol, as determined by gel permeation chromatography (GPC). w An example of an α-pinene-based resin is Dercolyte™ A 115 from DRT Corporation, which has a molecular weight M of approximately 900 g / mol. w .

[0069] In one respect, the hydrocarbon resin is derived from styrene and α-methylstyrene. Due to the observed viscoelastic properties of the tread rubber composition, such as complex modulus and storage modulus, loss modulus, tanδ, and loss compliance at different temperatures / frequency / strains, the presence of styrene / α-methylstyrene resins in conjunction with rubber blends containing styrene-butadiene elastomers is considered advantageous herein. The properties of complex modulus and storage modulus, loss modulus, tanδ, and loss compliance are understood to be well known to those skilled in the art. The molecular weight distribution of the resin is visualized as the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) value, and is considered herein to be in the range of approximately 1.5 / 1 to approximately 2.5 / 1, which is considered a relatively narrow range. This is considered advantageous due to the selective compatibility with the polymer matrix and due to the intended use of tires under wet and dry conditions over a wide temperature range. The glass transition temperature (Tg) of the copolymer resin is considered herein to be in the range of approximately 20°C to approximately 100°C, or approximately 50°C to approximately 70°C. g The appropriate measurement is a DSC according to ASTM D6604 or its equivalent. Styrene / α-methylstyrene resin herein is considered to be a copolymer of styrene and α-methylstyrene in a styrene / α-methylstyrene molar ratio of about 0.40 to about 1.50. In one aspect, such a resin can suitably be prepared, for example, by cationic copolymerization of styrene and α-methylstyrene in a hydrocarbon solvent. Thus, the contemplated styrene / α-methylstyrene resin can be characterized, for example, by its chemical structure, i.e., its styrene and α-methylstyrene content and softening point, and, if desired, by its glass transition temperature, molecular weight, and molecular weight distribution. In one embodiment, the styrene / α-methylstyrene resin comprises about 40 to about 70% styrene-derived units and correspondingly about 60 to about 30% α-methylstyrene-derived units. In one embodiment, the styrene / α-methylstyrene resin has a softening point according to ASTM No. E-28 at about 80°C to about 145°C. Suitable styrene / α-methylstyrene resins are available as Resin 2336 from Eastman or as Sylvares SA85 from Arizona Chemical.

[0070] In one respect, the additive is a sulfur donor. Representative examples of sulfur donors include elemental sulfur (free sulfur), amine disulfides, polymeric polysulfides, and sulfur olefin adducts. In another respect, the sulfur vulcanizing agent is elemental sulfur. The sulfur donor can be used, for example, in amounts from 0.5 phr to 8 phr, or from 1 phr to 3 phr.

[0071] In one respect, the additive is an antioxidant (also known as an anti-degradation agent). Representative antioxidants can be, for example, diphenyl-p-phenylenediamine, such as those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. If used, the typical amount of antioxidant can, for example, include 1 phr to 5 phr.

[0072] In one respect, the additive is an anti-ozone agent. Representative anti-ozone agents include, but are not limited to, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD) and N,N'-o-tolyl-p-phenylenediamine (DTPD). If used, the typical amount of anti-ozone agent may, for example, comprise 1 phr to 5 phr. In some respects, anti-ozone agent is included in an amount of approximately 1 phr to 5 phr.

[0073] In one respect, the additive is wax. If used, the typical amount of wax can range from 1 phr to 5 phr.

[0074] In one respect, the additive is zinc oxide. If used, the typical amount of zinc oxide can range from 1 phr to 5 phr.

[0075] In some respects, accelerators can be used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized rubber. In one embodiment, a single accelerator system, i.e., a primary accelerator, can be used. The primary accelerator can be used in a total amount of 0.5 phr to 4 phr, or 0.8 phr to 1.5 phr. In another embodiment, a combination of a primary accelerator and a secondary accelerator can be used, wherein the secondary accelerator is used in a smaller amount, such as 0.05 phr to 3 phr, to activate and improve the properties of the vulcanized rubber. These combinations of accelerators may be expected to produce a synergistic effect on the final properties and be slightly better than the effect produced by using either accelerator alone. In addition, accelerators with a post-curing effect that are not affected by normal processing temperatures but produce satisfactory vulcanization at ordinary vulcanization temperatures can be used. Vulcanization retarders may also be used. Suitable types of accelerators that can be used in this invention are, for example, amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfinamides, dithiocarbamates, and xanthates. In one embodiment, the primary accelerator is a sulfinamide. If an auxiliary accelerator is used, it can be, for example, a guanidine, a dithiocarbamate, or a thiuram compound. Suitable guanidines include diphenylguanidine, etc. Suitable thiurams include tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabenzylthiuram disulfide.

[0076] In one respect, the additive is an oil. Examples of such oils include, but are not limited to, aromatic, alkanes, cycloalkanes, and low-PCA oils, such as MES, TDAE, SRAE, and heavy cycloalkanes. PCA oils may include those with a polycyclic aromatic hydrocarbon content of less than 3% by weight, as determined by the IP346 method. The oil may be a vegetable oil or a vegetable oil derivative (such as sunflower oil, soybean oil, or canola oil) or a blend of multiple oils, particularly sunflower oil. Some representative examples of available vegetable oils include soybean oil, sunflower oil, canola oil (rapeseed oil), corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil.

[0077] After the elastomer composite material has been prepared, it is vulcanized to produce a vulcanized elastomer composite material. In one aspect, vulcanization can be carried out at a temperature of about 100°C to about 200°C or 110°C to about 180°C. Vulcanization methods may include heating in a press or mold, or heating with superheated steam or hot air. The vulcanized elastomer composite material can be built, shaped, or molded into any desired shape or article.

[0078] In one aspect, the vulcanized elastomer composite material is a component of the tire, such as the tread, tire sub-tread, base, sidewall, wire-skim, or any combination thereof. In another aspect, the tire can be a radial tire, a pneumatic tire, a non-pneumatic tire, a truck tire, or a passenger car tire. The tire can be, for example, a winter tire and / or may have a three-peak mountain snowflake symbol. Therefore, the tire may have multiple tread blocks with multiple sipes.

[0079] The elastomeric composites described herein, once vulcanized, possess performance properties comparable to or improved upon those of elastomers prepared using conventional fillers and methods. In one aspect, the vulcanized elastomeric composite has one or more comparable or improved properties compared to elastomeric composites made from furnace black, such as N234 or N326. In another aspect, the vulcanized elastomeric composite exhibits composite performance characteristics similar to those of furnace black, wherein the surface area ratio of the furnace black, as defined by ASTM D6556, exhibits at least 15% higher performance characteristics than furnace black using dry-blended equivalent complexes of carbon black derived from the same carbon oxides as the elastomeric composite.

[0080] In another aspect, compared with elastomeric composites made by dry mixing, vulcanized elastomeric composites made by liquid processing as described herein have one or more equivalent or improved properties. In one aspect, the Z-value of vulcanized elastomeric composites made by liquid processing is at least 15% higher than that of the same vulcanized elastomeric composites made by dry mixing.

[0081] The dispersion of filler in the elastomer matrix can be represented by the Z-value, which, after crosslinking, is measured according to standard ISO 11345 according to the method described by S. Otto et al. in Kautschuk Gummi Kunststoffe, 58th edition, NR 7-8 / 2005.

[0082] The Z-value is calculated based on the percentage of undispersed surface area of ​​the filler (“% undispersed surface area”), which is measured using a “disperGRADER+” machine (provided by Dynisco with its operating instructions and “disperDATA” operating software): Z = 100 − (%undispersed surface area) / 0.35 The percentage of undispersed surface area is measured by a camera observing the sample surface area under 30° incident light. Bright spots are associated with fillers and agglomerates, while dark spots are associated with the rubber matrix; digital processing converts the image into a black and white image, making it possible to determine the percentage of undispersed surface area, as described by S. Otto in the aforementioned literature.

[0083] A higher Z-value indicates better dispersion of the filler in the elastomer matrix (a Z-value of 100 corresponds to perfect dispersion, and a Z-value of 0 corresponds to moderate dispersion). A Z-value greater than or equal to 80 is considered to correspond to a surface area in which the filler is very well dispersed in the elastomer matrix.

[0084] aspect The disclosure is described in accordance with the following numbering system, which should not be confused with the claims.

[0085] Aspect 1. An elastomeric composite material comprising a carbon material derived from a carbon oxide compound uniformly dispersed in an elastomer.

[0086] Aspect 2. The elastomeric composite material of aspect 1, wherein the carbon oxide compound comprises carbon dioxide, carbon monoxide, or a combination thereof.

[0087] Aspect 3. An elastomeric composite material of aspect 1 or 2, wherein the carbon material derived from carbon oxide compounds comprises carbon oxide gas that has been reduced.

[0088] Aspect 4. An elastomeric composite material of any one of Aspects 1-3, wherein the carbon material derived from carbon oxide compounds is generated by contacting the carbon oxide gas with a reducing agent gas stream in the presence of a catalyst.

[0089] Aspect 5. The elastomeric composite material of aspect 4, wherein the reducing agent gas stream comprises hydrogen or hydrocarbon gas.

[0090] Aspect 6. The elastomeric composite material of aspect 5, wherein the hydrocarbon gas comprises natural gas or synthesis gas.

[0091] Aspect 7. The elastomeric composite material of aspect 5, wherein the hydrocarbon gas comprises methane.

[0092] Aspect 8. An elastomeric composite material of any one of Aspects 4-7, wherein the catalyst comprises transition metal atoms selected from Group VI metals, Group VII metals and mixtures thereof.

[0093] Aspect 9. An elastomeric composite material of any one of Aspects 4-7, wherein the catalyst comprises a metal oxide compound selected from beryllium oxide, magnesium oxide, calcium oxide, strontium oxide and barium oxide.

[0094] Aspect 10. An elastomeric composite material of aspect 1, wherein the carbon material derived from carbon oxide gas is produced by a method comprising the steps of: (a) mixing the carbon oxide gas and a reducing gas stream to form a reactive gas mixture, and (b) injecting the reactive gas mixture into a reaction zone in the presence of a catalyst, wherein the catalyst reacts with the reaction mixture to form the carbon material derived from carbon oxide gas.

[0095] Aspect 11. An elastomeric composite material of any one of Aspects 1-10, wherein the method of producing the elastomeric composite material comprises reacting a continuous flow of a first fluid containing the elastomeric material with a continuous flow of a second fluid containing the carbon material derived from the carbon oxide to form a mixture with the elastomeric material and produce the elastomeric composite material.

[0096] Aspect 12. An elastomeric composite material of any one of Aspects 1-10, wherein the elastomeric composite material is produced by a method comprising the following steps: (a) A continuous flow of a first fluid containing the elastomer is fed into a reactor comprising a mixing zone and a discharge end; (b) A continuous flow of a second fluid comprising the carbon material derived from carbon oxides is fed into the mixing zone of the reactor to form an elastomeric composite material, wherein the elastomeric composite material is conveyed as a continuous flow to the discharge end; and (c) Discharge the elastomer composite material from the outlet end of the reactor.

[0097] Aspect 13. An elastomeric composite material of aspect 11 or 12, wherein the carbon material derived from carbon oxide is milled before being mixed with the elastomer.

[0098] Aspect 14. An elastomeric composite material of any one of Aspects 1-13, wherein the elastomeric material comprises natural rubber, a chlorinated derivative of natural rubber, or butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene wherein the alkyl group is a C1 to C3 alkyl group, a homopolymer, copolymer or terpolymer of acrylonitrile, ethylene or propylene.

[0099] Aspect 15. An elastomeric composite material of any one of Aspects 1-14, wherein the method does not include mixing the additive with the elastomeric material and the carbon material derived from carbon oxides.

[0100] Aspect 16. An elastomeric composite material of any one of Aspects 1-14, wherein the method further comprises mixing at least one additive with the elastomeric material and the carbon material derived from carbon oxides.

[0101] Aspect 17. The elastomeric composite material of aspect 16, wherein the at least one additive is selected from anti-ozone agents, antioxidants, plasticizers, processing aids, resins, flame retardants, extender oils, lubricants, and any combination thereof.

[0102] Aspect 18. An elastomeric composite material of any one of Aspects 1-17, wherein the carbon material derived from carbon oxide is about 20 phr to about 120 phr of the elastomeric composite material.

[0103] Aspect 19. A vulcanized elastomer composite material comprising an elastomer composite material of any one of aspects 1-18 that has been vulcanized.

[0104] Aspect 20. Aspect 19 of a vulcanized elastomer composite material, wherein the vulcanized elastomer composite material exhibits one or more performance characteristics similar to furnace black, wherein the surface area ratio of the furnace black, as defined by ASTM D6556, exhibits at least 15% higher performance characteristics than furnace black using dry-mix equivalent complexes of carbon black derived from the same carbon oxide as the elastomer composite material.

[0105] Aspect 21. Aspect 19 of a vulcanized elastomer composite material, wherein when the elastomer composite material is produced by a liquid method, the Z-value of the elastomer composite material is at least 15% higher than that of an elastomer composite material produced by a dry-mixing method using the same amount of carbon material derived from carbon oxide compounds.

[0106] Aspect 22. An article comprising the vulcanized elastomer composite material of aspect 19.

[0107] Articles of aspect 23. Articles of aspect 22, wherein the articles of aspect 23 comprise tires or tire assemblies.

[0108] Articles of aspect 24 and 23, wherein the tire assembly comprises a tire tread, a tire sub-tread, a tire wire-skim, a tire sidewall, or a cushiongum for retreading the tire.

[0109] Aspect 25. A method for producing an elastomeric composite material comprising a carbon material derived from carbon oxides, the method comprising mixing an elastomer with the carbon material derived from carbon oxides, wherein the carbon material derived from carbon oxides is uniformly dispersed in the elastomer.

[0110] Having described aspects of this disclosure, the following embodiments illustrate some additional aspects of this disclosure. Although aspects of this disclosure have been described in conjunction with the following embodiments and corresponding text, it is not intended to limit the aspects of this disclosure to such description. Rather, it is intended to cover all alternatives, modifications, and equivalents that fall within the spirit and scope of this disclosure. Example

[0111] The elastomeric composites were prepared according to the formulations shown in Table 1, with amounts given in phr. Referring to Table 1, control composition R1 was prepared using furnace black (N326). Samples C1 and C2 were prepared by dry processing using the method in Example B of U.S. Patent No. 6,048,923. Samples I1 and I2 were prepared by liquid processing using the method in Example A of U.S. Patent No. 6,048,923, except for slurry homogenization.

[0112] Table 1 1. TSR-20 natural rubber 2. N326 carbon black 3. CO2-derived carbon black from Seerstone: ~15% ash content 4. Liquid-phase masterbatch of NR latex and CO2-derived carbon black, with 3-6% ash content. 5. Mixed p-phenylenediamine type 6. Sulfinate type.

[0113] These complexes were vulcanized and their physical properties were tested, and the results are provided in Table 2. Table 2 discloses the mechanical test results for reference composition R1, two control compositions C1 and C2, and two corresponding compositions of the present invention I1 and I2. It is known that carbon black with a higher specific surface area and / or structure can produce vulcanized rubber composites with higher levels of reinforcement and hysteresis. When comparing C1 with I1 and similarly comparing C2 with I2, it is evident that the compositions of the present invention exhibit similar hysteresis, 300% modulus, tensile strength, and Grosch abrasion properties to carbon black with a higher specific surface area and / or structure, without compromising the final tensile elongation of the complex. This variation is noteworthy because these compositions contain the same type of carbon black with the same loading, wherein C1 and I1 contain carbon black equivalent to ~45 PHR when ash content is taken into account, and C2 and I2 contain carbon black equivalent to ~51 PHR. Reference compound R1 uses N326 at ~47 PHR, a semi-reinforcing ASTM carbon black grade, and includes its properties when using the liquid-phase masterbatch technology described herein, exhibiting a directional shift towards providing sufficient reinforcement for applications requiring higher reinforcement. For all carbon black / natural rubber compounds conventionally used in tires, a tensile strength of 20 MPa is insufficient. For example, the tread or base of a radial truck tire with a tensile strength of only 20 MPa cannot provide the required level of toughness for this application. The use of the invention disclosed herein increases the tensile strength and therefore toughness of rubber compounds with the same material composition to a level that makes them feasible for such applications.

[0114] Table 2 1. Data obtained from the Instron Tensile Tester based on ASTM D638. 2. Data obtained from Alpha Technologies' RPA 2000 Rubber Process Analyzer, based on ASTM D5289. 3. Data obtained using VMI LAT100.

[0115] It should be emphasized that the above embodiments of this disclosure are merely possible implementation examples set forth for the purpose of clearly understanding the principles of this disclosure. Many changes and modifications can be made to the above embodiments without substantially departing from the spirit and principles of this disclosure. All such modifications and changes are intended to be included within the scope of this disclosure and are protected by the following claims.

Claims

1. An elastomer composite material comprising a carbon material derived from a carbon oxide compound uniformly dispersed in an elastomer.

2. The elastomeric composite material according to claim 1, wherein the carbon oxide compound comprises carbon dioxide, carbon monoxide, or a combination thereof.

3. The elastomeric composite material according to claim 1 or 2, wherein the carbon material derived from the carbon oxide compound comprises reduced carbon oxide gas.

4. The elastomeric composite material according to any one of claims 1-3, wherein the carbon material derived from carbon oxide compounds is generated by contacting the carbon oxide gas with a reducing agent gas stream in the presence of a catalyst.

5. The elastomeric composite material according to claim 4, wherein the reducing agent gas stream comprises hydrogen or hydrocarbon gas.

6. The elastomeric composite material according to claim 5, wherein the hydrocarbon gas comprises natural gas or syngas.

7. The elastomeric composite material according to claim 5, wherein the hydrocarbon gas comprises methane.

8. The elastomeric composite material according to any one of claims 4-7, wherein the catalyst comprises transition metal atoms selected from Group VI metals, Group VII metals, and mixtures thereof.

9. The elastomeric composite material according to any one of claims 4-7, wherein the catalyst comprises a metal oxide compound selected from beryllium oxide, magnesium oxide, calcium oxide, strontium oxide and barium oxide.

10. The elastomeric composite material of claim 1, wherein the carbon material derived from carbon oxide gas is produced by a method comprising the steps of: (a) mixing the carbon oxide gas and a reducing gas stream to form a reactive gas mixture, and (b) injecting the reactive gas mixture into a reaction zone in the presence of a catalyst, wherein the catalyst reacts with the reaction mixture to form the carbon material derived from carbon oxide gas.

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