WO2024254466A1 - Agents de couplage provenant de pneus usagés et utilisation dans un caoutchouc pour pneu - Google Patents

Agents de couplage provenant de pneus usagés et utilisation dans un caoutchouc pour pneu Download PDF

Info

Publication number
WO2024254466A1
WO2024254466A1 PCT/US2024/033032 US2024033032W WO2024254466A1 WO 2024254466 A1 WO2024254466 A1 WO 2024254466A1 US 2024033032 W US2024033032 W US 2024033032W WO 2024254466 A1 WO2024254466 A1 WO 2024254466A1
Authority
WO
WIPO (PCT)
Prior art keywords
feedstock
tire
ethanol
tire component
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/033032
Other languages
English (en)
Inventor
Terrence E. Hogan
Mark W. Smale
William S. Niaura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Americas Tire Operations LLC
Original Assignee
Bridgestone Americas Tire Operations LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Americas Tire Operations LLC filed Critical Bridgestone Americas Tire Operations LLC
Publication of WO2024254466A1 publication Critical patent/WO2024254466A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
    • C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/065—Ethanol, i.e. non-beverage with microorganisms other than yeasts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only

Definitions

  • Embodiments of the present invention are directed toward a process for converting used tires to silane coupling agents.
  • the silane coupling agents can then be used within tire formulations that include silica filler.
  • Used tires include a significant amount of carbonaceous material. Recycling the carbon into other carbon-based materials presents numerous challenges due, at least in part, to the fact that a majority of the carbon is tied up in a vulcanized network. As a result, technologically efficient modes of recycling used tire is fairly limited and includes, for example, mechanically grinding the vulcanized rubber product and using the ground rubber for various uses such as filler within composites. Withan eye toward carbon efficiency, other modes of recycling carbon are desired.
  • One or more embodiments of the present invention provide a process comprising (a) providing a feedstock that includes carbonaceous materials; (b) gasifying the feedstock to produce a gaseous stream including carbon monoxide, hydrogen, and carbon dioxide; (c) converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide to ethanol; (d) reacting at least a portion of the ethanol with chloropropyltrichlorosilane to produce chloropropyltriethoxysilane; and (e) reacting at least a portion of the chloropropyltriethoxysilane with sulfur and sodium hydrosulfide to produce a bis (triethoxypropyl) sulfide.
  • a tire component comprising a cured rubber matrix with silica filler dispersed therein, where the silica filler is at least partially coupled to the cured rubber matrix through a silane coupling agent, where the silane coupling agent is synthesized using ethanol obtained from constituents of a gaseous stream that is obtained from the gasification of a feedstock including carbonaceous materials.
  • Yet other embodiments of the present invention provide a tire including a tire component as provided above, where the tire includes greater than 40 wt %, or 50 wt %, or 60 wt %, or 70 wt %, or 80 wt %, or 90 wt %, or 99 wt % sustainable material.
  • Embodiments of the invention are based, at least in part, on the discovery of a process for consuming used tires in the production of silane coupling agents.
  • the silane coupling agents can advantageously be used within tire formulations that include silica filler to ultimately manufacture tires and tire components.
  • the silane coupling agents are produced by thermally decomposing used tires to form a gaseous stream. One or more components of this gaseous stream are then converted to ethanol, which is then reacted with chloropropyltrichlorosilane to produce chloropropyltriethoxysilane. The chloropropyltriethoxysilane is then converted to a bis (triethoxysilylpropyl) sulfide, which can be used as a coupling agent within rubber formulations that include silica filler.
  • the process of the present invention provides a feedstock, which may include tire feedstock, and the feedstock is converted, via thermal decomposition, to a gaseous stream that includes hydrogen, carbon monoxide, and optionally carbon dioxide.
  • This gaseous stream which may be referred to as synthesis gas or syngas, is then converted to ethanol by using biological fermentation processes.
  • the ethanol is then reacted with chloropropyltrichlorosilane, in the absence of water, to produce chloropropyltriethyoxysilane.
  • the chloropropyltriethyoxysilane is then reacted with sulfur and sodium hydrosulfide to produce bis(triethoxysilylpropyl) sulfides such as bis(triethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl) disulfide.
  • the feedstock that is thermally decomposed to form the gaseous stream may include tire feedstock from used tires, which may also be referred to as used tire feedstock or simply tire feedstock.
  • tire feedstock may include vulcanized polymer, carbon black filler, silica, resins, oils, fibrous yarn, and metal.
  • the vulcanized polymer may include the sulfur-crosslinked residue of natural rubber and/or one or more synthetic elastomers including diene polymers and copolymers.
  • the used tire feedstock may include shredded or otherwise ground tires with one or more constituents of the used tire removed.
  • the tire feedstock may be treated to remove metal by methods known in the art e.g. magnetic separation].
  • the used tire feedstock may be optionally treated to remove fibrous reinforcement such as fiber yarn or cord, which the skilled person understands is often found in conjunction with the vulcanized rubber within many tire components.
  • the used tire feedstock may be optionally treated to remove inorganic materials such as silica filler, which the skilled person appreciates is often found in used tire components.
  • the tire feedstock can be processed into tire shreds, tire chips, or ground or crumb rubber and fed to the thermal decomposition unit.
  • the tire feedstock is characterized by relatively low amounts of metal, which low amounts may result from pre-treatment of the tire feedstock to remove at least a portion of the metal that is typically present in used tires.
  • the tire feedstock may include less than 25 wt %, in other embodiments less than 15 wt %, and in other embodiments less than 1 wt % metal based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the tire feedstock is characterized by relatively low amounts of fibrous yarn or cord, which low amounts may result from pre-treatment of the tire feedstock to remove at least a portion of the fibrous yarn or cord that is typically present in used tires.
  • the tire feedstock following pre-treatment, includes less than 5 wt %, in other embodiments less than 4 wt %, in other embodiments less than 3 wt %, in other embodiments less than 2 wt %, and in other embodiments less than 1 wt % fibrous yarn or cord based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the tire feedstock is characterized by relatively low amounts of inorganic filler (e.g. silica], which low amounts may result from pretreatment of the tire feedstock to remove inorganic filler that is typically present in used tires.
  • inorganic filler e.g. silica
  • the tire feedstock includes less than 30 wt %, in other embodiments less than 20 wt %, in other embodiments less than 10 wt %, and in other embodiments less than 5 wt % inorganic filler based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the used tire feedstock includes tire remains from passenger tires. In other embodiments, the used tire feedstock includes tire remains from non-passenger tires such as, but not limited to, truck and bus tires, off-road vehicle tires, agricultural tires, and race tires.
  • the used tires are mechanically treated (e.g. ground or shredded) to form a ground or shredded material (i.e. the feedstock is ground or shredded).
  • This ground or shredded material i.e. the tire feedstock
  • crumb may be characterized by an advantageous compacted density.
  • the feedstock may have a compacted density of greater than 640 kg/m 3 , in other embodiments greater than 720 kg/m 3 , and in other embodiments greater than 770 kg/m 3 , where density is determined by ASTM D 698-07.
  • the feedstock provided to the thermal decomposition unit includes used tires and optionally complementary feedstock.
  • the complementary feedstock which may also be referred to as co-feed, includes carbonaceous materials other than the tire feed stock.
  • Carbonaceous material refers to any carbon material whether in solid, liquid, gas, or plasma state.
  • Non-limiting examples of carbonaceous materials include carbonaceous liquid product, industrial liquid recycle, municipal solid waste (MSW or msw) including municipal solid waste with higher biomass content and/or with decreased recyclable material content, urban waste, agricultural material, forestry material, wood waste, construction material, vegetative material, industrial waste, fermentation waste, petrochemical coproducts, alcohol production coproducts, coal, plastics, waste plastic, coke oven tar, lignin, black liquor, polymers, waste polymers, polyethylene terephthalate (PETA), polystyrene (PS), sewage sludge, animal waste, crop residues, energy crops, forest processing residues, wood processing residues, livestock wastes, poultry wastes, food processing residues, ethanol coproducts, spent grain, spent microorganisms, municipal waste, construction waste, demolition waste, biomedical waste, hazardous waste, or their combinations.
  • MSW or msw municipal solid waste with higher biomass content and/or with decreased recyclable material content
  • urban waste agricultural material, forestry material, wood waste, construction
  • the carbonaceous material includes biomass.
  • the biomass is bagasse including, but not limited to, the bagasse of sugar cane, sorghum, and guayule plant.
  • the feedstock includes a blend of used tires and municipal solid waste, wherein the municipal solid waste can include biomass.
  • the feedstock includes used tires and municipal solid waste that is substantially exclusive of biomass (i.e. substantially petroleum-based solid municipal waste).
  • the feedstock includes used tires and biomass.
  • the feedstock includes used tires and municipal solid waste that has had most of the recyclable plastics removed i.e. substantially exclusive of recyclable plastics).
  • recyclable glass and metal is also substantially removed from the municipal solid waste component.
  • the guayule bagasse is produced as the result of a process to extract rubber and resin from the guayule plant, such as described in U.S. Publication No. 2022/0356273, which is incorporated herein by reference. Methods for the desolventization of guayule bagasse are described in U.S. Patent No. 10,132,563, which is also incorporated herein by reference.
  • the guayule bagasse contains no more than 1 wt % organic solvent (based upon the total weight of the dried bagasse).
  • the dried bagasse contains no more than 0.5 wt % organic solvent (based upon the total weight of the dried bagasse).
  • the dried bagasse may contain a quantity of water and higher boiling point terpenes. In certain embodiments, the total quantity of water and higher boiling point terpenes in the dried bagasse may be higher than the content of organic solvents.
  • the co-feed e.g. biomass or municipal waste
  • the co-feed may be characterized by a compacted density of less than 600 kg/m 3 , in other embodiments less than 580 kg/m 3 , and in other embodiments less than 560 kg/m 3 , where density is determined by ASTM D 698-07.
  • the feedstock may be characterized by the amount of co-feed (e.g. biomass or municipal waste).
  • the feedstock includes from about 0 to about 95, in other embodiments from about 1 to about 75, and in other embodiments from about 2 to about 55 wt % co-feed with the balance including used tire.
  • the feedstock includes less than 95, in other embodiments less than 80, and in other embodiments less than 70 wt % co-feed.
  • the feedstock includes greater than 10, in other embodiments greater than 20, in other embodiments greater than 30, in other embodiments greater than 40, in other embodiments greater than 50, and in other embodiments greater than 70 wt % used tires, with the balance including complementary feedstock.
  • the feedstock is substantially, and in certain embodiments exclusively, comprised of those carbonaceous materials identified above other than tire feedstock; i.e. the feedstock is substantially or exclusively comprised of the co-feed materials identified above.
  • the feedstock includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 99 wt % municipal solid waste.
  • the feedstock includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 99 wt % biomass.
  • the feedstock (which may include tire feedstock and optionally co-feed) is thermally decomposed into gaseous streams including hydrogen, carbon monoxide, and optionally carbon dioxide by employing techniques that are generally known in the art.
  • these processes may include gasification processes, and it is also known that these processes can be tailored to control the chemical nature of the resulting gaseous stream.
  • the degree of combustion can be controlled by controlling the amount of oxygen present during thermal decomposition.
  • the step of thermal decomposition takes place in a substantially inert environment.
  • Processes that may be used for the thermal decomposition step may include pyrolysis or gasification reactions as disclosed in U.S. Publication Nos. 2021/0207037; 2019/0295734; 2019/0249089; 2018/0273415; 2017/0009162; 2017/0002271; 2016/0107913; 2016/0068773; 2016/0024404; 2014/0182205; 2014/0157667; and 2014/0100294, which are incorporated herein by reference.
  • the tire feedstock and the co-feed can be introduced to the same thermal decomposition unit simultaneously.
  • the tire feedstock and the co-feed can be pre-mixed at a desired ratio to form the feedstock that is fed to the thermal decomposition unit.
  • separate streams of tire feedstock and co-feed can be separately and individually fed to the thermal decomposition unit at a desired rate.
  • the two feedstocks [i.e. the tire feedstock and the co-feed) can be sequentially treated within the same thermal decomposition unit.
  • the two feedstocks [i.e. the tire feedstock and the co-feed) can be treated within separate thermal decomposition units operating in parallel, and then the gaseous streams produced by the respective units can be combined to attain the desired ratio of gaseous constituents.
  • the gaseous product stream produced by thermal decomposition of the feedstock includes carbon monoxide, hydrogen and optionally carbon dioxide.
  • the gaseous product stream includes from about 5 to about 50, or in other embodiments from about 7 to about 25, or in other embodiments from about 8 to about 15 volume percent carbon dioxide.
  • the gaseous product stream includes from about 10 to about 85, or in other embodiments from about 20 to about 65, or in other embodiments from about 25 to about 45 volume percent hydrogen.
  • the gaseous product stream includes from about 20 to about 85, or in other embodiments from about 30 to about 75, or in other embodiments from about 40 to about 60 volume percent carbon monoxide.
  • the gaseous product stream produced by thermal decomposition includes from about 40 to about 80 wt %, in other embodiments from about 45 to about 75 wt %, and in other embodiments from about 50 to about 70 wt % carbon (i.e. carbon within carbon-based compounds) based on the total weight of the gaseous product stream.
  • the gaseous stream is conditioned [i.e. treated) prior to converting the gaseous stream to ethanol.
  • the gaseous product stream from thermal decomposition may be pressurized.
  • pressurization of the gaseous stream achieves sufficient pressure to overcome counter forces within the bioreactor. As the skilled person understands, this will permit flow of the gas through the bioreactor and allow inert gases (e.g. nitrogen) within the gaseous stream to enter the head space of the reactor.
  • the gaseous stream is pressurized to a pressure of from about 5 to about 20 barr.
  • the gaseous stream can be cooled.
  • the gaseous stream can be cooled, for example, within a heat exchanger such as a water- cooled unit.
  • the gaseous stream is cooled to a temperature below that which would otherwise have a deleterious impact on the microorganism culture within the bioreactor.
  • the gaseous stream is cooled to a temperature of from about 25 to about 45 °C prior to delivery to the bioreactor.
  • the gaseous stream can be treated to remove undesirable constituents that may be entrained within the stream.
  • the gaseous stream can be treated within a scrubber prior to being introduced to the bioreactor.
  • this may include the use of a catalyst (e.g. iron oxide] to remove sulfur compounds such as hydrogen sulfide.
  • the stream may also be treated to remove halides (e.g. treatment with calcium or sodium carbonate with particular interest in removing hydrogen cyanides].
  • Exemplary systems for removing hydrogen sulfide from gaseous streams include those available from EcoVapor (Denver, Colorado]. Other methods include the use of caustic such as those systems available from DMT under the tradename Sulfurex BF (Netherlands].
  • constituents of the gaseous stream are converted to ethanol that is contained within an ethanol-containing stream; i.e. a product stream that includes ethanol.
  • the gaseous stream is supplemented with hydrogen prior to converting the gaseous stream to an ethanol-containing stream.
  • the gaseous stream is converted to ethanol via biosynthetic techniques.
  • syngas can be converted to ethanol by fermentation utilizing microorganisms, such as bacteria.
  • the microorganisms may be acetogenic autotrophic microbes.
  • Acetogenic microbes i.e. bacteria
  • the acetyl-CoA is then converted to organic products, such as acetic acid and ethanol.
  • some microorganisms e.g.
  • acetogens can reduce the acetic acid (e.g. an organic acid) into an alcohol (e.g. ethanol).
  • This acetogenic mechanism, as well as the microorganism chosen, may be considered relative to preferentially producing ethanol.
  • Microorganisms other than acetogens may be suitable with different pathways to reaching ethanol.
  • One or more useful microorganisms may simultaneous uptake both CO and H 2 in the syngas.
  • certain microorganisms can reduce C02 to CO in the presence of excess hydrogen.
  • useful microorganisms and techniques for their use are disclosed in "A Techno-Economic Assessment of Bioethanol Production from Switchgrass Through Biomass Gasification and Syngas Fermentation” Regis et al, Energy 274, 127318, (2023).
  • the syngas is converted to ethanol via thermochemical techniques.
  • thermochemical techniques exist to convert syngas to ethanol.
  • two-step processes exist whereby syngas can be converted to methanol using a hydrogen to carbon monoxide ratio of 2:1. These reactions typically take place in the gas phase using copper-based catalysts.
  • the resulting product stream which is typically saturated with water, can be purified by using known distillation techniques.
  • the methanol can then be catalytically converted to ethanol.
  • One-step catalytic techniques are also known.
  • An exemplary thermochemical process for converting syngas to ethanol is described in U.S. Patent No. 9,115,046, which is incorporated herein by reference.
  • the resultant ethanol is contained with an ethanol- containing stream.
  • a crude ethanol-containing stream which is obtained directly from the bioreactor in which the ethanol is synthesized, is delivered to downstream steps.
  • the ethanol-containing stream is purified to produce an ethanol-containing stream that is higher in ethanol content.
  • the ethanol-containing stream exiting the step wherein syngas is converted to ethanol i.e.
  • the bioreactor and delivered to the downstream steps where ethanol is further converted (optionally after purification) includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % ethanol based upon the entire weight of the ethanol-containing stream.
  • Ethanol within the ethanol-containing stream is reacted with chloropropyltrichlorosilane to produce chloropropyltriethoxysilane.
  • chloropropyltrichlorosilane can be reacted with chloropropyltrichlorosilane in the absence of water to produce chloropropyltriethoxysilane and hydrochloric acid, which may be drawn off by vacuum or captured with a base.
  • Ethanol may serve as a solvent for the reaction, and then the ethanol may be separated from the reaction medium as a distillate during distillation.
  • Chloropropyltriethoxysilane within the chloropropyltriethoxysilane-containing stream is reacted with sulfur and sodium hydrosulfide to produce a bis(triethoxypropyl) sulfide such as bis(triethoxypropyl)tetrasulfide or bis(triethoxypropyl)disulfide.
  • the reaction can take place within a biphasic system that includes, as the aqueous phase, a saturated sodium chloride solution, and as the organic phase, toluene.
  • a phase-transfer catalyst such as tetrabutylammonium bromide, can be used to catalyze the reaction, which can proceed at elevated temperatures (e.g.
  • the reaction product generally includes equal parts of bis (triethoxypropyl) tetrasulfide, bis(triethoxypropyl) disulfide, and polysulfide by-product. These reactions are generally known as disclosed in U.S. Patent Nos. 6,680,398 and 5,583,245, which are incorporated herein by reference.
  • a crude bis(triethoxypropyl) sulfide-containing stream obtained directly from the reactor is used within the tire formulations.
  • the bis (triethoxypropyl) sulfide-containing stream is purified to produce a bis (triethoxypropyl) sulfide stream that is higher in the desired bis(triethoxypropyl) sulfide content.
  • the bis(triethyoxypropyl) sulfide-containing stream exiting this reaction step includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % bis(triethoxypropyl) sulfide based upon the entire weight of the bis(triethoxypropyl) sulfide-containing stream.
  • the bis (triethoxypropyl) sulfides produced by the methods of this invention can be used in the production of tire components.
  • these sulfides can be used as silane coupling agents within vulcanizable compositions that include silica as a filler.
  • practice of the present invention provides a method by which waste material, in particular waste material from used tires, is used in the manufacture of useful tires.
  • Practice of the present invention not only offers a method for recycling tires by employing used tires as a feedstock to produce silane coupling agents that can be included into formulations for producing tire components, but the practice of the present invention also advantageously provides a method whereby a tire is produced that has a relatively high content of sustainable constituents, which include recycled materials, naturally-derived materials and/or materials synthesized from bio-synthesized feedstock or bio-based materials.
  • these tires or tire components include threshold amounts of coupling agents of this invention while being characterized by high sustainable content.
  • the tires or tire components of the present invention can include greater than 40 wt %, in other embodiments greater than 50 wt %, and in other embodiments greater than 60 wt % sustainable materials.
  • the tire or tire components include from about 40 to about 90 wt %, in other embodiments from about 45 to about 85 wt %, and in other embodiments from about 50 to about 80 wt % sustainable material.
  • the coupling agent component of the tires or tire components of the present invention include greater than 10 wt %, in other embodiments greater than 20 wt %, in other embodiments greater than 30 wt %, in other embodiments greater than 40 wt %, in other embodiments greater than 45 wt %, and in other embodiments greater than 50 wt % coupling agents of this invention, which includes silane coupling agents produced according to embodiments of the present invention.
  • tire components are produced by preparing and vulcanizing rubber compositions, which are often referred to as vulcanizable rubber compositions or simply rubber compositions.
  • the vulcanizable rubber compositions include a rubber component, filler, wax, and curative.
  • Other ingredients that may be included in the vulcanizable rubber composition include extender oils, processing oils, resins, and antidegradants.
  • the rubber component of the vulcanizable rubber compositions includes a vulcanizable elastomer, which may also be referred to as an elastomer, a vulcanizable rubber, or simply as a rubber.
  • a vulcanizable elastomer which may also be referred to as an elastomer, a vulcanizable rubber, or simply as a rubber.
  • the vulcanizable elastomer is capable of being cured, which may also be referred to as vulcanized, to form an elastomeric composition.
  • the rubber component includes one or more synthetic polymers.
  • These synthetic polymers may include, for example and without limitation, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co- isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof.
  • the rubber component of the vulcanizable rubber compositions of this invention includes one or more circular synthetic rubbers, which is vulcanizable rubber produced from used tires. These circular synthetic rubbers may be used alone as the rubber component or in combination with synthetic polymers.
  • the rubber component may include one or more natural rubbers.
  • Natural rubber may be used alone as the rubber component or in combination with synthetic polymers and/or circular synthetic rubber.
  • synthetic rubber is synthesized by and obtained from plant life.
  • natural rubber can be obtained from Hevea rubber trees, guayule shrub, gopher plant, mariola, rabbitbrush, milkweeds, goldenrods, pale Indian plantain, rubber vine, Russian dandelions, mountain mint, American germander, and tall bellflower.
  • the rubber compositions of this invention include from about 30 to about 65 wt %, in other embodiments from about 35 to about 60 wt %, and in other embodiments from about 40 to about 55 wt % elastomer, based on the total weight of the tire component.
  • the rubber compositions include fillers such as organic and inorganic fillers.
  • organic fillers include carbon black and starch.
  • inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, mica, talc (hydrated magnesium silicate), and clays (hydrated aluminum silicates).
  • a mixture of different fillers may be advantageously employed.
  • the amount of total filler employed in the rubber compositions can be up to about 150 parts by weight per 100 parts by weight of rubber (phr), with about 30 to about 125 phr, or about 40 to about 110 phr being typical. In certain embodiments the total filler content is greater than about 100 phr. In other embodiments, the total filler content is from about 50 to about 100 phr, and in in further embodiments from about 55 to about 95 phr.
  • carbon blacks include furnace blacks, channel blacks, and lamp blacks. More specific examples of carbon blacks include super abrasion furnace blacks, intermediate super abrasion furnace blacks, high abrasion furnace blacks, fast extrusion furnace blacks, fine furnace blacks, semi-reinforcing furnace blacks, medium processing channel blacks, hard processing channel blacks, conducting channel blacks, and acetylene blacks.
  • the carbon blacks may have a surface area (EMSA) of at least 20 m 2 /g and in other embodiments at least 35 m 2 /g; surface area values can be determined by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) technique.
  • the carbon blacks may be in a pelletized form or an unpelletized flocculent form. The preferred form of carbon black may depend upon the type of mixing equipment used to mix the rubber compound.
  • carbon black can be sourced from a recycled material.
  • Such recycled material can include reclaimed or recycled vulcanized rubber, whereby the vulcanized rubber is typically reclaimed from manufactured articles such as a pneumatic tire, an industrial conveyor belt, a power transmission belt, and a rubber hose.
  • the recycled carbon black may be obtained by a pyrolysis process or other methods known for obtaining recycled carbon black.
  • a recycled carbon black can be formed from incomplete combustion of recycled rubber feedstock or rubber articles.
  • the recycled carbon black can be formed from the incomplete combustion of feedstock including oil resulting from the tire pyrolysis process.
  • the carbon blacks utilized in the preparation of the vulcanizable elastomeric compositions can be in pelletized form or an unpelletized flocculent mass.
  • the amount of carbon black employed in the rubber compositions can be up to about 75 parts by weight per 100 parts by weight of rubber (phr), with about 5 to about 60 phr, or about 10 to about 55 phr being typical.
  • the rubber composition can further include filler in the form of one or more recycled rubbers in a particulate form.
  • Recycled particulate rubber is typically broken down and reclaimed (or recycled) by any of a plurality of processes, which can include physical breakdown, grinding, chemical breakdown, devulcanization, cryogenic grinding, a combination thereof, etc.
  • the term recycled particulate rubber can relate to both vulcanized and devulcanized rubber, where devulcanized recycle or recycled rubber (reclaim rubber) relates to rubber which has been vulcanized, ground into particulates and may have further undergone substantial or partial devulcanization.
  • the recycled particulate rubber used in the rubber composition is essentially free of recycled rubber resulting from devulcanization.
  • the “recycled particulate rubber” comprises cured, i.e., vulcanized (crosslinked) rubber that has been ground or pulverized into particulate matter having a mean average particle size as discussed below.
  • Certain silicas may be considered sustainable materials.
  • Some commercially available silicas which may be used as sustainable materials for the current invention include Hi-SilTM 215, Hi-SilTM 233, and Hi-SilTM 190 (PPG Industries, Inc.; Pittsburgh, Pa.).
  • Other suppliers of commercially available silica include Grace Davison (Baltimore, Md.), Degussa Corp. (Parsippany, N.J.], Rhodia Silica Systems (Cranbury, N.J.], and J.M. Huber Corp. (Edison, N.J.].
  • Other sustainable silicas include those derived from rice husk ash.
  • silicas may be characterized by their surface areas, which give a measure of their reinforcing character.
  • the Brunauer, Emmet and Teller (“BET”] method (described in ]. Am. Chem. Soc., 1939, vol. 60, 2 p. 309-319] is a recognized method for determining the surface area.
  • the BET surface area of silica is generally less than 450 m 2 /g.
  • Useful ranges of surface area include from about 32 to about 400 m 2 /g, about 100 to about 250 m 2 /g, and about 130 to about 240 m 2 /g, and about 170 to about 220 m 2 /g.
  • the silica may have a BET surface area of 190 to about 280 m 2 /g.
  • the pH’s of the silicas are generally from about 5 to about 7 or slightly over 7, or in other embodiments from about 5.5 to about 6.8.
  • the amount of silica employed in the rubber compositions can be from about 1 to about 150 phr or in other embodiments from about 5 to about 130 phr.
  • the useful upper range is limited by the high viscosity imparted by silicas.
  • the silica employed in the rubber composition is derived from rice husk ash only, and in other embodiments the rubber compositions do not include silica from non-rice husk ash derived processes.
  • silica is used together with carbon black, the amount of the silica or carbon black individually can be as low as about 1 phr.
  • the amounts of coupling agents and shielding agents range from about 4 wt % to about 20 wt % based on the weight of silica used.
  • the weight ratio or silica to total filler may be from about 5 wt % to about 99 wt % of the total filler, in other embodiments from about 10 wt % to about 90 wt % of the total filler, or in yet other embodiments from about 50 wt % to about 85 wt % of the total filler.
  • the silica and carbon black fillers employed in the rubber composition are selected from the group consisting of sustainable pyrolysis carbon black and/or rice husk ash derived silica.
  • a silane coupling agent is typically employed when silica is used as a filler in the vulcanizable compositions.
  • the coupling agents of this invention are used within the vulcanizable compositions.
  • the coupling agents of this invention may be the only silane coupling agents used.
  • the coupling agents of this invention are used in conjunction with conventional silane coupling agents.
  • a multitude of rubber curing agents may be employed, including sulfur or peroxide-based curing systems. Curing agents are described in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol. 20, pgs. 365-468, (3 rd Ed. 1982), particularly Vulcanization Agents and Auxiliary Materials, pgs. 390-402, and A.Y. Coran, Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, (2 nd Ed. 1989), which are incorporated herein by reference. Vulcanizing agents may be used alone or in combination. WAX
  • the rubber composition may include one or more natural waxes.
  • a natural wax, or one with no petroleum as its raw material can include carnauba wax, candelilla wax (e.g., extracted from candelilla flowers), rice wax (e.g., separated from rice bran oil) and Japan wax (e.g., extracted from Japanese wax tree).
  • the rubber compositions of this invention include from about 1 to about 20 parts by weight, or in other embodiments from about 2 to about 15 parts by weight total wax per 100 parts by weight rubber.
  • the rubber compositions of this invention include threshold amounts of sustainable waxes, which includes natural waxes. The amount of sustainable wax, relative to the total weight of wax included, may be from about 1 wt % to about 99 wt %, or in other embodiment from about 20 wt % to about 80 wt % of the total wax. In certain embodiments, the rubber composition includes sustainable waxes only.
  • oils sustainable oils, which include plant-based oils and biobased oils
  • Plant-based oils may include plant-based triglycerides.
  • Exemplary oils include, without limitation, palm oil, soybean oil (also referred to herein as soy oil), rapeseed oil, sunflower seed, peanut oil, cottonseed oil, oil produced from palm kernel, coconut oil, olive oil, corn oil, grape seed oil, hemp oil, linseed oil, rice oil, safflower oil, sesame oil, mustard oil, flax oil.
  • oils obtained from beech nuts, cashews, mongongo nuts, macadamia nuts, pine nuts, hazelnuts, chestnuts, acorns, almonds, pecans, pistachios, walnuts, or brazil nuts.
  • these oils can be produced by any suitable process such as mechanical extraction (e.g., using an oil mill), chemical extraction (e.g., using a solvent, such as hexane or carbon dioxide), pressure extraction, distillation, leaching, maceration, purification, refining, hydrogenation, sparging, etc.
  • Bio-based oils can include oils produced by a recombinant cell.
  • bio-oils produced by recombinant cells can be produced using a select strain of algal cells that are fed with a supply of sugars (e.g., sucrose) and then allowed to ferment and produce a bio-oil with a selected profile; after sufficient growth or fermentation has taken place, the bio-oil is isolated from the cells and collected.
  • sugars e.g., sucrose
  • the rubber compositions of this invention can include from about 1 to about 70 parts by weight, or in other embodiments from about 5 to about 50 parts weight total oil per 100 parts by weight rubber.
  • the amount of sustainable oil, relative to the total weight of oil included, may be from about 1 wt % to about 99 wt %, or in other embodiment from about 20 wt % to about 80 wt %.
  • Other ingredients that are typically employed in rubber compounding may also be added to the rubber compositions. These include accelerators, accelerator activators, oils, plasticizer, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and antidegradants such as antioxidants and antiozonants.
  • All ingredients of the rubber compositions can be mixed with standard mixing equipment such as Banbury or Brabender mixers, extruders, kneaders, and two-rolled mills.
  • the ingredients are mixed in two or more stages.
  • a so-called masterbatch which typically includes the rubber component and filler, is prepared.
  • the masterbatch may exclude vulcanizing agents.
  • the masterbatch may be mixed at a starting temperature of from about 25 °C to about 125 °C with a discharge temperature of about 135 °C to about 180 °C.
  • the vulcanizing agents may be introduced and mixed into the masterbatch in a final mixing stage, which is typically conducted at relatively low temperatures so as to reduce the chances of premature vulcanization.
  • additional mixing stages sometimes called remills, can be employed between the masterbatch mixing stage and the final mixing stage.
  • remill stages are often employed where the rubber composition includes silica as the filler.
  • Various ingredients including the polymers of this invention can be added during these remills.
  • the mixing procedures and conditions particularly applicable to silica- fille d tire formulations are described in U.S. Patent Nos. 5,227,425; 5,719,207; and 5,717,022, as well as European Patent No. 890,606, all of which are incorporated herein by reference.
  • the initial masterbatch is prepared by including the polymer and silica in the substantial absence of coupling agents and shielding agents.
  • the polymers are mixed with various other ingredients [e.g. filler and curative) to produce a rubber composition (also referred to as vulcanizable composition), and the vulcanizable composition is then processed into tire components according to ordinary tire manufacturing techniques, which generally include standard rubber shaping and molding techniques.
  • the tire components may include, but are not limited to, tire treads, sidewalls, subtreads, body ply skims, and bead filler.
  • the various tire components are then assembled into a green tire (i.e. an uncured tired), placed within a mold, and then vulcanized.
  • vulcanization is effected by heating the vulcanizable composition in a mold; e.g., it may be heated to about 140 °C to about 180 °C.
  • Cured or crosslinked rubber compositions may be referred to as vulcanizates, which generally contain three-dimensional polymeric networks that are thermoset.
  • the other ingredients, such as fillers and processing aids, may be evenly dispersed throughout the crosslinked network.
  • Pneumatic tires can be made as discussed in U.S. Patent Nos. 5,866,171; 5,876,527; 5,931,211; and 5,971,046, which are incorporated herein by reference.
  • the tires can include fabric reinforcement made by using non-petroleum materials in place of synthetic fibers.
  • non-petroleum materials for example, mechanical recycled fibers, chemical recycled fibers, or bio-based fibers can be used.
  • the tires can include metal reinforcement made from recycled steel and/or other circular or sustainable metals. These non-petroleum fabrics and recycled metals can be used exclusively within the tires or in combination with traditional fabric and/or metal reinforcement.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Biotechnology (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

Un procédé comprend (a) la fourniture d'une matière première qui comprend des matériaux carbonés ; (b) la gazéification de la matière première pour produire un flux gazeux comprenant du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone ; (c) la conversion d'au moins une partie du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone en éthanol ; (d) la mise en réaction d'au moins une partie de l'éthanol avec du chloropropyltrichlorosilane pour produire du chloropropyltriéthoxysilane ; et (e) la mise en réaction d'au moins une partie du chloropropyltriéthoxysilane avec du soufre et de l'hydrosulfure de sodium pour produire un bis(triéthoxypropyl)sulfure.
PCT/US2024/033032 2023-06-07 2024-06-07 Agents de couplage provenant de pneus usagés et utilisation dans un caoutchouc pour pneu Pending WO2024254466A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363506748P 2023-06-07 2023-06-07
US63/506,748 2023-06-07

Publications (1)

Publication Number Publication Date
WO2024254466A1 true WO2024254466A1 (fr) 2024-12-12

Family

ID=93796459

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/033032 Pending WO2024254466A1 (fr) 2023-06-07 2024-06-07 Agents de couplage provenant de pneus usagés et utilisation dans un caoutchouc pour pneu

Country Status (1)

Country Link
WO (1) WO2024254466A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4072701A (en) * 1975-09-24 1978-02-07 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of sulfur containing organosilicon compounds
US20070112119A1 (en) * 2005-11-14 2007-05-17 Sumitomo Rubber Industries, Ltd. Rubber composition and pneumatic tire using the same for tread
US20120073292A1 (en) * 2010-09-27 2012-03-29 Saudi Arabian Oil Company Process for the gasification of waste tires with residual oil
WO2012062633A1 (fr) * 2010-11-09 2012-05-18 Ineos Commercial Services Uk Limited Procédé et dispositif de production d'éthylène par préparation de gaz de synthèse
US20170334805A1 (en) * 2015-01-13 2017-11-23 Sekisui Chemical Co., Ltd. Butadiene production system and butadiene production method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4072701A (en) * 1975-09-24 1978-02-07 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of sulfur containing organosilicon compounds
US20070112119A1 (en) * 2005-11-14 2007-05-17 Sumitomo Rubber Industries, Ltd. Rubber composition and pneumatic tire using the same for tread
US20120073292A1 (en) * 2010-09-27 2012-03-29 Saudi Arabian Oil Company Process for the gasification of waste tires with residual oil
WO2012062633A1 (fr) * 2010-11-09 2012-05-18 Ineos Commercial Services Uk Limited Procédé et dispositif de production d'éthylène par préparation de gaz de synthèse
US20170334805A1 (en) * 2015-01-13 2017-11-23 Sekisui Chemical Co., Ltd. Butadiene production system and butadiene production method

Similar Documents

Publication Publication Date Title
Deng et al. Research progress on sustainability of key tire materials
WO2020230631A1 (fr) Matériau composite silice-carbone et sa méthode de production
US20250043044A1 (en) Butadiene production from used tires
JP2015098539A (ja) タイヤ用ゴム組成物及び空気入りタイヤ
WO2024254466A1 (fr) Agents de couplage provenant de pneus usagés et utilisation dans un caoutchouc pour pneu
JP6069240B2 (ja) 冬用空気入りタイヤ及びその製造方法
WO2024254475A1 (fr) Polyéthylène téréphtalate produit à partir de pneus usagés
WO2024254458A1 (fr) Production de polyéthylène à partir de pneus usagés
US20250257187A1 (en) Butadiene production from used tires
WO2024254485A1 (fr) Production de butadiène à partir de pneus usagés
US20250257188A1 (en) Butadiene production from used tires
WO2024254453A1 (fr) Production de styrène à partir de pneus usagés et utilisation en caoutchouc de pneu
WO2024254469A1 (fr) Polyamides produits à partir de pneus usagés
RU2844812C2 (ru) Получение бутадиена из отработавших шин
US20250263355A1 (en) Butadiene production from used tires
US20250263354A1 (en) Butadiene production from used tires
US20250257165A1 (en) Butadiene production from used tires
US20250277068A1 (en) Gasification process
CN118524997A (zh) 利用废旧轮胎的丁二烯生产
JP6317498B2 (ja) スタッドレスタイヤ用トレッド用ゴム組成物、及びスタッドレスタイヤ
Sampath et al. Advancements in sustainable materials for environmentally responsible tyre production: a comprehensive review
JP6042400B2 (ja) 空気入りタイヤ
RU2024118436A (ru) Получение бутадиена из отработавших шин
JP6045555B2 (ja) 空気入りタイヤ
JP6304924B2 (ja) サイドウォール用ゴム組成物、及び空気入りタイヤ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24820138

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE