WO2025007008A2 - Compositions pour pneus à faible résistance au roulement - Google Patents

Compositions pour pneus à faible résistance au roulement Download PDF

Info

Publication number
WO2025007008A2
WO2025007008A2 PCT/US2024/036190 US2024036190W WO2025007008A2 WO 2025007008 A2 WO2025007008 A2 WO 2025007008A2 US 2024036190 W US2024036190 W US 2024036190W WO 2025007008 A2 WO2025007008 A2 WO 2025007008A2
Authority
WO
WIPO (PCT)
Prior art keywords
silane
tire tread
grafted
composition
tread composition
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.)
Ceased
Application number
PCT/US2024/036190
Other languages
English (en)
Other versions
WO2025007008A3 (fr
Inventor
Krishnamachari Gopalan
Robert Lenhart
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.)
Cooper Standard Automotive Inc
Original Assignee
Cooper Standard Automotive Inc
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 Cooper Standard Automotive Inc filed Critical Cooper Standard Automotive Inc
Publication of WO2025007008A2 publication Critical patent/WO2025007008A2/fr
Publication of WO2025007008A3 publication Critical patent/WO2025007008A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • C08K3/02—Elements
    • C08K3/06—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • compositions and additives for making tire treads are provided.
  • a tire composition for forming tire treads includes a styrene-butadiene rubber and a butadiene rubber. Characteristically, the weight ratio of the styrene-butadiene rubber to the butadiene rubber is from 2:1 to 4: 1.
  • the tire tread composition also includes a polyolefin component selected from the group consisting of silane-grafted polyolefins, non-silane grafted polyolefins, and combinations thereof.
  • the tire tread composition also includes a filler selected from the group consisting of carbon black, silica, and combinations thereof and an additive composition.
  • a tread section for a tire is provided.
  • the tread section is formed from the tire tread composition described herein. Characteristically, the tread section includes a plurality of tire treads.
  • a tire tread composition in another aspect, includes a base composition for tire treads and a tread additive elastomeric composition including a component selected from the group consisting of a silane-grafted polyolefin, a non-silane-grafted polyolefin, and combinations thereof.
  • FIGURE 1 Schematic illustration of a pneumatic tire having a tread block made with a tire tread composition.
  • FIGURE 2 Spider graph summarizing the tire properties for treads made with the tire tread compositions.
  • Ri where i is an integer
  • Ri include hydrogen, alkyl, lower alkyl, Ci-6 alkyl, C 6 -io aryl, C 6 -io heteroaryl, -NO 2 , -NH 2 , -N(R’R”), -N(R’R”R”’) + L-, Cl, F, Br, -CF 3 , -CCI3, -CN, - SO3H, -PO3H2, -COOH, -CO2R’, -COR’, -CHO, -OH, -OR’, -O M + , -SO 3 M + , -PO 3 M + , -COO M + , - CF2H, -CF2R’, -CFH2, and -CFR’R” where R’, R” and R’” are C1-10 alkyl or Ce-is aryl groups M is a metal atom (e.g., Na, K, Li, etc.)
  • alkyl refers to C1-20 inclusive, linear (i.e., “straight-chain”), branched, saturated or at least partially and in some cases fully unsaturated i.e., alkenyl and alkynyl) hydrocarbon chains, including for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, and allenyl groups.
  • Branched refers to an alkyl group in which a lower alkyl group, such as methyl, ethyl or propyl, is attached to a linear alkyl chain.
  • Lower alkyl refers to an alkyl group having 1 to about 8 carbon atoms (i.e., a Ci-8 alkyl), e.g., 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.
  • Higher alkyl refers to an alkyl group having about 10 to about 20 carbon atoms, e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
  • integer ranges explicitly include all intervening integers.
  • the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.
  • the range 1 to 100 includes 1, 2, 3, 4. . . . 97, 98, 99, 100.
  • intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1. to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits.
  • concentrations, temperature, and reaction conditions e.g.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, etc.
  • concentrations, temperature, and reaction conditions e.g., pH, etc.
  • concentrations, temperature, and reaction conditions e.g., pH, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 10 percent of the values indicated rounded to three significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • concentrations, temperature, and reaction conditions can be practiced with plus or minus 10 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
  • BR means butadiene rubber
  • SBR means styrene-butadiene rubber.
  • LSBR liquid styrene-butadiene rubber
  • SSBR solution styrene-butadiene rubber
  • FIG. 1 provides a schematic illustration of a pneumatic tire having a tread section that is formed from a thread composition with improved rolling resistance.
  • Pneumatic tire 10 includes tread block 12 disposed over undertread 14, which is disposed over carcass 16. Cap piles 20 and belts 22 are interposed between the undertread 14 and carcass 16. Sidewall 23, which abuts thread block 12, is also depicted.
  • the tire tread compositions set forth herein are used for forming tread section 14.
  • Tread block 12 includes treads 24 defined by the tread rubber and interposed between blocks 26. Tread block 12 can also include ribs 28, which is a pattern of tread features aligned around the circumference of the tire. Tread block 12 also includes shoulder sections 30 and 32 which have dimples 34 and sipes 36 defined by the tread rubber therein.
  • a tire tread composition used to form the tread section of Figure 1 is provided.
  • the tire tread composition includes a styrene-butadiene rubber and a butadiene rubber. Characteristically, the weight ratio of the styrene-butadiene rubber to the butadiene rubber is from 2:1 to 4:1.
  • the tire tread composition also includes a polyolefin component selected from the group consisting of silane-grafted polyolefins, non-silane grafted polyolefins, and combinations thereof.
  • the tire tread composition includes a filler selected from the group consisting of carbon black, silica, and combinations thereof and an additive composition.
  • the silica is present in an amount from about 20 weight percent to 40 weight percent of the total weight of the tire tread composition.
  • the carbon black is present in an amount from about 1 weight percent to 40 weight percent of the total weight of the tire tread composition.
  • the carbon black is present in an amount from about 1 weight percent to 4 weight percent of the total weight of the tire tread composition.
  • the additive composition includes one or more additives.
  • the one or more additives include a component selected from the group consisting of a nucleating agents (e.g., talc), a plasticizer, one or more process aids, a curative agent (e.g., peroxide, sulfur), one or more accelerators, one or more activators, one or more antioxidants, a wax, and combinations thereof.
  • a nucleating agents e.g., talc
  • a plasticizer e.g., one or more process aids
  • a curative agent e.g., peroxide, sulfur
  • accelerators e.g., peroxide, sulfur
  • accelerators e.g., peroxide, sulfur
  • activators e.g., peroxide, sulfur
  • antioxidants e.g., a wax
  • wax e.g., a wax
  • Process aids are agents that improve flow and processability. Examples of process aids include but are not limited to, stearic acid
  • the tire tread composition includes a plasticizer in an amount from about 5 weight percent to 20 weight percent of the total weight of the tire tread composition.
  • the plasticizer is present in an amount of at least 1 weight percent, 3 weight percent, 5 weight percent, 7 weight percent, or 10 weight percent of the total weight of the tire tread composition.
  • the plasticizer is present in an amount of at most 25 weight percent, 20 weight percent, 18 weight percent, 15 weight percent, or 10 weight percent of the total weight of the tire tread composition.
  • the additive composition includes a coupling agent.
  • the coupling agent is an organosilane with disulfide groups or tetrasulfide groups.
  • Examples of such coupling agents include, but are not limited to, bis(triethoxysilylpropyl)tetrasulfide, bis(triethoxy sily lpropyl)disulfide, bis(triethoxy silylpropyl)disulfide, 3 - thiocyanatopropyltriethoxysilane, and the like.
  • the coupling agent is present in an amount from about 1 weight percent to 5 weight percent of the total weight of the tire tread composition.
  • the coupling agent is present in an amount of at least 0.5 weight percent, 1 weight percent, 1.5 weight percent, 2 weight percent, or 3 weight percent of the total weight of the tire tread composition. In some further refinements, the coupling agent is present in an amount of at most 8 weight percent, 7 weight percent, 6.5 weight percent, 6 weight percent, or 5 weight percent of the total weight of the tire tread composition.
  • the additive composition includes an activator is selected from the group consisting of stearic acid, zinc oxide, and combinations thereof.
  • the additive composition includes stearic acid in an amount from 0.1 to 1.5 weight percent of the total weight of the tire tread composition.
  • the additive composition includes zinc oxide in an amount from 0.3 to 3 weight percent of the total weight of the tire tread composition.
  • the additive composition includes a wax.
  • the wax in an amount from 0.3 to 3 weight percent of the total weight of the tire tread composition.
  • the wax in an amount of at least 0.1 weight percent, 0.2 weight percent, 0.3 weight percent, 0.5 weight percent, or 1 weight percent of the total weight of the tire tread composition.
  • the wax in an amount of at most 5 weight percent, 4 weight percent, 3 weight percent, 2.5 weight percent, or 2 weight percent of the total weight of the tire tread composition.
  • the additive composition includes antioxidants.
  • the antioxidant can be based on p-phenylenediamine.
  • a specific example is A 1 -(4-Methylpentan-2-yl)-2V 4 - phenylbenzene-l,4-diamine.
  • the antioxidant is a sterically hindered amine.
  • a specific example of this type of antioxidant is 2,2,4-trimethyl-l,2-dihydroquinoline.
  • the antioxidants are present in an amount from 0.3 to 4 weight percent of the total weight of the tire tread composition.
  • the additive composition includes a curative or combinations of curatives.
  • the curative is sulfur (e.g., a sulfur curing agent or sulfur curing system) which can form crosslinking involving disulfide links or sulfide links, typically, after a silane-grafted polyolefin and/or a non- silane-grafted polyolefin is added to the tire tread composition, a further refinement, the sulfur curative is present in an amount from 0.1 to 2 weight percent of the total weight of the tire tread composition.
  • the curative is a peroxide, and in particular, an organoperoxide. Peroxide promotes crosslinking of polymer chains by C-C bond.
  • the peroxide curative is present in an amount from 0.1 to 5 weight percent of the total weight of the tire tread composition.
  • Peroxide can be added to contribute to crosslinking of grafted or non-grafted polyolefins, (see Table 2 below).
  • the polyolefins can be grafted and then added to tire tread composition.
  • the curative includes both a peroxide and sulfur to provide a dual curing system.
  • the outsole composition allows for a dual curing system. In this instance, the sulfur formed sulfur bridges within the polymer in the base composition. The presence of peroxide forms carbon-carbon bonds (C-C bonds) in the polymers in the outsole composition and in the polymer in the base composition.
  • the additive composition includes accelerators in an amount from 0.1 to 2 weight percent of the total weight of the tire tread composition.
  • accelerators include but are not limited to, N-cyclohexyl-2-benzothioazole sulfenamide, diphenyl guanidine, thiazole, and sulfenamide boosters.
  • the accelerators are present in an amount from 0.1 to 2 weight percent of the total weight of the tire tread composition.
  • the polyolefin component includes a silane-grafted olefin block copolymer and/or a non- silane-grafted olefin block copolymer.
  • the polyolefin component is a non-silane grafted polyolefins.
  • the non-silane grafted polyolefins is an olefin block copolymer.
  • the olefin block copolymer is present in an amount from about 2 weight percent to 8 weight percent of the total weight of the tire tread composition.
  • the non-silane-grafted polyolefin includes a polyethylene, polybutylene, polystyrene, a styrene block copolymer, an ethylene a-olefin copolymer, or combinations thereof.
  • the non-silane-grafted polyolefin includes a low-density polyethylene, a high-density polyethylene, an ultrahigh molecular polyolefin, or combinations thereof.
  • the non-silane-grafted polyolefin is selected from the group consisting of ethylene/a-olefin copolymers, olefin block copolymers, and combinations thereof.
  • the polyolefin component is a silane-grafted polyolefin.
  • the silane-grafted polyolefin is a silane-grafted olefin block copolymer.
  • the olefin block copolymer is present in an amount from about 2 weight percent to 8 weight percent of the total weight of the tire tread composition.
  • the silane-grafted polyolefin includes a silane-grafted polyethylene, a silane-grafted butylene, a silane-grafted styrene, a silane-grafted styrene block copolymer, a silane-grafted ethylene a-olefin copolymer, or combinations thereof.
  • the silane-grafted polyolefin includes a silane-grafted low-density polyethylene, a silane-grafted high-density polyethylene, a silane-grafted ultrahigh molecular polyolefin, or combinations thereof.
  • the silane-grafted polyolefin is selected from the group consisting of silane-grafted ethylene/a-olefin copolymers, silane-grafted olefin block copolymers, and combinations thereof.
  • the silane-grafted polyolefin is formed from a blend that includes a base polyolefin and a silane crosslinker having the following formula: wherein Ri, R2, and R3 are each independently H or lower alkyl or higher alkyl. In a refinement, Ri, R2, and R3 are each independently H or C1-8 alkyl. In a refinement, Ri, R2, and R3 are each methyl, ethyl, propyl, or butyl. Additional details of silane-grafted polyolefins and silane grafting are found in US Pat. Nos 10/774,168 and 10/779,608, the entire disclosures of which are hereby incorporated by reference in its entirety. In a refinement, the silane grafted silane-grafted polyolefin can be described by the following formula: polymer ⁇ backbone
  • the polymer backbone can be a polymer or copolymer backbone.
  • the silane-grafted polymer is mixed with a silanol-forming condensation catalyst and then exposed to humidity and/or heat to effect crosslinking of the copolymer in a two-step reaction.
  • the composition can be cross-linked via sulfonic acid catalyst (e.g., ‘Ambicat’) or a tin-based catalyst where the ambient moisture is sufficient to crosslink over a longer time period (e.g., about 48 hours).
  • the water hydrolyzes the silane to produce a silanol.
  • the silanol then condenses to form intermolecular, irreversible Si-O-Si crosslink sites. Additional details of silane-grafted polyolefins and silane grafting are found in US Pat. Nos 10/774,168 and 10/779,608, the entire disclosures of which are hereby incorporated by reference in its entirety.
  • the number average molecular weight of the silane-grafted polyolefins may be in the range of from about 4,000 g/mol to about 30,000 g/mol, including from about 5,000 g/mol to about 25,000 g/mol and from about 6,000 g/mol to about 14,000 g/mol.
  • the weight average molecular weight of the grafted polymers may be from about 8,000 g/mol to about 60,000 g/mol, including from about 10,000 g/mol to about 30,000 g/mol.
  • the density of the base polyolefin is less than 1.0 g/cm 3 , including less than about 0.92 g/cm 3 .
  • the density may be from about 0.85 g/cm 3 to about 0.96 g/cm 3 .
  • the density is at least 0.84 g/cm3, including at least about 0.862 g/cm 3 .
  • the tire tread composition includes a nanofiller (i.e., at least one dimension less than 100 nm).
  • nanofillers include carbon nanotubes, nanoclays, graphene, carbon nanofibers, cellulose nanofibers, nanoscale silica particles, and combinations thereof.
  • the tire tread composition includes a condensation catalyst when the polyolefin component includes a silane-grafted polyolefin.
  • the condensation catalyst promotes the formation of silane crosslinking.
  • the condensation catalyst can include, for example, organic bases, carboxylic acids, and organometallic compounds (e.g., organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc, and tin).
  • the condensation catalyst can include fatty acids and metal complex compounds such as metal carboxylates; aluminum triacetyl acetonate, iron triacetyl acetonate, manganese tetraacetyl acetonate, nickel tetraacetyl acetonate, chromium hexaacetyl acetonate, titanium tetraacetyl acetonate and cobalt tetraacetyl acetonate; metal alkoxides such as aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide, titanium propoxide and titanium butoxide; metal salt compounds such as sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctoate, di
  • the condensation catalyst can include ibutyltindilaurate, dioctyltinmaleate, dibutyltindiacetate, dibutyltindioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, and cobalt naphthenate.
  • a single condensation catalyst or a mixture of condensation catalysts may be utilized.
  • the condensation catalyst(s) may be present in an amount from about 0.01 wt % to about 8 wt %, based on the total weight of the expanded polymeric polymer sheet.
  • the tread composition can include a peroxide initiator (e.g., a peroxide curing agent).
  • a peroxide initiator e.g., a peroxide curing agent
  • the peroxide initiators can independently include a peroxide selected from the group consisting of hydrogen peroxide and organoperoxides such as alkyl hydroperoxides, dialkyl peroxides, and diacyl peroxides.
  • peroxide examples include, but are not limited to, an organic peroxide selected from the group consisting of di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexyne-3, l,3-bis(t-butyl- peroxy-isopropyl)benzene, n-butyl-4,4-bis(t-butyl-peroxy)valerate, benzoyl peroxide, t- butylperoxybenzoate, t-butylperoxy isopropyl carbonate, t-butylperbenzoate, bis(2- methylbenzoyl)peroxide, bis(4-methylbenzoyl)peroxide, t-butyl peroctoate, cumene hydroperoxide, methyl ethyl ketone peroxide, lauryl peroxide, ter
  • a tire tread composition includes a base composition for tire treads (i.e., a base tire tread composition) and a tread additive elastomeric composition.
  • a base tire tread composition is a composition that forms tire treads even without a silane-grafted polyolefin being added.
  • the tire additive elastomeric composition includes a component selected from the group consisting of a silane-grafted polyolefin, a non-silane-grafted polyolefin, and combinations thereof.
  • the tread additive elastomeric composition is combined with the base composition for tire treads or tank track pads to achieve low rolling resistance. Details for the silane- grafted polyolefins, the non-silane-grafted polyolefins, the peroxides, and the silane crosslinkers are described above.
  • the tread additive elastomeric composition includes the silane- grafted polyolefin.
  • the silane-grafted polyolefin can include a silane-grafted polyethylene, a silane-grafted butylene, a silane-grafted styrene, a silane-grafted styrene block copolymer, a silane-grafted ethylene a-olefin copolymer, or combinations thereof.
  • the silane-grafted polyolefin includes a silane-grafted low density polyethylene, a silane-grafted high density polyethylene, a silane-grafted ultrahigh molecular polyolefine, or combinations thereof.
  • the first silane-grafted polyolefin is a silane-grafted olefin block copolymer.
  • the silane-grafted polyolefin is selected from the group consisting of silane-grafted olefin homopolymers, silane-grafted blends of homopolymers, copolymers of two or more olefins, silane-grafted blends of copolymers of two or more olefins, and a combination of silane-grafted olefin homopolymers blended with copolymers of two or more olefins.
  • the tread additive elastomeric composition includes a non-silane- grafted polyolefin.
  • the non-silane grafted polyolefins is an olefin block copolymer.
  • the non-silane-grafted polyolefin includes a polyethylene, polybutylene, polystyrene, a styrene block copolymer, an ethylene a-olefin copolymer, or combinations thereof.
  • the non-silane-grafted polyolefin includes a low-density polyethylene, a high-density polyethylene, an ultrahigh molecular polyolefin, or combinations thereof.
  • the non-silane-grafted polyolefin is selected from the group consisting of ethylene/a-olefin copolymers, olefin block copolymers, and combinations thereof.
  • the number average molecular weight of the non-silane-grafted polyolefins may be in the range of from about 4,000 g/mol to about 30,000 g/mol, including from about 5,000 g/mol to about 25,000 g/mol and from about 6,000 g/mol to about 14,000 g/mol.
  • the weight average molecular weight of the grafted polymers may be from about 8,000 g/mol to about 60,000 g/mol, including from about 10,000 g/mol to about 30,000 g/mol.
  • the density of the non-silane-grafted polyolefins is less than 1.0 g/cm 3 , including less than about 0.92 g/cm 3 .
  • the density may be from about 0.85 g/cm 3 to about 0.96 g/cm 3 .
  • the density is at least 0.84 g/cm3, including at least about 0.862 g/cm 3 .
  • the cis-to-trans ratio for the polyolefins set forth above is greater than 1 and preferably greater than 2.
  • These polyolefins include the base polyolefins from which the silane- grafted polyolefin is formed, as well as the polyolefins for the non-silane-grafted polyolefins.
  • the cis-to-trans ratio of the polyolefins set forth above is at least 0, 1, 2, 3, or 5.
  • the cis-to-trans ratio of the polyolefins set forth above is at most 10, 8, 7, 6, or 5.
  • the polyolefins set forth above have a total unsaturation from 20 to 100 unsaturated bonds per 100,000 CH n groups where n is an integer label for the number of Hs (e.g., 1 or 2). In a refinement, the polyolefins set forth above have a total unsaturation from 40 to 60 unsaturated bonds per 100,000 CH n groups. In some refinement, the polyolefins set forth above have a total unsaturation of at least 5, 10, 20, 30, 40, 50, 60, or 70 unsaturated bonds per 100,000 CH n groups.
  • the polyolefins set forth above have a total unsaturation of at most 150, 120, 100, 90, 80, or 70 unsaturated bonds per 100,000 CH n groups.
  • a typical base (standard) composition for tire treads includes synthetic rubbers, natural rubbers, sulfur, and various fillers. Examples of synthetic rubbers include polybutadiene rubbers and styrene-butadiene rubbers.
  • the base composition is a tread composition that a tire manufacturer typically uses for making treads.
  • the tread additive elastomeric composition set forth herein includes an elastomeric component and one or more additives.
  • the one or more additives include a component selected from the group consisting of a polymer carrier, additives that increase tensile strength, a traction enhancer, a reinforcing filler, silane-terminated liquid polybutadiene, one or more process aids, a curative agent (e.g., sulfur), a butadiene rubber, a hydrocarbon resin, one or more accelerators, one or more activators, one or more antioxidants, a wax, and combinations thereof.
  • Process aids are agents that improve flow and processability. Examples of process aids include but are not limited to, octadecanoic acid and polyethylene glycol. Traction enhancers improve the wet traction in tire treads formed from the tire tread composition.
  • a traction enhancer is SBR, and in particular, SBR with high styrene content.
  • Activators assist in promoting chemical reactions. Examples of activators include but are not limited to, stearic Acid and ZnO.
  • Accelerators s are compounds that increase the reaction rate. Examples of accelerators include but are not limited to, N-cyclohexyl-2-benzothioazole sulfenamide, diphenyl guanidine, thiazole and sulfenamide boosters.
  • the tire tread composition includes from about 30 to 95 weight percent of the base (e.g., standard) tread composition and about 70 to 5 weight percent of the tread additive composition. In a refinement, the tire tread composition includes from about 30 to 90 weight percent of the base (e.g., standard) tread composition and about 70 to 1- weight percent of the tread additive composition. In a refinement, the tire tread composition includes from about 30 to 63 weight percent of the base (e.g., standard) tread composition and about 70 to 37 weight percent of the tread additive composition.
  • the tire tread composition includes 5 weight percent, 10 weight percent, at least 20 weight percent, 30 weight percent, 40 weight percent, or 50 weight percent of the base (e.g., standard) tire tread composition and/or at most 80 weight percent, 70 weight percent, 60 weight percent, or 50 weight percent of the base tire tread composition.
  • the tire tread composition includes the tread additive elastomeric composition in an amount from about 5 to 50 phr.
  • the tire tread composition includes the tread additive elastomeric composition in an amount from about 5 to 30 phr.
  • the tire tread composition includes the tread additive elastomeric composition in an amount of at least 1, 5, 7, 10, 12 or 15 phr and at most 60, 50, 40, 35, 30, 25, 20 or 18 phr.
  • a silane-grafted polyolefin is formed as described above with a peroxide.
  • This silane-grafted polyolefin is added to a typical base (standard) composition, which is subsequently cured with a sulfur curing agent and/or a peroxide curing agent.
  • Table 1 provides examples of tire tread compositions used to make treads.
  • Example 1 is a control sample used to compare the improvements of examples 2 and 3.
  • Table 2 provides the composition used to form the silane-grafted olefin block copolymer. It should be appreciated that practice within (i.e., +/-), in increasing order of preference, 30%, 20%, 10%, 5%, or 2% of the amounts indicated in Tables 1 and 2 are also contemplated.
  • Figure 2 shows the improvement in rolling resistance achieved by examples 2 and 3.
  • Table 1 Tire tread compositions used to make treads.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de bande de roulement de pneu comprend un caoutchouc styrène-butadiène et un caoutchouc butadiène. De manière caractéristique, le rapport en poids du caoutchouc styrène-butadiène au caoutchouc butadiène est de 2 : 1 à 4 : 1. La composition de bande de roulement de pneu comprend également un composant polyoléfine choisi dans le groupe constitué par les polyoléfines greffées par silane, les polyoléfines non greffées par silane, et des combinaisons de celles-ci. La composition de bande de roulement de pneu comprend également une charge choisie dans le groupe constitué par le noir de carbone, la silice et des combinaisons de ceux-ci et une composition d'additif.
PCT/US2024/036190 2023-06-28 2024-06-28 Compositions pour pneus à faible résistance au roulement Ceased WO2025007008A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363523768P 2023-06-28 2023-06-28
US63/523,768 2023-06-28

Publications (2)

Publication Number Publication Date
WO2025007008A2 true WO2025007008A2 (fr) 2025-01-02
WO2025007008A3 WO2025007008A3 (fr) 2025-05-15

Family

ID=93940069

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/036190 Ceased WO2025007008A2 (fr) 2023-06-28 2024-06-28 Compositions pour pneus à faible résistance au roulement

Country Status (1)

Country Link
WO (1) WO2025007008A2 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5769975A (en) * 1996-01-25 1998-06-23 The Standard Products Company Tire tread with cured portion and uncured end sections/wing portions
CN102414034A (zh) * 2009-04-30 2012-04-11 道康宁公司 硅烷改性的弹性体组合物
US9493637B2 (en) * 2011-04-22 2016-11-15 The Yokohama Rubber Co., Ltd. Tire rubber composition and studless tire
RU2635608C2 (ru) * 2013-09-26 2017-11-14 Дзе Йокогама Раббер Ко., Лтд. Каучуковая композиция для шины и зимняя нешипованная шина
CN109563329A (zh) * 2016-12-10 2019-04-02 库珀标准汽车公司 聚烯烃弹性体组合物及其制备方法
CN117561171A (zh) * 2021-06-08 2024-02-13 库珀标准汽车公司 用于低滚动阻力轮胎的Fortrex添加剂

Also Published As

Publication number Publication date
WO2025007008A3 (fr) 2025-05-15

Similar Documents

Publication Publication Date Title
US5006603A (en) Fiber-reinforced rubber composition and production process and use thereof
EP1474298B1 (fr) Bande de roulement pour pneumatique
US20050171267A1 (en) Tire with component of rubber composition comprised of functionalized styrene/butadiene elastomer, silica and styrene/alpha methylstyrene resin
US10301455B2 (en) Tire comprising a composition comprising a polyfunctional acrylate derivative and a peroxide
CN105283323B (zh) 包含含有由多元羧酸交联的烯属环氧弹性体的橡胶组合物的轮胎
US10421858B2 (en) Rubber composition comprising an epoxide elastomer cross-linked by a polycarboxylic acid
US8148473B2 (en) Sulfur-containing conjugated diolefin copolymer rubber, and rubber composition comprising the same
WO2006054808A1 (fr) Procede pour la fabrication de caoutchouc de polybutadiene et de compositions de caoutchouc
CN107207794A (zh) 环氧化聚丁二烯中的反应性二氧化硅
US20030199626A1 (en) Addition of polar polymer to improve tear strength and processing of silica filled rubber
US20220389202A1 (en) Fortrex additive for low rolling resistance tires
EP3703956B1 (fr) Pneumatique pourvu d'une couche interne a base d'au moins un elastomere isoprenique, une resine renforçante et un sel metallique
JP7731881B2 (ja) シランカップリング剤組成物およびそれを含むゴム組成物
WO2025007008A2 (fr) Compositions pour pneus à faible résistance au roulement
US20040082702A1 (en) Rubber with polyethylene and phenylene bismaleimide and tire with component thereof
KR20170134719A (ko) 중합체의 관능화 방법
WO2024025591A1 (fr) Additif fortrex pour pneus à faible résistance au roulement
TWI623526B (zh) 環狀碳酸酯疊氮化物
WO2019166737A1 (fr) Utilisation de l'oxyde de magnesium pour la reticulation de polymeres
EP3157972A1 (fr) Procede de preparation d'une composition de caoutchouc comprenant un elastomere epoxyde reticule par un poly-acide carboxylique
FR3060012A1 (fr) Pneumatique muni d'une composition comprenant un elastomere dienique, un acrylate de zinc, un peroxyde et un anti-oxydant specifique
KR102947410B1 (ko) 타이어용 고무 조성물 및 그 제조방법
KR102770743B1 (ko) 타이어 트레드용 고무 및 그를 포함한 타이어
WO2025054232A1 (fr) Composition de flanc de pneu
RU2379319C2 (ru) Способ получения полибутадиенового каучука и резиновая композиция

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE