WO2024025591A1 - Additif fortrex pour pneus à faible résistance au roulement - Google Patents

Additif fortrex pour pneus à faible résistance au roulement Download PDF

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Publication number
WO2024025591A1
WO2024025591A1 PCT/US2022/051757 US2022051757W WO2024025591A1 WO 2024025591 A1 WO2024025591 A1 WO 2024025591A1 US 2022051757 W US2022051757 W US 2022051757W WO 2024025591 A1 WO2024025591 A1 WO 2024025591A1
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WIPO (PCT)
Prior art keywords
silane
composition
grafted
tread
additive
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Application number
PCT/US2022/051757
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English (en)
Inventor
Krishnamachari Gopalan
Robert Lenhart
Original Assignee
Cooper-Standard Automotive, Inc.
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Publication date
Application filed by Cooper-Standard Automotive, Inc. filed Critical Cooper-Standard Automotive, Inc.
Publication of WO2024025591A1 publication Critical patent/WO2024025591A1/fr

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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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms

Definitions

  • compositions and additives for making tire treads are provided.
  • a tire tread composition in at least one aspect, includes a base tire tread composition for tire treads and a tread additive composition.
  • the tread additive composition includes an elastomeric component which includes a first silane-grafted polyolefin.
  • the first silane-grafted polyolefin has a density from 0.84 to 0.94 g/cm 3 .
  • the tire tread composition includes one or more additives. Characteristically, the tread additive composition and the one or more additives if present are dispersed within the base composition.
  • a tread additive composition to be combined with a base composition for tire treads or tank track pads to achieve low rolling resistance is provided.
  • the tread additive composition includes an elastomeric component having a first silane-grafted polyolefin elastomer and/or silane-grafted styrene- ethylene-butylene- styrene elastomer.
  • the tread additive can also include one or more additives selected from the group consisting of a polymer carrier, additives that increase tensile strength, a traction enhancer, a reinforcing filler, a 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 antioxidants, a wax, and combinations thereof.
  • a curative agent e.g., sulfur
  • a tread additive composition to be combined with a base composition for tire treads or tank track pads_to achieve low rolling resistance includes an elastomeric component that can include a silane-grafted polyolefin, a first additive component, and a second additive component.
  • the elastomeric component includes a first silane-grafted polyolefin elastomer and/or silane-grafted styrene-ethylene-butylene-styrene elastomer.
  • the reinforcing component includes a polymer carrier, a reinforcing filler, silane-terminated liquid polybutadienes, and one or more process aids.
  • the second additive component includes a butadiene rubber, a hydrocarbon resin, sulfur; and one or more accelerators.
  • the tread additive composition can decrease rolling resistance, improve fuel economy and improve abrasion resistance for extended tire life when combined with a base composition for tire treads as compared to treads formed from the base composition for tire treads without the tread additive composition.
  • a tire tread composition for forming tire treads or tank track pads includes the tread additive composition set forth herein and a base composition for tire treads.
  • a tire tread is fabricated by forming the tire tread composition of into tire treads and then curing the tread composition.
  • the tire tread composition for forming tire treads includes the tread additive composition set forth herein and a base composition for tire treads.
  • a tread additive composition to be combined with a base composition for tire treads or tank track pads to achieve low rolling resistance.
  • the tread additive composition includes an elastomeric component that includes a first silane-grafted polyolefin (e.g, a silane-grafted polyolefin elastomer) and one or more additives.
  • the one or more additives include one or more process aids, a curative agent; and one or more accelerators.
  • a tire tread composition includes tread additive composition that includes an elastomeric component that includes a first silane-grafted polyolefin, and a base composition for tire treads.
  • FIGURE 1 Schematic illustration of a pneumatic tire having a tread block made with a tread additive composition that improves rolling resistance.
  • FIGURE 2A Bar chart showing the results of resilience testing.
  • FIGURE 2B Bar chart showing the results of Goodrich Heat build-up experiments.
  • FIGURE 3 Bar chart showing aging results after aging at 100 °C for 72 hrs.
  • FIGURE 4 Spider graph summarizing the comparison between Examples 1-4 with base composition 1.
  • Ri where i is an integer
  • Ri include hydrogen, alkyl, lower alkyl, Ci-6 alkyl, Ce-io aryl, Ce-io heteroaryl, alylaryl (e.g., Ci-s alkyl Ce-io aryl), -NO2, -NH2, -N(R’R”), -N(R’R”R’”) + E- , Cl, F, Br, -CF 3 , -CCI3, -CN, -SO3H, -PO3H2, -COOH, -CO 2 R’, -COR’, -CHO, -OH, -OR’, -O M + , - SO 3 ’M + , -PO 3 M + , -C00 M + , -CF 2 H, -CF 2 R’, -CFH 2 , and -CFR’R” where R’, R” and R’” are Ci-10 alkyl or Ce-18 aryl groups, M + is
  • the term “about” means that the amount or value in question may be the specific value designated or some other value in its neighborhood. Generally, the term “about” denoting a certain value is intended to denote a range within +/- 5% of the value. As one example, the phrase “about 100” denotes a range of 100+/- 5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the invention can be obtained within a range of +/- 5% of the indicated value.
  • the term “and/or” means that either ah or only one of the elements of said group may be present.
  • a and/or B shall mean “only A, or only B, or both A and B”. In the case of “only A”, the term also covers the possibility that B is absent, i.e. “only A, but not B”.
  • the term “one or more” means “at least one” and the term “at least one” means “one or more.”
  • the terms “one or more” and “at least one” include “plurality” and “multiple” as a subset. In a refinement, “one or more” includes “two or more.”
  • the term “substantially,” “generally,” or “about” may be used herein to describe disclosed or claimed embodiments.
  • the term “substantially” may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, “substantially” may signify that the value or relative characteristic it modifies is within + 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic.
  • 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.
  • the term “less than” includes a lower non-included limit that is 5 percent of the number indicated after “less than.”
  • “less than 20” includes a lower non-included limit of 1 in a refinement. Therefore, this refinement of “less than 20” includes a range between 1 and 20.
  • the term “less than” includes a lower non-included limit that is, in increasing order of preference, 20 percent, 10 percent, 5 percent, or 1 percent of the number indicated after “less than.”
  • concentrations, temperature, and reaction conditions e.g., pressure, pH, flow rates, etc.
  • 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.
  • values of the subscripts can be plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures. For example, if CH2O is indicated, a compound of formula C(o.8-i.2)H(i.6-2.4)0(o.8-i.2). In a refinement, values of the subscripts can be plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures. In still another refinement, values of the subscripts can be plus or minus 20 percent of the values indicated rounded to or truncated to two significant figures.
  • ultra-high molecular weight polyethylene means a polyethylene containing extremely long chains, and has a molecular weight of 1 million Daltons or more, typically 2 to 7.5 million Daltons. In a refinement, ultra-high molecular weight polyethylene has a density of at least 0.93
  • high-density polyethylene means a polyethylene having density is at least equal to 0.941 g/cm 3 . In a refinement, high-density polyethylene” has a density from about 0.941 to about 0.960 g/cm 3 .
  • low density polyethylene means polyethylene having a density of 0.880 g/cm 3 or more and less than 0.940 g/cm 3 .
  • 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 additives and 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 includes a base tire tread composition for tire treads and a tread additive composition.
  • the tread additive composition includes an elastomeric component which includes a first silane-grafted polyolefin.
  • the first silane-grafted polyolefin has a density from 0.84 to 0.94 g/cm 3 .
  • the tire tread composition includes one or more additives. Characteristically, the tread additive composition and the one or more additives if present, are dispersed within the base composition.
  • a tread additive elastomeric composition which is combined with the base composition for tire treads or tank track pads to achieve low rolling resistance.
  • 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 styrenebutadiene 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, a 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-benzo thioazole sulfenamide, Diphenyl Guanidine, Thiazole and sulfenamide boosters.
  • the tire tread composition includes one or more additives includes one or more of ethylene vinyl acetate in an amount of 3 to 12 phr; silica in an amount of 1 to 6 phr; silane- terminated liquid polybutadienes in an amount of 0.5 to 5 phr; octadecanoic acid in an amount of 0.01 to 0.5 phr; polyethylene glycol in an amount of 0.01 to 0.5 phr; polybutadiene rubber in an amount of 3 to 12 phr; LSBR in an amount of 3 to 12 phr; a hydrocarbon resin in an amount of 3 to 12 phr; 2,5- bis(tert-butylperoxy)-2,5-dimethylhexane in an amount of 0.5 to 5 phr; sulfur in an amount of 0.1 to 1.5 phr; n-cyclohexyl-2-benzothioazole sulfenamide in an amount of 0.05
  • 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 base e.g., standard
  • 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. In a refinement, the tire tread composition includes the tread additive elastomeric composition in an amount from about 5 to 30 phr. In some refinements, the tire tread composition includes the tread additive elastomeric composition in an amount of at least 1, 5, 7, 10, 12 or 15 phr or at most 60, 50, 40, 35, 30, 25, 20 or 18 phr.
  • the tire tread composition includes the first silane-grafted polyolefin is present in a sufficient amount such that tire tread formed from the tire tread composition has a tensile strength less than about 20 MPa.
  • the tire tread composition includes the first silane grafted polyolefin in an amount from about 5 to 30 phr. In some refinements, the tire tread composition includes the first silane grafted polyolefin in an amount of at least 1, 5, 7, 10, 12, or 15 phr or at most 40, 35, 30, 25, 20 or 18 phr.
  • the one or more additives includes a first additive component and/or a second additive component.
  • the elastomeric component provides the improvement in rolling resistance achieved with the tread additive composition.
  • the first additive component provides mechanical strength and processability to the elastomeric component.
  • the second additive component provides the component necessary for crosslinking and curing the additive elastomeric composition.
  • the tread additive elastomeric composition can decrease rolling resistance, improve fuel economy, and improve abrasion resistance for extended tire life when combined with a base composition for tire treads as compared to treads formed from the base composition for tire treads without the tread additive composition.
  • the tread composition includes from about 35 to 55 weight percent of the base tread composition and about 45 to 30 weight percent of the elastomeric component, 15 to 5 weight percent of the first additive component, and 10 to 2 weight percent of the second additive component.
  • a complete tread composition includes at least about 1 weight percent, 3 weight percent, 5 weight percent, 8 weight percent, 10 weight percent, or 15 weight percent of the first additive component and/or at most about 30 weight percent, 25 weight percent, 18 weight percent, 15 weight percent, 13 weight percent, or 10 weight percent of the first additive component.
  • a complete tread composition includes at least about 0.5 weight percent, 1 weight percent, 1.5 weight percent, 2 weight percent, 2.5 weight percent, 3 weight percent, or 5 weight percent of the second additive component and/or at most about 20 weight percent, 15 weight percent, 13 weight percent, 10 weight percent, 8 weight percent, or 5 weight percent of the first additive component.
  • the silane grafted polyolefin and/or the tread additive elastomeric composition has a density less than 0.94 g/cm 3 .
  • the silane grafted polyolefin has a density of at most in increasing order of preference about 0.94 g/cm 3 , 0.935 g/cm 3 , 0.93 g/cm 3 , 0.925 g/cm 3 , 0.92 g/cm 3 , 0.915 g/cm 3 , 0.910 g/cm 3 , 0.905 g/cm 3 or 0.90 g/cm 3 .
  • the silane grafted polyolefin has a density of at least, in increasing order of preference, about in increasing order of preference, about 0.80 g/cm 3 , 0.89 g/cm 3 , 0.895 g/cm 3 , 0.90 g/cm 3 , 0.905 g/cm 3 , or 0.91 g/cm 3 .
  • the treads formed from the complete tire composition have a Shore A hardness from about 60 to 75 (as determined by ASTM D2240- 15(2021)). In a refinement, the treads formed from the complete tire composition have a Shore A hardness of a least 50, 55, 60, or 65 and/or at most 80, 75, 73, 70 or 68 (as determined by ASTM D2240-15(2021)).
  • the elastomeric component includes a first silane-grafted polyolefin (e.g., an elastomer thereof) and/or a silane-grafted styrene-ethylene-butylene-styrene polymer (e.g., an elastomer thereof such as silane-grafted hydrogenated styrene- ethylene-butylene- styrene elastomer).
  • the first silane-grafted polyolefin is formed from an elastomeric component reaction blend that includes a first polyolefin and a silane crosslinker.
  • the elastomeric component reaction blend is reacted in a reactive extrusion reactor to form the elastomeric component.
  • the elastomeric component is pelletized after extrusion.
  • the elastomeric component reaction blend further includes a first peroxide initiator.
  • the first silane-grafted polyolefin elastomer is an olefin block copolymer.
  • the olefin block copolymer has a density of less than about 0.9 g/cm 3 . Typically, the density is greater than about 0.8 g/cm 3 .
  • the olefin block copolymer has a first melt index less than about 5.
  • the first 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, and combinations thereof.
  • the first 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 silane crosslinker of the elastomeric component reaction blend has the following formula: wherein Ri, R2, and R3 are each independently H or C1-8 alkyl. In a further refinement, Ri, R2, and R3 are each methyl, ethyl, propyl, or butyl. In another refinement, the elastomeric component reaction blend includes at least one additional silane-grafted polyolefin elastomer.
  • the elastomeric component has a glass transition temperature less than -30 °C. Therefore, a complete tread composition is blended with the base tire composition to achieve a glass transition temperature greater than -40 °C (e.g., -40 to 0 °C). Glass transition temperature greater than -20 °C are needed in order to improve the wet traction for the tires at ambient temperatures greater than about 10 °C.
  • the elastomeric component has a compression set of from about 5.0% to about 35.0%, as measured according io ASTM D 395 (22 hrs @80° C.).
  • a tread additive elastomeric composition to be combined with a base composition for tire treads or tank track pads to achieve low rolling resistance is provided.
  • 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 includes a first additive component and a second additive component.
  • the elastomeric component provides the improvement in rolling resistance achieved with the tread additive composition.
  • the first additive component provides mechanical strength and processability to the elastomeric component.
  • the second additive component provides the component necessary for crosslinking and curing the additive elastomeric composition.
  • the tread additive elastomeric composition can decrease rolling resistance, improve fuel economy and improve abrasion resistance for extended tire life when combined with a base composition for tire treads as compared to treads formed from the base composition for tire treads without the tread additive composition.
  • the one or more additives include one or more additives selected from the group consisting of polymer carriers, reinforcing fillers, silane-terminated liquid polybutadienes, one or more process aids, butadiene rubbers, hydrocarbon resins, peroxides, curatives (e.g., sulfur), accelerators (e.g., for crosslinking - sulfur crosslinking), reinforcing fillers, wax, antioxidant, silane- terminated liquid polybutadienes, one or more process aids, and combinations thereof.
  • curatives e.g., sulfur
  • accelerators e.g., for crosslinking - sulfur crosslinking
  • reinforcing fillers wax, antioxidant, silane- terminated liquid polybutadienes, one or more process aids, and combinations thereof.
  • the one or more additives includes any combination of polymer carriers, a reinforcing filler, wax, antioxidant, silane-terminated liquid polybutadienes, one or more process aids, butadiene rubbers, hydrocarbon resins, peroxides, curatives (e.g., sulfur), accelerators for crosslinking (e.g., sulfur crosslinking), reinforcing fillers, silane-terminated liquid polybutadienes, one or more process aids, and combinations thereof. It should be appreciated that one more examples of each component can be used in the at least one additive component.
  • the one or more additives components includes one or more process aids, a curative agent, and one or more accelerators.
  • a first additive component includes one or more of a polymer carrier, a reinforcing filler, silane-terminated liquid polybutadienes, and one or more process aids.
  • the first additive component includes any combination of a polymer carrier, a reinforcing filler, silane-terminated liquid polybutadienes, and one or more process aids.
  • the first additive component includes a polymer carrier, a reinforcing filler, silane-terminated liquid polybutadienes, and one or more process aids.
  • a useful reinforcing filler is silica.
  • process aids include but are not limited to stearic acid, octadecanoic acid, polyethylene glycol, and any combinations thereof.
  • the polymer carrier is an ethylene vinyl acetate or an ethylene vinyl acetate copolymer.
  • the ethylene vinyl acetate copolymer has a vinyl acetate content from about 10 to 50 mole percent.
  • the ethylene vinyl acetate copolymer has a vinyl acetate content of at least 5 mole percent, 10 mole percent, 15 mole percent, 20 mole percent, or 25 mole percent.
  • ethylene vinyl acetate copolymer has a vinyl acetate content of at most 60 mole percent, 50 mole percent, 40 mole percent, 35 mole percent, or 30 mole percent.
  • a second additive component includes an additive selected from the group consisting of butadiene rubbers, hydrocarbon resins, an optional second peroxide, curatives (e.g., sulfur), and one or more accelerators (e.g. for sulfur crosslinking), and combinations thereof.
  • process accelerators include but are not limited to N-cyclohexyl-2-benzo thioazole sulfenamide and diphenyl guanidine.
  • the second additive component includes an additive selected from the group consisting of butadiene rubbers, hydrocarbon resins, an optional second peroxide, curatives (e.g., sulfur), and one or more accelerators (e.g. for sulfur crosslinking), and combinations thereof.
  • the tread additive elastomeric composition allows for a dual curing system.
  • the sulfur formed sulfur bridges within the polymer in the base composition.
  • the presence of peroxide forms carbon-carbon bonds in the polymers in the tread additive elastomeric composition and in the polymer in the base composition.
  • the first silane-grafted polyolefin elastomer is present in an amount from about 40 to 85 weight percent of the total weight of the tread additive composition; the linear, non-reactive polydimethylsiloxane is present in an amount from about 0.005 to 0.3 weight percent of the total weight of the tread additive composition; the polymer carrier is present in an amount from about 5 to 20 weight percent of the total weight of the tread additive composition; the reinforcing filler is present in an amount from about 1 to 10 weight percent of the total weight of the tread additive composition; the silane-terminated liquid polybutadienes is present in an amount from about 1 to 7 weight percent of the total weight of the tread additive composition; the butadiene rubber is present in an amount from about 2 to 15 weight percent of the total weight of the tread additive composition; and sulfur is present in in an amount from about 0.1 to 2 weight percent of the total weight of the tread additive composition.
  • the first silane-grafted polyolefin elastomer is present in an amount of at least about 10 weight percent, 20 weight percent, 25 weight percent, 30 weight percent, 40 weight percent, 45 weight percent, or 50 weight percent of the total weight of the tread additive elastomeric composition and/or at most 90 weight percent, 85 weight percent, 80 weight percent, 75 weight percent, or 70 weight percent of the total weight of the tread additive composition;
  • the linear, non- reactive poly dimethylsiloxane is present in an amount from about 0 weight percent, 0.001 weight percent, 0.003 weight percent, 0.005 weight percent, 0.01 weight percent, 0.05 weight percent, or 0.
  • the polymer carrier is present in an amount of at least 1 weight percent, 2 weight percent, 3 weight percent, 5 weight percent, 8 weight percent, 10 weight percent, 13 weight percent, and 15 weight percent of the total weight of the tread additive elastomeric composition and/or at most 30 weight percent, 25 weight percent, 22 weight percent, 20 weight percent, 18 weight percent, 15 weight percent, or 13 weight percent, of the total weight of the tread additive composition;
  • the reinforcing filler is present in an amount from about 0.5 weight percent, 1 weight percent, 1 weight percent, 3 weight percent, 5 weight percent, 7 weight percent, or 10 weight percent, of the total weight of the tread additive elastomeric composition and/or at most 30 weight percent, 25 weight percent, 20 weight percent, 18 weight percent, 15 weight percent, 12 weight percent, or 10 weight percent
  • the antioxidant is present in an amount from about 0.001 to 0.3 weight percent of the total weight of the tread additive composition.
  • the one or more process aids are present in an amount from about 0.01 to 2 weight percent of the total weight of the tread additive composition.
  • the one or more accelerator in an amount from about 0.1 to 2 weight percent of the total weight of the tread additive composition.
  • the first peroxide initiator is present in an amount from about 0.005 to 0.3 weight percent of the total weight of the tread additive elastomeric composition and the second peroxide initiator is present in an amount from about 0.5 to 7 weight percent of the total weight of the tread additive composition.
  • the silane-grafted polyolefin is present in an amount from about 30 to about 80 wt % of the total weight of the tread additive composition
  • activators are present in an amount from about 6 to about 18 wt % of the total weight of the tread additive composition
  • wax is present in an amount from about 1 to about 12 wt % of the total weight of the tread additive composition
  • antioxidants are present in an amount from about 1 to about 12 wt % of the total weight of the tread additive composition
  • hydrocarbon resin is present in an amount from about 3 to about 18 wt % of the total weight of the tread additive composition
  • curatives are present in an amount from about 1 to about 10 wt % of the total weight of the tread additive composition
  • accelerators are present in an amount of at least 1 weight percent, 3 weight percent, 6 weight percent, 10 weight percent, or 12 weight percent of the total weight of the tread additive elastomeric composition and/or at most 30 weight percent, 25 weight percent, 20 weight percent, 18 weight percent,
  • the silane-grafted polyolefin is present in an amount of at least about 10 weight percent, 20 weight percent, 25 weight percent, 30 weight percent, 40 weight percent, 45 weight percent, or 50 weight percent of the total weight of the tread additive elastomeric composition and/or at most 90 weight percent, 85 weight percent, 80 weight percent, 75 weight percent, or 70 weight percent of the total weight of the tread additive composition; activators are present in an amount of at least 1 weight percent, 2 weight percent, 5 weight percent, 7 weight percent, or 10 weight percent of the total weight of the tread additive elastomeric composition and/or at most 30 weight percent, 25 weight percent, 20 weight percent, 180 weight percent, or 15 weight percent of the total weight of the tread additive composition; wax is present in an amount of at least Oweight percent, 0.5 weight percent, 1 weight percent, 2 weight percent, or 5 weight percent of the total weight of the tread additive elastomeric composition and/or at most about 25 weight percent, 20 weight percent, 18 weight percent, 15 weight percent
  • the first silane- grafted polyolefin is present in an amount from about 30 to about 80 wt % of the total weight of the tread additive composition
  • the one or more process aids are present in an amount from about 6 to about 18 wt % of the total weight of the tread additive composition
  • the curative agent is present in an amount from about 1 to about 10 wt % of the total weight of the tread additive composition
  • the one or more accelerators are present in an amount from about 6 to about 18 wt % of the total weight of the tread additive composition.
  • the one or more additives further include a hydrocarbon resin, one or more antioxidants, and a wax.
  • the hydrocarbon resin is present in an amount from about 3 to about 18 wt % of the total weight of the tread additive composition
  • the one or more antioxidants are present in an amount from about 1 to about 12 wt % of the total weight of the tread additive composition
  • the wax is present in an amount from about 1 to about 12 wt % of the total weight of the tread additive composition.
  • the first silane-grafted polyolefin elastomer and/or the at least one additional silane-grafted polyolefin elastomer is selected from the group consisting of silane-grafted ethylene/oc-olefin copolymers silane-grafted olefin block copolymers, and combinations thereof.
  • the first silane-grafted polyolefin (e.g., elastomer) and/or the at least one additional silane-grafted polyolefin (e.g., elastomer) is selected from the group consisting of silane-grafted olefin homopolymers, silane-grafted blends of homopolymers, silane-grafted copolymers of two or more olefins, silane-grafted blends of copolymers of two or more olefins, and a combination of olefin homopolymers blended with copolymers of two or more olefins.
  • the first silane-grafted polyolefin (e.g., elastomer) and/or the at least one additional silane-grafted polyolefin (e.g., elastomer) are each independently a silane- grafted homopolymer or silane-grafted copolymer of an olefin selected from the group consisting of ethylene, propylene, 1-butene, 1-propene, 1-hexene, 1-octene, C9-I6 olefins, and combinations thereof.
  • the first silane-grafted polyolefin (e.g., elastomer) and/or the at least one additional silane-grafted polyolefin (e.g., elastomer) each independently include a silane- grafted polyolefin selected from the group consisting of silane-grafted block copolymers, silane- grafted ethylene propylene diene monomer polymers, silane-grafted ethylene octene copolymers, silane-grafted ethylene butene copolymers, silane-grafted ethylene a-olefin copolymers, silane-grafted 1-butene polymer with ethene, silane-grafted polypropylene homopolymers, silane-grafted methacrylate -butadiene-styrene polymers, silane-grafted polyolefins with isotactic propylene units with random ethylene distribution, silane-grafted
  • the tread additive elastomeric composition can include a first peroxide initiator and a second peroxide initiator.
  • the first and second 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 , 1 ,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,
  • the tread composition includes polybutadiene rubber, natural rubber, solution styrene-butadiene rubber, sulfur coupling agent, and a plurality of additives.
  • a coupling agent is bis(triethoxysilylpropyl) polysulfide.
  • the additives are selected from the group consisting of reinforcing fillers such as silica, carbon black, plasticizer, activators, accelerators, antiozonants, and combinations thereof.
  • activators include stearic acid and zinc oxide.
  • An example of an antiozonant is N-l,3-Dimethylbutyl-N'-phenyl-p-phenylenediamine, a microcrystalline paraffin blend, and combinations thereof.
  • the tire tread composition includes tread additive elastomeric composition that includes an elastomeric component that includes a first silane-grafted polyolefin, and a base composition for tire treads.
  • the elastomeric component further incudes one or more additives. Examples for the tread additive composition, the one or more additives, and the base composition are those set forth above and in the examples.
  • Table 1 provides an exemplary base composition for a tire tread.
  • Tables 2, 3, and 4 provide examples 1-3 of complete tread compositions using the tread additive compositions set forth above.
  • Table 5 provides example 4 which is a that includes polybutadiene rubber, natural rubber, and a solution of styrene-butadiene rubber. It should be appreciated that these compositions can be formulated with values that are plus and minus 20 percent of the indicated values.
  • Table 1 Base Composition for a tire tread.
  • Figure 2 A provides the results of resilience testing.
  • the resilience of the various compounds was tested by using DIN resilience tester (DIN 53512 and ISO 4662) obtained from QMESYS Company Ltd.
  • the hammer of the instrument was allowed to strike the samples ( ⁇ 6 mm thickness) for about 5 times to eliminate internal defects; the values of the remaining hits were recorded.
  • Three samples were tested for each composition, and their results were averaged.
  • the hammer attached to the pendulum strikes the 6 mm thick sample and bounces back, and the bounce back is measured as a %, from the height it was dropped. The higher the bounce back, the higher resilience and lower the rolling resistance.
  • Figure 2B provides the results of Goodrich Heat build-up experiments.
  • Figure 3 A shows the heat build-up due to repetitive compression/relaxation at high speed to simulate the tire tread going through a contact patch (simulating the running of a tire).
  • the ASTM D623, Method A, test method subjects a cylindrical specimen to rapidly oscillating compressive stresses under controlled conditions. The heat build-up is measured, as well as the permanent (compression) set. The conditions used for these tests were: Base temperature: 100°C (212°F) Length of stroke: 4.45 mm (0.175 in) Static load: 244.6 N (55 Ibf) Conditioning time: 20 min. Running time: 25 and 60 minutes. A lower temperature rise is better for the tire and is proportional to the resilience and rolling resistance. The samples are taken after the test and measured for the permanent set and again, lower the set is better.
  • Figure 3 provides a bar chart showing aging results after aging at 100 °C for 72 hrs. Adding the additives of this invention, improves the heat aging performance of the control compound with higher tensile, minimum loss of elongation and minimal gain in modulus, after heat aging. This improvement in heat aging will provide a consistent performance of the tire over a period of time.
  • Figure 4 provides a spider graph summarizing the comparison between Examples 1-4 with base composition 1.
  • examples 1-4 show better fuel economy, winter traction, dry handing, and DIN.
  • Table 7 provides weight percentages for additional tire additive compositions.
  • Table 8 provides weight compositions of tire compositions with a base tire composition and the additive compositions of Table 7.
  • Table 9 provides PHR values for tire compositions a base tire composition combined with the additive compositions of Table 7. It should be appreciated that these compositions can be formulated with values that are plus and minus 20 percent of the indicated values.
  • Table 7. Weight percentages for additional tire additive compositions.
  • Table 8 Weight percentages for tire compositions a base tire composition combined with the additive compositions of Table 7.

Abstract

Une composition de bande de roulement de pneu comprend une composition de bande de roulement de pneu de base pour bandes de roulement de pneu et une composition d'additif de bande de roulement. La composition d'additif de bande de roulement comprend un composant élastomère qui comprend une première polyoléfine greffée au silane. Dans un perfectionnement, la première polyoléfine greffée au silane a une densité de 0,84 à 0,94 g/cm3. Dans un autre perfectionnement, la composition de bande de roulement de pneu comprend un ou plusieurs additifs. De manière caractéristique, la composition d'additif de bande de roulement et le ou les additifs s'ils sont présents sont dispersés dans la composition de base.
PCT/US2022/051757 2022-07-25 2022-12-04 Additif fortrex pour pneus à faible résistance au roulement WO2024025591A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080167421A1 (en) * 2005-07-11 2008-07-10 Selim Yalvac Silane-Grafted Olefin Polymers, Compositions and Articles Prepared Therefrom, and Methods For Making the Same
KR100869904B1 (ko) * 2007-09-21 2008-11-24 금호타이어 주식회사 내마모 성능이 향상된 타이어 트레드용 고무 조성물
US20120059121A1 (en) * 2009-04-30 2012-03-08 Michael Backer Elastomer Compositions Modified By Silanes
US20190184744A1 (en) * 2017-12-19 2019-06-20 The Goodyear Tire & Rubber Company Tire with tread to promote wet traction and reduce rolling resistance
US20210230403A1 (en) * 2018-05-24 2021-07-29 Exxonmobil Chemical Patents Inc. Propylene Ethylene Diene Terpolymer Polyolefin Additives for Improved Tire Tread Performance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080167421A1 (en) * 2005-07-11 2008-07-10 Selim Yalvac Silane-Grafted Olefin Polymers, Compositions and Articles Prepared Therefrom, and Methods For Making the Same
KR100869904B1 (ko) * 2007-09-21 2008-11-24 금호타이어 주식회사 내마모 성능이 향상된 타이어 트레드용 고무 조성물
US20120059121A1 (en) * 2009-04-30 2012-03-08 Michael Backer Elastomer Compositions Modified By Silanes
US20190184744A1 (en) * 2017-12-19 2019-06-20 The Goodyear Tire & Rubber Company Tire with tread to promote wet traction and reduce rolling resistance
US20210230403A1 (en) * 2018-05-24 2021-07-29 Exxonmobil Chemical Patents Inc. Propylene Ethylene Diene Terpolymer Polyolefin Additives for Improved Tire Tread Performance

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