WO2021126691A1 - Composés pour bande de roulement de pneumatique - Google Patents

Composés pour bande de roulement de pneumatique Download PDF

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Publication number
WO2021126691A1
WO2021126691A1 PCT/US2020/064484 US2020064484W WO2021126691A1 WO 2021126691 A1 WO2021126691 A1 WO 2021126691A1 US 2020064484 W US2020064484 W US 2020064484W WO 2021126691 A1 WO2021126691 A1 WO 2021126691A1
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Prior art keywords
rubber
phr
sbr
mpa
compound
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PCT/US2020/064484
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English (en)
Inventor
Alan A. Galuska
Xiao-Dong Pan
Alexander V. ZABULA
Mika L. SHIRAMIZU
Yong Yang
Carlos R. LOPEZ-BARRON
Edward J. Blok
Lubin Luo
Mark K. Davis
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Exxonmobil Chemical Patents. Inc.
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Publication of WO2021126691A1 publication Critical patent/WO2021126691A1/fr

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    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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

Definitions

  • the present disclosure relates to tire tread compounds comprising an immiscible blend of high trans-content cyclopentene rubber and another rubber, such as butadiene rubber, styrene-butadiene rubber, and/or natural rubber.
  • the present disclosure relates to tire tread compounds.
  • the rubber compound is the most important component in a tire that dictates wear, traction, and rolling resistance. It is a technical challenge to deliver excellent traction and low rolling resistance while providing good tread wear. The challenge lies in the trade-off between wet traction and rolling resistance/tread wear. More specifically, raising the compound glass transition temperature (Tg) would provide good wet traction, but at the same time, increase the rolling resistance and tread wear. There are needs to develop a rubber compound that can provide wet traction without lowering the rolling resistance and tread wear.
  • Tg compound glass transition temperature
  • references of interest include: US Pat. Nos. 5,120,779; 8,227,371; 8,604,148; 8,889,786; 8,889,806; 9,708,435; and 10,072,101; US Pat. App. Pub. Nos. 2002/0166629, 2009/0192277; 2012/0077945; 2013/0041122; 2016/0002382; 2016/0289352; 2017/0233560; 2017/0247479, 2017/0292013; 2018/0244837; and EP Pat. No. 2524935 Bl.
  • the present disclosure relates to tire tread compounds comprising an immiscible blend of high trans-content cyclopentene rubber and another rubber, such as butadiene rubber (BR), styrene-butadiene rubber (SBR), and/or natural rubber (NR).
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • NR natural rubber
  • the present disclosure includes is a rubber compound comprising: a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr of a high trans content ring-opening rubber comprising cyclopentene and a comonomer and having a trans content of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene rubber (BR), a styrene-butadiene rubber (SBR), and/or natural rubber (NR) that is immiscible with the high trans-content ring-opening rubber; c) 0 phr to 20 phr of an additional rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile
  • the present disclosure also includes a tire comprising the foregoing rubber compound.
  • the rubber compound may be in the sidewall of the tire and/or the tread of the tire.
  • the present disclosure also includes a method comprising: i) compounding components to produce a rubber compound, the components comprising: a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr of a high trans-content ring-opening rubber comprising cyclopentene and a comonomer and having a trans content of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene rubber (BR), a styrene-butadiene rubber (SBR), and/or a natural rubber (NR) that is immiscible with the high trans-content ringopening rubber; c) 0 phr to 20 phr of a rubber selected from the group consisting of polyisoprene rubber (IR), styrene-
  • Figure 1 is an example van Gurp-Palmen (vGP) plot of a linear CPR and a long chain branching CPR.
  • Figure 2A (FIG. 2A) and Figure 2B (FIG 2B) are gel permeation chromatography (GPC) plots for a linear CPR and a long chain branching (LCB) CPR, respectively.
  • GPC gel permeation chromatography
  • Figure 3 is a plot of land as a function of temperature from the dynamic mechanical temperature testing of the tread compounds.
  • Figure 4 is a plot of representative of engineering stress versus strain for the tested compounds.
  • Figure 5 is a plot of land as a function of temperature from the dynamic mechanical temperature ramp testing for the tested compounds.
  • Figure 6 is a plot of representative of engineering stress versus strain for the tested compounds.
  • Figure 7 is a plot of tand as a function of temperature from the dynamic mechanical temperature ramp testing for the tested compounds.
  • Figure 8 is a plot of representative of engineering stress versus strain for the tested compounds.
  • FIG. 9 is a plot of tand as a function of temperature from the dynamic mechanical temperature ramp testing for the tested compounds.
  • the present disclosure relates to tire tread compounds having an immiscible blend of high trans-content cyclopentene rubber (CPR) and another rubber like butadiene rubber (BR) and/or styrene-butadiene rubber (SBR).
  • CPR cyclopentene rubber
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • the trans-content of the CPR should be greater than about 35%.
  • the CPR can optionally also contain a small amount of co monomer (e.g., dicyclopentadiene (DCPD)) for formation of long-chain branching to improve the processability of the rubber compound.
  • DCPD dicyclopentadiene
  • the rubber compound described herein may be used for the production of treads for any type of rubber tires (e.g., passenger automobile tires, truck tires, motorcycle tires, and the like).
  • the tires typically comprise an outer surface having a tread portion and sidewalls.
  • the rubber compound described herein may be used to produce at least a part of the tread portion or sidewall.
  • an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • alkene is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a “polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • copolymer includes terpolymers and the like. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole% propylene derived units, and so on.
  • the term “immiscible” when describing rubbers refers to compositions that form phase-separated domains when melt blended and cooled to room temperature. Further, an immiscible blend can be identified where the T g of each phase is clearly distinguishable.
  • Shore A (avg) hardness is determined according to ASTM D 2240 (15 sec delay). [0024] The glass transition temperature (T g ) is measured by ASTM E1356-08(2014) with a ramping rate of 10°C/min.
  • the mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units can be determined using 3 ⁇ 4 NMR where the different chemical shift of a hydrogen atom can be associated with each comonomer. Then, the relative intensity of the NMR associated with said hydrogens provides a relative concentration of each of the comonomers.
  • the ratio of cis to trans in a polymer can be determined by 13 C NMR using the relevant olefinic resonances. A carbon in a configuration has a smaller NMR chemical shift than a carbon in a trans configuration.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight.
  • the molecular weight distribution, molecular weight moments (Mw, Mn, Mw/Mn) and long chain branching indices were determined by using a Polymer Char GPC-IR (gel permeation chromatography-infrared), equipped with three in-line detectors, a 18-angle light scattering (“LS”) detector, a viscometer and a differential refractive index detector (“DRI”). Three Agilent PLgel 10 pm Mixed-B LS columns were used for the GPC tests herein. The nominal flow rate was 0.5 mL/min, and the nominal injection volume was 200 pL. The columns, viscometer and DRI detector were contained in ovens maintained at 40°C.
  • GPC-IR gel permeation chromatography-infrared
  • THF tetrahydrofuran
  • BHT butylated hydroxytoluene
  • the conventional molecular weight was determined by combining universal calibration relationship with the column calibration which was performed with a series of monodispersed polystyrene (PS) standards ranging from 300 g/mole to 12,000,000 g/mole.
  • PS monodispersed polystyrene
  • M molecular weight
  • the LS molecular weight, M, at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering and determined using the following equation:
  • AR( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • “c” is the polymer concentration determined from the DRI analysis
  • A2 is the second virial coefficient
  • P( ⁇ ) is the form factor for a mono-disperse random coil
  • ⁇ ] avg, of the sample was calculated using the following equation: where the summations are over the chromatographic slices, i, between the integration limits.
  • the branching index (g’ vis or simply g’) is defined as the ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight.
  • the branching index g' is defined mathematically as: [0034]
  • the M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • the Mark-Houwink parameters "a" and "K” are 0.725 and 0.000291.
  • Melt index ratio is the high load melt index of the polymer measured at 190°C and 21.6 kg load per ASTM D1238-13 (121) divided by the melt index of the polymer measured at 190°C and 2.16 kg load per ASTM D1238-13 (12).
  • Dynamic properties (storage modulus (G’) and energy loss (land)) were determined via dynamic temperature ramp testing at 10 Hz and at the heating rate of 2°C/min with an Advanced Rheometric Expansion System (ARES) from Rheometric Scientific, Inc. Such testing employed a torsional rectangular geometry. The strain amplitude was at 0.20% below 0°C (or 10°C) while it was raised to 2.0% at and above 0°C (or 10°C). Six data points were collected per minute, and all tests ended at 100°C.
  • G storage modulus
  • Land energy loss
  • Stress/strain properties (tensile strength, elongation at break, modulus values (Modl00%, MOD200%, MOD300%), energy at break) were measured at room temperature using an Instron 4202 or an Instron Series IX Automated Materials Testing System 6.03.08. Tensile strength measurements were made at ambient temperature; the specimens (dumb-bell shaped) had a width of 4.0 mm and a length of 16 mm length (between two tabs). Though the thickness of the test specimen was a nominal 2.00 mm, the thickness of the specimens varied and was measured manually by a Mitutoyo Digimatic Indicator connected to the system computer. The specimens were pulled at a crosshead speed of 20 inches/min (51 cm/min) and the stress/strain data was recorded.
  • a rubber compound described herein may comprise (a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr (or 20 phr to 80 phr, or 30 phr to 70 phr, or 35 phr to 55 phr) of a high trans-content ring-opening rubber comprising cyclopentene-derived units and having a trans content of greater than 20 mol% (or 20 mol% to 65 mol%, or 35 mol% to 65 mol%, or 40 mol% to 60 mol%, or 45 mol% to 55 mol%) and (b) 5 phr to 95 phr (or 20 phr to 80 phr, or 30 phr to 70 phr, or 45 phr to 65 phr) of a butadiene rubber (BR) and/or a styrene-butadiene rubber (SBR), and/or natural rubber (NR) that is immis
  • the rubber compound may also include (c) another rubber and/or (d) additives (e.g., filler, processing oil, and the like).
  • the high trans- content ring-opening rubber is synthesized by a ring-opening metathesis polymerization (ROMP), which involves the formation of polyolefins from the ring opening of one or more cyclic olefin monomers.
  • the cyclic olefin monomers are strained cyclic olefins that react with a ROMP catalyst to open and relieve the strain.
  • the term “monomer” or “comonomer,” as used herein, can refer to the monomer used to form the polymer (i.e., the unreacted chemical compound in the form prior to polymerization) and can also refer to the monomer after it has been incorporated into the polymer, also referred to herein as a “[monomer] -derived unit.”
  • the high /ran.v-content ring-opening rubbers described herein are synthesized with a cyclopentene monomer and one or more additional comonomers.
  • the comonomers may be used to tailor the properties of the high trans-content ring-opening rubber. For example, increasing the long chain branching may improve the processability of the high /ran.v-content ring-opening rubber.
  • Examples of comonomers from which the high trans-content ring-opening rubber may be synthesized may include, but are not limited to, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbomene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, tetracyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbornene- endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbornene-exo-2,3- carboxylic anhydride, and the like, any combination thereof.
  • Such comonomers can be functional monomers that include hydroxy groups (e.g., mono-hydroxynorborne and di-hydroxynorborne) or silane groups (e.g., (triethoxysilyl)-2-norbomene).
  • hydroxy groups e.g., mono-hydroxynorborne and di-hydroxynorborne
  • silane groups e.g., (triethoxysilyl)-2-norbomene
  • the high trans-content ring-opening rubbers described herein comprise cyclopentene-derived units and optionally one or more additional cyclic olefin comonomer-derived units.
  • the high /ran.v-content ring-opening rubbers described herein may have a Mw of 0.5 kDa to 1,000 kDa, or 10 kDa to 1,000 kDa, or 100 kDa to 1,000 kDa, or 250 kDa to 750 kDa, or 250 kDa to 550 kDa.
  • the high /ran.v-content ring-opening rubbers described herein may have a Mn of 0.1 kDa to 500 kDa, or 1 kDa to 250 kDa, or 10 kDa to 250 kDa, or 50 kDa to 250 kDa, or 100 kDa to 500 kDa.
  • the high trans- content ring-opening rubbers described herein may have a MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3. [0048]
  • the high trans- content ring-opening rubbers described herein may have a melt index ratio of 20 or greater (or 20 to 60, or 20 to 40, or 30 to 50, or 40 to 60).
  • the long chain branching can be qualitatively characterized by the analysis of the van Gurp-Palmen (vGP) plot according to the method described by Trinkle et al. (2002) Rheol. Acta., v.41, pg. 103.
  • the vGP plot is a plot of the loss angle versus the magnitude of the complex modulus (
  • complex modulus
  • a linear polymer is characterized by a monotonic decreasing dependence of the loss angle with
  • the level of LCB can be quantified by the GPC method with triple detector via the branching index (g’ vis ) described herein.
  • the high trans-content ring-opening rubbers described herein may have a g' vis of 0.3 to 0.9, 0.3 to 0.8, or 0.3 to 0.5, or 0.4 to 0.8, or 0.5 to 0.9.
  • the BR and/or SBR are immiscible with the high trans- content ring-opening rubber.
  • the Mooney viscosity of the BR as measured at 100°C may be 35 to 70, or 40 to 65, or 45 to 60.
  • the BR may be a high cA-polybutadiene (“cis-BR”).
  • cis-BR high cA-polybutadiene
  • “Cis -polybutadiene” or “high cis -poly butadiene” refers to a BR where 1,4 -cis polybutadiene is used to produce the cis- B R and the cis component in the cis -BR is at least 95%.
  • An example of a commercially available BR is DIENETM 140ND (a high cis BR, available from Firestone Polymers).
  • the BR may be a low cis -polybutadiene like those made with Li catalysts.
  • the BR may also include a variety of functional groups (including but not excluded to silanes, epoxides, amines, amides or combinations of these functional groups) on one or both chain ends, on the polymer backbone, or both on the polymer backbone and chain ends.
  • the SBR may be an emulsion-SBR (E-SBR), a solution SBR (S-SBR), a high styrene rubber (HSR), and the like.
  • the SBR may have a styrene content from 10 wt% to 60 wt%, or 10 wt% to 50 wt%, or 15 wt% to 30 wt%.
  • the SBR may have a vinyl content from 5 wt% to 60 wt%, or 5 wt% to 40 wt%, or 20 wt% to 50 wt%.
  • the SBR may also include a variety of functional groups (including but not excluded to silanes, epoxides, amines, amides or combinations of these functional groups) on one or both chain ends, on the polymer backbone, or both on the polymer backbone and chain ends.
  • functional groups including but not excluded to silanes, epoxides, amines, amides or combinations of these functional groups
  • SBRs examples include, but are not limited to, NIPOL® (a SBR, available from Zeon Corp.) and SBR elastomers available from JSR Corporation, which include JSR 1500 (25 wt% styrene), JSR 1502 (25 wt% styrene), JSR 1503 (25 wt% styrene), JSR 1507 (25 wt% styrene), JSR 0202 (45 wt% styrene), JSR SL552 (25 wt% styrene), JSR SL574 (15 wt% styrene), JSR SL563 (20 wt% styrene), JSR 0051, JSR 0061, or the like.
  • NIPOL® a SBR, available from Zeon Corp.
  • JSR elastomers available from JSR Corporation, which include JSR 1500 (25 wt% styrene), JSR 1502 (
  • the SBR may have a Mooney viscosity at 100°C (ML 1+4, ASTM D1646-17) of from 30 to 120, or 40 to 80.
  • the weight ratio of SBR to BR can be 10:90 to 90:10, or 10:90 to 50:50, or 50:50 to 90:10.
  • Another rubber that is immiscible with the high /ram-content ring-opening rubber can be included in the rubber compound at 1 phr to 20 phr, or 5 phr to 20 phr, or 1 phr to 10 phr, or 10 phr to 20 phr.
  • second rubbers may include, but are not limited to, of natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (including various microstructures such as low cis BR, high cis BR, and high trans BR (turns bond content in butadiene part of 70 to 95%)), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene- acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, acrylic rubber, epichlorohydrin rubber, fluororubber, silicone rubber, ethylene -propylene rubber, urethane rubber, and any combination thereof.
  • NR natural rubber
  • IR polyiso
  • the rubber compounds of the present disclosure contain other components and additives customarily used in rubber compounds, such as effective amounts of other processing aids, pigments, accelerators, cross-linking and curing materials, antioxidants, antiozonants, fillers, and/or clays.
  • fillers include, but are not limited to, calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, aluminum oxide, zinc oxide, starch, wood flour, carbon black, and the like, and any combination thereof.
  • the fillers may be any size and typically range, for example in the tire industry, from about 0.0001 pm to about 100 pm.
  • silica refers to any type or particle size silica or another silicic acid derivative, or silicic acid, processed by solution, pyrogenic, or like methods, including untreated, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicates, fumed silica, and the like.
  • Precipitated silica can be conventional silica, semi-highly dispersible silica, or highly dispersible silica.
  • An example of commercially available silica is ZEOSIL® 1165MP (amorphous precipitated silica, available from Solvay).
  • the clay may be, for example, montmorillonite, nontronite, beidellite, vokoskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, or mixtures thereof, optionally, treated with modifying agents.
  • the clay may contain at least one silicate.
  • the filler may be a layered clay, optionally, treated or pre-treated with a modifying agent such as organic molecules; the layered clay may comprise at least one silicate.
  • the silicate may comprise at least one “smectite” or “smectite-type clay” referring to the general class of clay minerals with expanding crystal lattices.
  • this may include the dioctahedral smectites which consist of montmorillonite, beidellite, and nontronite, and the trioctahedral smectites, which include saponite, hectorite, and sauconite.
  • synthetically prepared smectite-clays are also encompassed.
  • the silicate may comprise natural or synthetic phyllosilicates, such as montmorillonite, nontronite, beidellite, bentonite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite, and the like, as well as vermiculite, halloysite, aluminum oxides, hydrotalcite, and the like. Combinations of any of the above discussed silicates are also contemplated.
  • natural or synthetic phyllosilicates such as montmorillonite, nontronite, beidellite, bentonite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, stevensite, and the like.
  • the layered filler such as the layered clays described above may be modified, such as intercalated or exfoliated by treatment with at least one modifying agent.
  • Modifying agents are also known as swelling or exfoliating agents.
  • they are additives capable of undergoing ion exchange reactions with the cations present at the interlayer surfaces of the layered filler.
  • the modifying agent may be added as an additive to the composition at any stage; for example, the additive may be added to the elastomer, followed by addition of the layered filler, or may be added to a combination of at least one elastomer and at least one layered filler; or the additive may be first blended with the layered filler, followed by addition of the rubber in yet another example.
  • One or more silane coupling agents are used in the rubber compounds of the present disclosure. Coupling agents are particularly desirable when silica is the primary filler, or is present in combination with another filler, as they help bind the silica to the elastomer.
  • the coupling agent may be a bifunctional organosilane crosslinking agent.
  • organicsilane crosslinking agent is any silane coupled filler and/or crosslinking activator and/or silane reinforcing agent known to those skilled in the art including, but not limited to, vinyl triethoxysilane, vinyl-tris-(beta-methoxyethoxy)silane, methacryloylpropyltrimethoxysilane, gamma-amino-propyl triethoxysilane, gamma-mercaptopropyltrimethoxysilane, and the like, and mixtures thereof.
  • the filler may be carbon black or modified carbon black.
  • Examples of carbon black include, but are not limited to, N229, N351, N339, N220, N234, N110 N326, N330, N347, N351, N550, N650, N990, N660, and N762 provided in ASTM D3037-93, ASTM D1510-19, and ASTM D3765-04.
  • the filler may also be a blend consisting of any combination of carbon black, silica, and clay.
  • Fillers may be present in rubber compounds of the present disclosure individually or cumulatively when more than one filler is used in an amount of 10 phr to 100 phr, or 20 phr to 80 phr, or 60 phr to 100 phr.
  • the rubber compounds of the present disclosure and the articles made from those compositions are generally manufactured with the aid of at least one cure package, at least one curative, at least one crosslinking agent, and/or undergo a process to cure the rubber compound.
  • at least one curative package refers to any material or method capable of imparting cured properties to a rubber as is commonly understood in the industry.
  • rubber compounds are crosslinked to improve the mechanical properties of the polymer. Physical properties, performance characteristics, and durability of vulcanized rubber compounds are known to be related to the number (crosslink density) and type of crosslinks formed during the vulcanization reaction.
  • the rubber compounds of the present disclosure may be crosslinked by adding curative agents, for example, sulfur, metals, metal oxides, such as zinc oxide, peroxides, organometallic compounds, radical initiators, fatty acids, and other agents common in the art.
  • curative agents for example, sulfur, metals, metal oxides, such as zinc oxide, peroxides, organometallic compounds, radical initiators, fatty acids, and other agents common in the art.
  • Other known methods of curing that may be used include, peroxide cure systems, resin cure systems, and heat or radiation-induced crosslinking of polymers. Accelerators, activators, and retarders may also be used in the curing process.
  • compositions may be vulcanized (cured) by any suitable means, such as subjecting them to heat or radiation according to any conventional vulcanization process.
  • the amount of heat or radiation needed is that which is required to affect a cure in the composition, and the disclosure is not herein limited by the method and amount of heat required to cure the composition.
  • the vulcanization is conducted at a temperature ranging from 100°C to about 250°C, or 150°C to 200°C, for 1 to 150 minutes.
  • Halogen-containing rubbers may be crosslinked by their reaction with metal oxides.
  • metal oxides include, but are not limited to, ZnO, CaO, and PbO.
  • the metal oxide can be used alone or in conjunction with its corresponding metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.), or with the organic and fatty acids added alone, such as stearic acid, and optionally other curatives, such as sulfur or a sulfur compound, an alkylperoxide compound, diamines, or derivatives thereof.
  • Sulfur is the most common chemical vulcanizing agent for diene-containing rubbers.
  • the sulfur vulcanization system may consist of an activator to activate the sulfur, an accelerator, and a retarder to help control the rate of vulcanization.
  • Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form rubber-soluble complexes that then react with the sulfur to form sulfurating agents.
  • General classes of accelerators include amines, diamines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.
  • Accelerators help control the onset of and rate of vulcanization, and the number and type of crosslinks that are formed. Retarders may be used to delay the initial onset of cure in order to allow sufficient time to process the unvulcanized rubber.
  • the acceleration of the vulcanization process may be controlled by regulating the amount of the acceleration accelerant, often an organic compound.
  • the mechanism for accelerated vulcanization of natural rubber, BR, and SBR involves complex interactions between the curative, accelerator, activators, and polymers. Ideally, the entire available curative is consumed in the formation of effective crosslinks that join together two polymer chains and enhance the overall strength of the polymer matrix.
  • Numerous accelerators are known in the art and include, but are not limited to, the following: stearic acid, diphenyl guanidine (DPG), tetramethylthiuram disulfide (TMTD), benzothiazyl disulfide (MBTS), N-t-butyl-2-benzothiazole sulfenamide (TBBS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), and thioureas.
  • DPG diphenyl guanidine
  • TMTD tetramethylthiuram disulfide
  • MBTS benzothiazyl disulfide
  • TBBS N-t-butyl-2-benzothiazole sulfenamide
  • CBS N-cyclohexyl-2-benzothiazole-sulfenamide
  • thioureas include, but are not limited to, the following: stearic acid, diphenyl guanidine (
  • Curing agents may be present in the rubber compounds of the present disclosure at 0.2 phr to 10 phr, or 0.5 phr to 5 phr, or 0.75 phr to 2 phr.
  • the rubber compounds of the present disclosure may be compounded (mixed) by any conventional means known to those skilled in the art.
  • the mixing may occur in a single step or in multiple stages.
  • the ingredients are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mixing stage.
  • the final curatives are typically mixed in the final stage, which is conventionally called the “productive” mix stage.
  • the productive mix stage the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding non productive mix stage(s).
  • the rubbers, polymer additives, silica and silica coupler, and carbon black, if used, are generally mixed in one or more non-productive mix stages.
  • the terms “non- productive” and “productive” mix stages are well known to those having skill in the rubber mixing art.
  • the carbon black can be added in a different stage from zinc oxide and other cure activators and accelerators.
  • antioxidants, antiozonants, and processing materials are added in a stage after the carbon black has been processed with the rubbers, and zinc oxide is added at a final stage to maximize the compound modulus.
  • mixing with the clays is performed by techniques known to those skilled in the art, wherein the clay is added to the polymer at the same time as the carbon black. Further, additional stages may involve incremental additions of one or more fillers.
  • KADOX® 911 zinc oxide, available from Cary Company
  • antioxidants include, but are not limited to, SANTOFLEXTM 6PPD (No(l,3-dimethylbutyl)-N'-phenyl-p- phenylenediamine antioxidant, available from Eastman Chemical), AGERITE® RESIN D® (polymerized l,2-dihydro-2,2,4-trimethylquinoline antioxidant, available from Vanderbilt Chemicals), and the like.
  • mixing of the components may be carried out by combining the rubber components, filler and clay in any suitable mixing device, such as a two-roll open mill, BRABENDERTM internal mixer, BANBURYTM internal mixer with tangential rotors, Krupp internal mixer with intermeshing rotors, or preferably a mixer/extruder, by techniques known in the art.
  • Mixing may be performed at temperatures up to the melting point of the mbber(s) used in the composition for example, or 40°C to 250°C, or 100°C to 200°C.
  • Mixing should generally be conducted under conditions of shear sufficient to allow the clay to exfoliate and become uniformly dispersed within the rubber(s).
  • Processing aids include isoparaffins, polyalphaolefins (“PAOs”) and polybutenes (a subgroup of PAOs). These three classes of compounds can be described as paraffins, which can include branched, cyclic, and normal structures, and blends thereof. These processing aids can be described as comprising Ce to C200 paraffins in one embodiment, and Cx to C100 paraffins in another embodiment.
  • processing aids can include esters, polyethers, and polyalkylene glycols.
  • Other processing aids may be present or used in the manufacture of the rubber compositions of the invention.
  • Processing aids include, but are not limited to, plasticizers, tackifiers, extenders, chemical conditioners, homogenizing agents and peptizers such as mercaptans, petroleum and vulcanized vegetable oils, mineral oils, paraffinic oils, polybutene aids, naphthenic oils, aromatic oils, waxes, resins, rosins, and the like.
  • processing aids include, but are not limited to, NYTEX® 4700 (naphthenic processing oil, available from Nynas), NOCHEK® 4756A (paraffin wax blend, available from Sovereign Chemicals), and the like.
  • the processing aid is typically present or used in the manufacturing process from 1 phr to 70 phr, or 3 phr to 60 phr, or 5 phr to 50 phr.
  • the energy loss (land) is used as an indicator of potential tire properties like wet traction (land measured at 0°C or -10°C) and rolling resistance (tand measured at 60°C), where higher values indicate better wet traction and lower values indicate better rolling resistance.
  • the storage modulus (G’) measured at 60°C provides an indication of the potential handling of a tire, where higher values indicate better handling.
  • the tensile properties e.g., Modl00%, Mod200%, and Mod300%, each of which are the stress required to elongate the sample by a given percentage
  • the vulcanized rubbers produced from the rubber compounds described herein may have a tand measured at -10°C of 0.40 to 0.70, or 0.45 to 0.65.
  • the vulcanized rubbers produced from the rubber compounds described herein may have a tand measured at 0°C of 0.30 to 0.55, or 0.35 to 0.5.
  • the vulcanized rubbers produced from the rubber compounds described herein may have a tand measured at 60°C of 0.10 to 0.20, or 0.13 to 0.17.
  • the vulcanized rubbers produced from the rubber compounds described herein may have a G’ measured at 0°C of 6 MPa to 10 MPa, or 7 MPa to 9.5 MPa.
  • the vulcanized rubbers produced from the rubber compounds described herein may have a Modl00% measured at room temperature of 3 MPa to 6 MPa, or 4 MPa to 5.5 MPa. [0094] The vulcanized rubbers produced from the rubber compounds described herein may have a Mod200% measured at room temperature of 8.5 MPa to 12 MPa, or 9 MPa to 11.5 MPa. [0095] The vulcanized rubbers produced from the rubber compounds described herein may have a Mod300% measured at room temperature of 14 MPa to 20 MPa, or 16 MPa to 20 MPa. [0096] The vulcanized rubbers produced from the rubber compounds described herein may have a tensile at break measured at room temperature of 15 MPa to 22 MPa, or 17 MPa to 20 MPa.
  • the vulcanized rubbers produced from the rubber compounds described herein may have an elongation at break measured at room temperature of 250% to 400%, or 275% to 350%. [0098] The vulcanized rubbers produced from the rubber compounds described herein may have an energy at break measured at room temperature of 2 J to 6 J, or 3 J to 5 J.
  • a first nonlimiting example embodiment is a rubber compound comprising: a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr of a high transcontent ring-opening rubber comprising cyclopentene and a comonomer and having a (runs content of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene rubber (BR), a styrene-butadiene rubber (SBR), and/or natural rubber (NR) that is immiscible with the high irarw -content ring-opening rubber; c) 0 phr to 20 phr of an additional rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene-acrylonitrile-butadiene copo
  • the first nonlimiting example embodiment may further include one or more of: Element 1: the rubber compound further comprising: f) 0.2 phr to 10 phr of a curing agent; Element 2: wherein the comonomer is selected from the group consisting of: cyclooctene, 1,5- cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbomene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, tetracyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carb
  • combinations include, but are not limited to, Elements 1 and 2 in combination; two or more of Elements 3-7 in combination; Elements 8 and 9 in combination; Element 1 in combination with one or more of Elements 2-9; Element 2 in combination with one or more of Elements 3-9; Element 3 in combination with one or more of Elements 4-9; Element 4 in combination with one or more of Elements 5-9; Element 5 in combination with one or more of Elements 6-9; Element 6 in combination with one or more of Elements 7-9; and Element 7 in combination with one or more of Elements 8-9.
  • a second nonlimiting example embodiment is a tire comprising the mbber compound of the first nonlimiting example embodiment (optionally including one or more of Elements 1-9).
  • the rubber compound may be in the sidewall of the tire and/or the tread of the tire.
  • a third nonlimiting example embodiment is a method comprising: i) compounding components to produce a mbber compound, the components comprising: a) 5 parts per hundred parts of mbber by weight (phr) to 95 phr of a high trans- content ring-opening mbber comprising cyclopentene and a comonomer and having a trans-content of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene mbber (BR), a styrene-butadiene mbber (SBR), and/or a natural mbber (NR) that is immiscible with the high trans-content ring opening mbber; c) 0 phr to 20 phr of a rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isopre
  • the third nonlimiting example embodiment may include one or more of: Element 2, Element 3; Element 4; Element 5; Element 6; Element 7; Element 8; Element 9; Element 10: the method further comprising: ia) molding the rubber compound into at least a portion of a tire after i) compounding and before ii) curing; Element 11: Element 10 and wherein the at least a portion of the tire comprises a sidewall of the tire; Element 12: Element 10 and wherein the at least a portion of the tire comprises a tread of the tire; Element 13: wherein the vulcanized rubber has a land measured at -10°C of 0.40 to 0.70; Element 14: wherein the vulcanized rubber has a land measured at 0°C of 0.30 to 0.55; Element 15: wherein the vulcanized rubber has a tand measured at 60°C of 0.10 to 0.20; Element 16: wherein the vulcanized rubber has a storage modulus (G’
  • Examples of combinations include, but are not limited to, two or more of Elements 2-9 in combination (including the combinations described above); one or more of Elements 2- 9 in combination with one or more of Elements 10-22; Element 10 in combination with Elements 11 and 12; Element 10 (optionally in combination with Elements 11 and 12) in combination with one or more of Elements 13-15; two or more of Elements 13-15 in combination; and two or more of Elements 13-22 in combination.
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.
  • This invention relates to rubber compound compositions comprising: a) 5 phr to 95 phr (or 20 phr to 80 phr, or 30 phr to 70 phr, or 35 phr to 55 phr) of a high /ran.v-content ring-opening rubber comprising cyclopentene and a comonomer and having a /ran.v-content of greater than 20 mol% (or 20 mol% to 65 mol%, or 35 mol% to 65 mol%, or 40 mol% to 60 mol%, or 45 mol% to 55 mol%), wherein the comonomer is selected from the group consisting of: cyclooctene, 1,5- cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbomene, nor
  • the SBR may have a vinyl content from 5 wt% to 60 wt%, or 5 wt% to 40 wt%, or 20 wt% to 50 wt%)), and/or natural rubber (NR) that is immiscible with the high /ran.v-content ring-opening rubber, wherein, when both are present, the SBR and the BR are present at a weight ratio of SBR to BR is 10:90 to 90:10 (or 10:90 to 50:50, or 50:50 to 90:10); c) 0 phr to 20 phr (or 1 phr to 20 phr, or 5 phr to 20 phr, or 1 phr to 10 phr, or 10 phr to 20 phr) of an additional rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copo
  • V a melt index ratio of 20 or greater (or 20 to 60, or 20 to 40, or 30 to 50, or 40 to 60).
  • the invention also relates to a tire comprising the foregoing rubber compound in the sidewall of the tire and/or the tread of the tire.
  • the invention also relates to a method comprising: i) compounding components to produce a rubber compound, the components comprising: a) 5 phr to 95 phr (or 20 phr to 80 phr, or 30 phr to 70 phr, or 35 phr to 55 phr) of a high /ran.v-content ring-opening rubber comprising cyclopentene and a comonomer and having a trans content of greater than 20 mol% (or 20 mol% to 65 mol%, or 35 mol% to 65 mol%, or 40 mol% to 60 mol%, or 45 mol% to 55 mol%), wherein the comonomer is selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene,
  • the SBR may have a vinyl content from 5 wt% to 60 wt%, or 5 wt% to 40 wt%, or 20 wt% to 50 wt%)), and/or natural rubber (NR) that is immiscible with the high /ran.v-content ring-opening rubber, wherein, when both are present, the SBR and the BR are present at a weight ratio of SBR to BR is 10:90 to 90:10 (or 10:90 to 50:50, or 50:50 to 90:10); c) 0 phr to 20 phr (or 1 phr to 20 phr, or 5 phr to 20 phr, or 1 phr to 10 phr, or 10 phr to 20 phr) of an additional rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copo
  • V a melt index ratio of 20 or greater (or 20 to 60, or 20 to 40, or 30 to 50, or 40 to 60); ia) optionally molding the rubber compound into at least a portion of a tire like the sidewall of the tire and/or the tread of the tire; and ii) curing the rubber compound to produce a vulcanized rubber; wherein the vulcanized rubber has one or more of the following properties:
  • V a Modl00% measured at room temperature of 3 MPa to 6 MPa (or 4 MPa to 5.5 MPa);
  • VII a Mod300% measured at room temperature of 14 MPa to 20 MPa (or 16 MPa to 20 MPa);
  • Embodiment Al is a rubber compound comprising: a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr of a high transcontent ring-opening rubber comprising cyclopentene and a comonomer and having a transcontent of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene rubber (BR), a styrene- butadiene rubber (SBR), and/or natural rubber (NR) that is immiscible with the high transcontent ring-opening rubber; c) 0 phr to 20 phr of an additional rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber,
  • Embodiment A2 which is the rubber compound of Embodiment Al, further comprising: f) 0.2 phr to 10 phr of a curing agent.
  • Embodiment A3 which is the rubber compound of Embodiment Al or A2, wherein the comonomer is selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, tetracyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and any combination thereof
  • Embodiment A4 is the rubber compound of Embodiment Al or A2 or A3, wherein the high /ran.v-content ring-opening rubber has a branching index (g’) pf 0.3 to 0.8.
  • the invention also relates to Embodiment A5, which is the rubber compound of Embodiment Al or A2 or A3 or A4, wherein the high /ran.v-content ring-opening rubber has a weight average molecular weight of 0.5 kDa to 1,000 kDa.
  • Embodiment A6 which is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5, wherein the high /ran.v-content ring-opening rubber has a number average molecular weight of 0.1 kDa to 500.
  • Embodiment A7 which is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6, wherein the high /ran.v-content ring-opening rubber has a molecular weight distribution of 1 to 10 kDa.
  • Embodiment A8 is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7, wherein the high /ran.v-content ringopening rubber has a melt index ratio of 20 or greater.
  • Embodiment A9 which is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8, wherein the SBR has a styrene content of 10 wt% to 60 wt%.
  • Embodiment A10 which is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9, wherein the SBR has a vinyl content of 5 wt% to 60 wt%.
  • Embodiment All which is the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10, wherein SBR and BR are present at a weight ratio of SBR to BR is 10:90 to 90: 10.
  • Embodiment A12 which is a tire comprising the rubber compound of the rubber compound of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 or A11.
  • Embodiment A13 which is the tire of Embodiment A 12, wherein a sidewall of the tire comprises the rubber compound.
  • Embodiment A 14 is the tire of Embodiment A12 or A13, wherein a tread of the tire comprises the rubber compound.
  • Embodiment Bl is a method comprising: i) compounding components to produce a rubber compound, the components comprising: a) 5 parts per hundred parts of rubber by weight (phr) to 95 phr of a high /ran.v-content ring-opening rubber comprising cyclopentene and a comonomer and having a trans -content of greater than 20 mol%; b) 5 phr to 95 phr of a butadiene rubber (BR), a styrene-butadiene rubber (SBR), and/or a natural rubber (NR) that is immiscible with the high trans-content ring-opening rubber; c) 0 phr to 20 phr of a rubber selected from the group consisting of polyisoprene rubber (IR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer
  • Embodiment B2 which is the method of Embodiment Bl, further comprising: ia) molding the rubber compound into at least a portion of a tire after i) compounding and before ii) curing.
  • Embodiment B3 is the method of Embodiment B2, wherein the at least a portion of the tire comprises a sidewall of the tire.
  • Embodiment B4 is the method of Embodiment B2 or B3, wherein the at least a portion of the tire comprises a tread of the tire.
  • Embodiment B5 which is the method of Embodiment Bl or B2 or B3 or B4, wherein the vulcanized rubber has a land measured at -10°C of 0.40 to 0.70.
  • Embodiment B6 which is the method of Embodiment B 1 or B2 or B3 or B4 or B5, wherein the vulcanized rubber has a land measured at 0°C of 0.30 to 0.55.
  • Embodiment B7 which is the method of Embodiment Bl or B2 or B3 or B4 or B5 or B6, wherein the vulcanized rubber has a tand measured at 60°C of 0.10 to 0.20.
  • Embodiment B8 is the method of Embodiment Bl or B2 or B3 or B4 or B5 or B6 or B7, wherein the vulcanized rubber has a storage modulus (G’) measured at 0°C of 6 MPa to 10 MPa.
  • Embodiment B9 which is the method of Embodiment B 1 or B2 or B3 or B4 or B5 or B6 or B7 or B8, wherein the vulcanized rubber has a Mod 100% measured at room temperature of 3 MPa to 6 MPa.
  • Embodiment B10 which is the method of Embodiment Bl or B2 or B3 or B4 or B5 or B6 or B7 or B8 or B9, wherein the vulcanized rubber has a Mod200% measured at room temperature of 8.5 MPa to 12 MPa.
  • Embodiment B 11 which is the method of Embodiment Bl or B2 or B3 or B4 or B5 or B6 or B7 or B8 or B9 or B10, wherein the vulcanized rubber has a Mod300% measured at room temperature of 14 MPa to 20 MPa.
  • Embodiment B 12 which is the method of Embodiment B1 or B2 or B3 or B4 or B5 or B6 or B7 or B8 or B9 or B10 or B11, wherein the vulcanized rubber has a tensile at break measured at room temperature of 15 MPa to 22 MPa.
  • Embodiment B 13 which is the method of Embodiment B1 or B2 or B3 or B4 or B5 or B6 or B7 or B8 or B9 or B10 or Bll or B12, wherein the vulcanized rubber has an elongation at break measured at room temperature of 250% to 400%.
  • Embodiment B 14 which is the method of Embodiment B1 or B2 or B3 or B4 or B5 or B6 or B7 or B8 or B9 or B10 or Bll or B12 or B13, wherein the vulcanized rubber has an energy at break measured at room temperature of 2 J to 6 J.
  • CPR cyclopentene ring-opening rubbers
  • CPR 1 The catalyst was formed in situ by adding solid (d-MeC 6 H 4 O) 2 AlCl (1.77 mmol) to a solution of WCk (0.88 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (monomer) (2.64 mol), triethylaluminum (activator) (1.77 mmol), and toluene (900 mL) at 0°C.
  • CPR 2 The catalyst was formed in situ by adding solid (4-MeC 6 H 4 O) 2 AlCl (3.8 mmol) to a solution of WCl 6 (1.9 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (monomer) (3.67 mol), triethylaluminum (activator) (3.8 mmol), and toluene (900 mL) at 0°C. After reaction at 0°C for 3 hours, a solution of BHT (3.8 mmol) in ethanol (50 mL) and toluene (100 mL) was added.
  • CPR 3 The catalyst was formed in situ by first adding 1-hexanol (3.03 mmol) dropwise to the solution of triisobutylaluminum (TIBAL) (3.03 mmol) in toluene (100 mL) at -35 °C. The temperature of the reaction mixture was allowed to rise up to 20°C.
  • TIBAL triisobutylaluminum
  • CPR 4 The catalyst was formed in situ by first adding 1-hexanol (3.03 mmol) dropwise to the solution of triisobutylaluminum (TIBAL) (3.03 mmol) in toluene (80 mL) at -35°C. The temperature of the reaction mixture was allowed to rise up to 20°C. Then, a solution of WCl 6 (1.52 mmol) in toluene (20 mL) was added to the resultant mixture. After stirring for 15 minutes at 20°C to form the catalyst, the resulting mixture was added to a solution containing cyclopentene (monomer) (3.03 mol) at 20°C.
  • TIBAL triisobutylaluminum
  • CPR 5 The catalyst was formed in situ by first adding 1-hexanol (3.03 mmol) dropwise to the solution of triisobutylaluminum (TIBAL) (3.03 mmol) in toluene (80 mL) at -35°C. The temperature of the reaction mixture was allowed to rise up to 20°C. Then, a solution of WCl 6 (1.52 mmol) in toluene (20 mL) was added to the resultant mixture. After stirring for 15 minutes at 20°C to form the catalyst, the resulting mixture was added to a solution containing cyclopentene (monomer) (3.03 mol) at 20°C.
  • TIBAL triisobutylaluminum
  • CPR 6 was synthesize by a similar method as CPR 1-5.
  • CPR6 and linear CPR were analyzed using the GPC method with triple detector.
  • FIG. 2A is GPC plot for the linear CPR
  • FIG. 2B is the GPC plot for CPR 6.
  • the linear polymer has a Mw of 252 kDa, a MWD of 1.38, and a g’ vis of 0.98.
  • CPR 6 has a Mw of 582 kDa, a MWD of 2.29, and a g’ vis of 0.81.
  • All tire tread compounds were prepared with a BRABENDERTM mixer employing a three-stage mixing procedure where components were mixed in a first pass, mixing without component addition occurred in the second pass, and additional components were added and mix in the third pass.
  • each compound was tested for cure behavior with a dynamic mechanical analyzer ATD 1000 (available from Alpha Technologies) or a curemeter MDR 2000 (available from Alpha Technologies). The testing was at 160°C for 45 minutes at 1.67 Hz and 7.0% strain.
  • ATD 1000 available from Alpha Technologies
  • MDR 2000 available from Alpha Technologies
  • the testing was at 160°C for 45 minutes at 1.67 Hz and 7.0% strain.
  • one tensile pad (3.0 inch by 6.0 inch, ⁇ 2.0 mm in thickness) was cured under high pressure in a mold heated at 160°C for a time to 90% cure (tc90) plus 2 minutes. The tc90 time was determined during the cure test for the corresponding compound.
  • Specimens were die-cut out from the tensile pad for each compound for both dynamic temperature ramp testing with an Advanced Rheometric Expansion System (ARES) (available from Rheometric Scientific, Inc.) and tensile testing at room temperature.
  • RAS Advanced Rheometric Expansion System
  • a rectangular strip was die-cut out of the cured tensile pad for dynamic temperature ramp testing at 10 Hz and at the heating rate of 2°C/min with the ARES.
  • Such testing employed a torsional rectangular geometry.
  • the strain amplitude was at 0.20% below 0°C (or 10°C) while it was raised to 2.0% at and above 0°C (or 10°C).
  • Six data points were collected per minute, and all tests ended at 100°C.
  • Micro-dumbbell specimens (according to ISO 37, Type III specimens) were employed for the tensile testing at room temperature. For most compounds, five specimens were tested for each compound. The values for modl00%, mod300%, tensile at break, and elongation at break listed in the tables below were the average values for each quantity of a compound.
  • Example 1 Three compounds were prepared according to Table 2 where an R in parentheses is used to indicate the compound is a reference compound. The properties of the compounds are provided in Table 3.
  • FIG. 3 is a plot of tand as a function of temperature from the dynamic temperature ramp testing for the tested compounds. The tire rolling resistance predictor, land at 60°C, is lowest for Compound 3 made of CPR 1 (82% /ram-content).
  • FIG. 4 is a plot of representative of engineering stress versus strain for the tested compounds. The highest tensile strength is obtained for Compound 3, arising from the strong propensity of strain-induced crystallization for high-trans CPR.
  • Example 2 Three compounds were prepared according to Table 4. The properties of the compounds are provided in Table 5. Table 4 Table 5
  • FIG. 5 is a plot of land as a function of temperature from the dynamic temperature ramp testing for the tested compounds. Only one peak in land appears for Compound 4, indicating a miscible blend of cis-BR and SBR. In contrast, two peaks in land emerges for Compound 5, indicating an immiscible blend of SBR and CPR 1 (82% irans-content).
  • the tire wet traction predictor, land at 0°C (or at -10°C), is obviously higher for Compound 5 made of an immiscible blend.
  • the tire rolling resistance predictor, land at 60°C, is also lower for Compound 5.
  • G’ at 60°C is higher for Compound 5, predicting a good tire handling performance. Therefore, a tread compound made of an immiscible blend of high -trans CPR and SBR can simultaneously improve tire wet traction and tire handling behavior while reduce tire rolling loss.
  • FIG. 6 is a plot of representative of engineering stress versus strain for the tested compounds.
  • the tensile strength is higher for Compound 5, in comparison to that for Compound 4.
  • a higher tensile strength can potentially contribute to a better tire wear resistance.
  • Example 3 Three compounds were prepared according to Table 6 where an R in parentheses is used to indicate the compound is a reference compound. Compounds 6 and 7 were mixed as described above. Both SBR and BR (or CPR) were mixed together from the beginning during the first stage of mixing. Compound 8 was prepared via the so-called Y-mixing. Here for the first stage of mixing, SBR was mixed along with the proportional portion (60%) of all other ingredients while CPR was mixed along with the proportional portion (40%) of all other ingredients in separate batches. In a second stage, mixing was performed with no addition of ingredients. Proper weights from the two batches were then combined for the third stage of mixing. The properties of the compounds are provided in Table 7.
  • FIG. 7 is a plot of tand as a function of temperature from the dynamic temperature ramp testing for the tested compounds.
  • the tire rolling resistance predictor, land at 60°C becomes higher for Compound 8 prepared via Y-mixing, in comparison to that for Compound 7 prepared via regular mixing.
  • both Compounds 7 and 8 still have a lower land at 60°C than that for Compound 6 made of a miscible blend of c/.v-BR and SBR indicating a better tire rolling resistance.
  • FIG. 8 is a plot of representative of engineering stress versus strain for the tested compounds. Both tensile strength and elongation at break are higher for Compound 8 via Y-mixing, in comparison to those for the regularly mixed Compound 7.
  • Example 4 Five compounds were prepared according to Table 8. The properties of the compounds are provided in Table 9. Table 8 Table 9
  • FIG. 9 is a plot of tand as a function of temperature from the dynamic temperature ramp testing for the tested compounds.
  • the tire wet traction predictor land at 0°C (or at -10°C) is obviously higher for Compounds 9 to 12 made of an immiscible (Compounds 10 to 12) or partially compatible/miscible blend (Compound 9).
  • the tire rolling resistance predictor, land at 60°C is also lower for these compounds in comparison to those for Compound 13.
  • G’ at 60°C is higher for Compounds 9 through 12, predicting a better tire handling performance.
  • a tread compound made of an immiscible or partially compatible/miscible blend of CPR and SBR can simultaneously improve tire wet traction and tire handling behavior while reduce tire rolling loss.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un composé de caoutchouc qui comprend a) 5 à 95 phr d'un caoutchouc à ouverture de cycle à teneur élevée en trans comprenant du cyclopentène et un comonomère et ayant une teneur en trans supérieure à 20 % en moles; b) 5 à 95 phr d'un caoutchouc butadiène (BR), d'un caoutchouc styrène-butadiène (SBR) et/ou d'un caoutchouc naturel (NR) qui est non miscible avec le caoutchouc à ouverture de cycle à teneur élevée en trans; c) 0 à 20 phr d'un caoutchouc supplémentaire; d) 10 à 100 phr d'une charge; et e) 0 à 70 phr d'un auxiliaire de traitement.
PCT/US2020/064484 2019-12-16 2020-12-11 Composés pour bande de roulement de pneumatique WO2021126691A1 (fr)

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