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WO2025038257A1 - Compositions d'élastomères et procédés associés - Google Patents

Compositions d'élastomères et procédés associés Download PDF

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Publication number
WO2025038257A1
WO2025038257A1 PCT/US2024/039235 US2024039235W WO2025038257A1 WO 2025038257 A1 WO2025038257 A1 WO 2025038257A1 US 2024039235 W US2024039235 W US 2024039235W WO 2025038257 A1 WO2025038257 A1 WO 2025038257A1
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Prior art keywords
elastomer
phr
elastomeric
composition
rubber
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English (en)
Inventor
Sunny Jacob
Krishnan Anantha Narayana IYER
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ExxonMobil Technology and Engineering Co
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ExxonMobil Technology and Engineering Co
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Publication of WO2025038257A1 publication Critical patent/WO2025038257A1/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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/283—Iso-olefin halogenated homopolymers or copolymers
    • 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

Definitions

  • the present disclosure relates to elastomer compositions and methods thereof.
  • the spare wheel was considered to be the only universal solution to sudden, irreversible loss of air pressure.
  • recent technological advancements have arisen that could potentially dispense with the need for having a spare tire.
  • the concept of “extended mobility” has been developed and is associated with techniques which allow the vehicle to run on the same tire after being damaged.
  • this concept comes with some limitations. For example, once damaged, the tire would not be able to traverse to a point of repair without having to stop. The damaged tire would then have to be changed before travel is to continue.
  • the present disclosure relates to elastomer compositions and methods thereof.
  • an elastomer composition includes a first elastomer and a second elastomer.
  • the first elastomer is a copolymer comprising p-methlystyrene, p- halomethylstyrene, and isobutylene derived repeat units and comprises about 30 phr to about 100 phr of the elastomeric composition.
  • the second elastomer comprises about 30 phr to about 75 phr of the elastomeric composition.
  • an elastomeric network includes a first elastomer, a second elastomer, and a nucleophilic compound.
  • the first elastomer is a copolymer comprising p- methly styrene, p-halomethylstyrene, and isobutylene derived repeat units and comprises about 30 phr to about 100 phr of the elastomeric composition
  • the second elastomer comprises about 30 phr to about 75 phr of the elastomeric composition
  • the nucleophilic compound is a crosslinking agents, the nucleophilic compound comprising about 1.4 phr to about 2.7 phr of the elastomeric compostion.
  • a method of making a tire component includes mixing a first elastomer and a second elastomer to form an elastomer composition in a mixing bowl at about 40 rpm.
  • the first elastomer is a copolymer comprising p-methlystyrene, p-halomethylstyrene, and isobutylene derived repeat units and comprises about 30 phr to about 100 phr of the elastomeric composition.
  • the second elastomer is butyl rubber and comprises about 30 phr to about 75 phr of the elastomeric composition.
  • the method further comprises blending the elastomer composition with a nucleophilic compound to form an elastomeric network.
  • the nucleophilic compound comprises about 1.4 phr to about 2.7 phr of the elastomeric network and the nucleophile to halide ratio is about 1:0.7 to about 1: 1.3.
  • the method further comprises integrating the elastomeric network into one or more components of a tire of a tire.
  • the interpenetrating elastomer networks of the present disclosure can implement an ionomeric network component, thereby providing the material with self-healing capabilities via the breaking and formation of the ion pair aggregations.
  • the ionomeric network possesses dynamic mechanical properties that are comparable to thermoset vulcanizates.
  • the interpenetrating elastomer networks can further implement a second rubber component to provide the material with viscoelastic properties. Such properties allow the material to form a gas impermeable seal if the material were to become damaged and subsequently self-healed.
  • the second rubber component may also be partially crosslinked, so as to provide the interpenetrating elastomeric network with increased mechanical properties.
  • Elastomer refers to a polymer or blend of polymers consistent with the ASTM D 1566 definition: “a material that is capable of recovering from large deformations, and can be, or already is, modified to a state in which it is essentially insoluble, if vulcanized, (but can swell) in a solvent.”
  • Elastomers are often also referred to as rubbers; the term elastomer may be used herein interchangeably with the term rubber.
  • Elastomers may have a melting point that cannot be measured by Differential Scanning calorimetry (DSC) or if it can be measured by DSC is less than 40° C., such as less than 20° C., such as less than 0° C.
  • Elastomers may have a glass transition temperature (Tg) of -50° C. or less as measured by DSC.
  • polymer may be used to refer to homopolymers, copolymers, terpolymers, etc.
  • copolymer is meant to include polymers having two or more monomers. Polymers, in some embodiments, may be produced (1) by mixing all multiple monomers at the same time or (2) by sequential introduction of the different comonomers. The mixing of comonomers may be done in one, two, or possible three different reactors in series and/or in parallel.
  • a polymer when a polymer is referred to as ‘'comprising” a monomer, the monomer is present in the polymer in the polymerized form of the monomer.
  • catalyst components are described as comprising neutral stable forms of the components, it is well understood by one skilled in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • diolefin refers to an unsaturated hydrocarbon having at least two unsaturated bonds between carbon atoms. While normally, a diolefm will have two double bonds, a molecule with additional double bonds or with one or more triple bonds may also function as a diolefin for purposes of the present disclosure.
  • composition refers to a mixture of two or more polymers, optionally including additional materials such as curing agents.
  • a composition can include the components of the compositions and/or reaction product(s) of two or more of the components. Blends may be produced by, for example, solution blending, melt mixing, or compounding in a shear mixer.
  • a composition/blend can be cured to form a “vulcanizate”. The vulcanizate can be used as a tire liner of the present disclosure.
  • the term “monomer” or “comonomer,” as used herein, can refer to the monomer used to form the polymer (z.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”.
  • monomers are discussed herein including C4-C7 isoolefm monomers, non-halogenated alkylstyrene monomers, halogenated sty rene monomers, and diolefin monomers.
  • phr means “parts per hundred parts rubber,” where the “rubber” is the total rubber content of the composition.
  • both the elastomers (such as BIMSM) of the present disclosure and additional rubbers, when present, are considered to contribute to the total rubber content.
  • a composition having 30 parts by weight of elastomer of the present disclosure and 70 parts by weight of a second rubber (e.g., butyl rubber) may be referred to as having 30 phr elastomer and 70 phr second rubber.
  • Other components added to the composition are calculated on a phr basis. That is. addition of 50 phr of oil means, for example, that 50 g of oil are present in the composition for every' 100 g of total rubber. Unless specified otherwise, phr should be taken as phr on a weight basis.
  • Mooney viscosity is the Mooney viscosity' of a polymer or polymer composition.
  • the polymer composition analyzed for determining Mooney viscosity should be substantially devoid of solvent.
  • the sample may be placed on a boiling-water steam table in a hood to evaporate a large fraction of the solvent and unreacted monomers, and then, dried in a vacuum oven overnight (12 hours, 90 °C) prior to testing, or the sample for testing may be taken from a devolatilized polymer (/. ⁇ ?., the polymer post-devolatilization in industrial-scale processes).
  • Mooney viscosity is measured using a Mooney viscometer according to ASTM DI 646- 19, but with the following modifications/clarifications of that procedure.
  • sample polymer is pressed between two hot plates of a compression press prior to testing.
  • the plate temperature is 125 °C+/-10 °C instead of the 50+/- 5 °C recommended in ASTM DI 646- 19, because 50 °C is unable to cause sufficient massing.
  • ASTM DI 646-19 allows for several options for die protection, should any two options provide conflicting results, PET 36 micron should be used as the die protection.
  • ASTM D1646-19 does not indicate a sample weight in Section 8; thus, to the extent results may vary based upon sample weight.
  • Mooney viscosity determined using a sample weight of 21.5+/— 2.7 g in the DI 646-19 Section 8 procedures will govern. Finally, the rest procedures before testing set forth in D1646-19 Section 8 are 23+/- 3 °C for 30 min in air; Mooney values as reported herein are determined after resting at 24+/-3 °C for 30 min in air. Samples are placed on either side of a rotor according to the ASTM D1646-19 test method; torque required to turn the viscometer motor at 2 rpm is measured by a transducer for determining the Mooney viscosity.
  • M Mooney viscosity number
  • L denotes large rotor (defined as ML in ASTM DI 646- 19)
  • 1 is the pre-heat time in minutes
  • 4 or 8 is the sample run time in minutes after the motor starts
  • 125 °C is the test temperature.
  • a Mooney viscosity of 90 determined by the aforementioned method would be reported as a Mooney viscosity of 90 MU (ML, 1+8 @ 125 °C) or 90 MU (ML, 1+4 @ 125 °C).
  • the Mooney viscosity may be reported as 90 MU; in such instance, it should be assumed that the just-described (ML, 1+4 @ 125 °C) method is used to determine such viscosity, unless otherwise noted.
  • a lower test temperature may be used (e.g., 100 °C), in which case Mooney is reported as Mooney Viscosity (ML, 1+8 @ 100 °C), or @ T °C where T is the test temperature.
  • the compositions can be comprised of at least one elastomeric network and can exhibit self-healing and self-sealing behavior.
  • the self-healing and self-sealing compositions comprise a blend of at least one elastomeric network and an additional elastomeric component, where the additional elastomeric component is optionally crosslinked.
  • the at least one elastomeric network participates predominantly in the self-healing behavior of the composition, while the additional elastomeric component participates predominantly in the self-sealing behavior.
  • the physical and rheological properties of the optionally crosslinked additional elastomeric component are considered, as those physical and rheological properties should be tailored to provide the overall composition added mechanical benefit without sacrificing self-sealing properties and efficiency.
  • an elastomer comprises a polymer made up of at least one olefinic monomer.
  • the olefinic monomer is selected from any one or more C4-C14 olefin monomers having at least one unsaturation, such as isoprene, butadiene, 1 -methylbutadiene.
  • an elastomer comprises halogenated butyl rubber.
  • '‘halogenated butyl rubber” refers to both butyl rubber and so-called “star- branched” butyl rubber.
  • the halogenated rubber component is a halogenated copolymer of a C4-C14 isoolefin and a C4-C14 multiolefin.
  • the halogenated rubber component is a blend of a polydiene or block copolymer, and a copolymer of a C4-C14 isoolefin and a conjugated, or a “star-branched” butyl polymer.
  • the halogenated butyl polymer of the present disclosure can thus be described as a halogenated elastomer comprising C4-C14 isoolefin derived units, multiolefin derived units, and halogenated multiolefin derived units, and includes both “halogenated butyl rubber” and so called “halogenated star-branched” butyl rubber.
  • the halogenated butyl rubber is brominated butyl rubber, and in another embodiment is chlorinated butyl rubber.
  • the halogenated butyl or star-branched butyl rubber may be halogenated such that the halogenation is primarily allylic in nature. This is typically achieved by free radical bromination, free radical chlorination, ionic bromination, or by such methods as secondary treatment of electrophilically halogenated rubbers, such as by heating the rubber, to form the allylic halogenated butyl and star-branched butyl rubber. Common methods of forming the allylic halogenated polymer are disclosed by Gardner et al. in U.S. Pat. Nos. 4,632.963, 4.649.178, and 4,703,091.
  • the halogenated butyl rubber is such that the halogenated multiolefin units are primary allylic halogenated units, and wherein the primary allylic configuration is present to at least 20 mole percent (relative to the total amount of halogenated multi olefin) in some embodiments, and at least 30 mole percent in other embodiments.
  • This arrangement can be described by the structure: where X is a halogen, such as chlorine or bromine, and q is a positive integer.
  • a commercial embodiment of the halogenated butyl rubber is Bromobutyl 2222 (Exxon Mobil Corporation) which has a Mooney viscosity of 27 to 37 (ML 1+8 at 125° C., ASTM 1646-17). and the bromine content is 1.8 to 2.2 weight percent relative to the Bromobutyl 2222. Further, cure characteristics of Bromobutyl 2222 are as follows: MH is from 28 to 40 dN m, ML is from 7 to 18 dN m (ASTM D2084-17).
  • Another commercial embodiment of the halogenated butyl rubber is Bromobutyl 2255 (Exxon Mobil Corporation).
  • Examples of isobutylene-isoprene copolymers include EXXONTM BUTYL 065, EXXONTM BUTYL 065 S, EXXONTM BUTYL 365, EXXONTM BUTYL 068, EXXONTM BUTYL 068S, EXXONTM BUTYL 268. EXXONTM BUTYL 268S, or combinations thereof.
  • Examples of non-halogenated and halogenated rubbers are provided in Table 1 (all available from ExxonMobil Chemical Company), where the balance of the composition is isobutylene.
  • an elastomer comprises a polymer made up of at least one non-halogenated sty rene monomer and/or halogenated styrene monomer.
  • the non-halogenated styrene monomer unit is selected from a-methylstyrene. tertbutylstyrene, styrene units substituted in the ortho, meta, or para position with a Ci to C5 alkyl or branched chain alkyl, and combinations thereof.
  • the sty rene monomer is a halogenated sty rene monomer selected from halomethylstyrene, styrene units substituted in the ortho, meta, or para position with a halogenated Ci to C5 alkyd or branched chain alkyl, and combinations thereof wherein the halogen may be chlorine or bromine.
  • the at least one non-halogenated alkylstyrene and/or halogenated alky lsty rene monomers independently comprise about 0.2 mol % to about 20 mol % paraisomer, such as about 0.3 mol % to about 10 mol %, such as about 0.4 mol % to about 7 mol %, such as about 0.5 mol % to about 5 mol %.
  • an elastomer is a copolymer comprising a backbone architecture of at least one of a random copolymer, a block copolymer, an alternating copolymer, or a gradient copolymer. In one or more embodiments, the elastomer is a random copolymer. In one or more embodiments, the elastomer is a block copolymer.
  • an elastomer is random copolymer of at least one C4- C14 isoolefin monomer (e.g., isobutylene), at least one non-halogenated alkydstyrene monomer (e.g., p-methylstyrene), and at least one halogenated alkydstyrene monomer (e.g., p- bromomethydstyrene).
  • non-halogenated alkydstyrene and halogenated alkylstyrene monomers each contain at least 80 wt%, such as at least 90 wt% para-isomer.
  • non-halogenated alkydstyrene and halogenated alkydstyrene monomers each contain about 0.2 mol % to about 20 mol % para-isomer based on the total mol % of alkylstyrene based monomers, such as about 0.3 mol % to about 10 mol %, such as about 0.4 mol % to about 7 mol %, such as about 0.5 mol % to about 5 mol %.
  • elastomers of the present disclosure may contain the following monomer units randomly spaced along the polymer chain: wherein R 10 and R 11 are independently hydrogen, alkyl, such as C1 to C7 alkyl, or primary or secondary alkyl halides and X is a functional group such as halogen. [0035] In some embodiments, R 10 and R 11 are hydrogen. Up to 60 mole percent of the para- substituted styrene present in the elastomer structure may be functionalized, and in other embodiments from 0.1 to 5 mol %. In yet another embodiment, the amount of functionalized para-substituted styrene units of an elastomer is 0.4 to 1 mol %.
  • the functional group X may be halogen or a combination of a halogen and some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides, and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; nitrile; amino and mixtures thereof.
  • These functionalized isoolefin copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in U.S. Pat. No. 5,162,445, and in particular, the functionalized amines as described below.
  • an elastomer is an elastomeric random copolymer of isobutylene, p-methylstyrene, and p-bromomethylstyrene where the p-methylstyrene and the p-bromomethylstyrene are present in a combined amount of 0.2 mol % to about 20 mol%, such as about 0.3 mol % to about 10 mol%, such as about 0.4 mol % to about 7 mol%, such as about 0.5 mol % to about 5 mol%, alternatively about 0.2 to about 40 wt %, alternatively about 0.5 to about 20 wt %.
  • halogenated elastomers are commercially available as EXXPROTM Elastomers (Exxon Mobil Corporation), and abbreviated as “BIMSM.” These elastomers can, if desired, have a substantially homogeneous compositional distribution such that at least about 95% by weight of the polymer has a combined p-methylstyrene and p-bromomethylstyrene content within about 15% of the combined p-methylstyrene and p-bromomethylstyrene content of the overall polymer.
  • an elastomer contains about 0.1 mol % to about 7.5 mol % halogenated alkylstyrene derived units, relative to the combined non-halogenated and halogenated alkylstyrene derived units in the polymer.
  • the amount of halogenated alkylstyrene derived units is about 0.2 mol % to about 3 mol %, such as about 0.3 mol % to about 2.8 mol %, such as about 0.3 mol % to about 2 mol %, such as about 0.4 mol % to about 1 mol %, wherein a desirable range may be any combination of any upper limit with any lower limit.
  • elastomeric copolymers contain about 0.3 wt % to about 4.5 wt % of bromine, based on the weight of the polymer, such as about 0.4 wt % to about 4 wt % bromine, such as about 0.6 wt % to about 1.5 wt % bromine.
  • the elastomer is a copolymer of C 4 to C 14 isoolefin derived units (or isomonoolefin), p-methylstyrene derived units, and p-halomethylstyrene derived units, wherein the p-halomethylstyrene units are present in the elastomer from about 0.4 mol % to about 1 mol % based on the total number of p-methylstyrene and p-halomethylstyrene derived units, and wherein the p-methylstyrene derived units are present from about 3 wt % to about 15 wt % based on the total weight of the polymer, or about 10 wt % to about 12 wt %.
  • the p-halomethylstyrene is p-bromomethylstyrene.
  • the elastomers can further include one or more diolefin monomers, where the C 4 to C 14 isoolefin is not the same as the diolefin.
  • diolefins include isoprene; cis-1,3-pentadiene; trans-1,3-pentadiene; cyclopentadiene; beta- pinene; limonene; or combinations thereof.
  • the diene monomers can be present in the elastomers in an amount of about 0.5 wt % to about 10 wt% of the polymer, such as about 1 wt% to about 8 wt%, such as about 2 wt% to about 5 wt%.
  • an elastomer includes at least one C 4 to C 14 isoolefin- derived monomer present at about 60 wt % to about 99 wt%, at least one non-halogenated alkylstyrene-derived monomer, and at least one halogenated alkylstyrene-derived monomer wherein the cumulative total of halogenated and non-halogentated alkylstyrene derived monomer comprises about 0.5 wt % to about 30 wt % of the elastomer.
  • the at least one halogenated alkylstyrene-derived monomer comprises about 0.1 mol % to about 7.5 mol % of the combined content of the cumulative total of alkylstyrene- derived monomers. In some embodiments, the at least one halogenated alkylstyrene-derived monomer can be present at about 0.5 wt % to about 10 wt %.
  • an elastomer can have a (ML, 1+8 @ 100 °C) Mooney viscosity less than about 65, such as about 20 to about 60, such as about 25 to about 50, such as about 30 to about 45, such as about 32 to about 37.
  • elastomers of the present disclosure can have a molecular weight distribution (MWD) of about 1 to about 5, such as about 1.5 to about 2.5.
  • elastomers can be characterized by a weight average molecular weight of about 2,000 g/mol to about 2,000,000 g/mol, and a number average molecular weight of about 2,500 g/mol to about 750,000 g/mol as determined by gel permeation chromatography.
  • Elastomeric and interpentrating networks Elastomer compositions of the present disclosure can be composed of multiple elastomer components, as have been previously disclosed. Without being bound by theory, blending various elastomer materials into an elastomeric composition allow the operator to tailor various physical and mechanical properties of the overall composition.
  • one or more halogenated elastomers are blended with one or more uncured secondary elastomers (denoted hereinafter as “component B”) to form a blend thereof, wherein the uncured secondary elastomer does not participate in ionomeric network formation.
  • a nucleophilic compound can be blended therewith to induce ionomeric network formation of the one or more halogenated elastomers, thereby forming an interpenetrating network composed of the one or more halogenated elastomers and the one or more uncured secondary elastomers.
  • component A can be represented by pendently a numerical value representing the number of respective repeat units along the polymer backbone.
  • each X is independently either bromine or chlorine.
  • the elastomeric polymer of component A has a number average molecular weight (M n ) of about 500,000 g/mol to about 5,000 g/mol, such as about 300,000 g/mol to about 6,000 g/mol, such as about 200,000 g/mol to about 7,000 g/mol, such as about 150,000 g/mol to about 10,000 g/mol, such as about 100,000 g/mol to about 15,000 g/mol, such as about 15,000 g/mol.
  • M n number average molecular weight
  • the ratio of m to n is about 1:0.7 to about 1:0.3, such as about 1:0.7 to about 1:0.5, such as about 1:0.5. In at least one alternative embodiment, the ratio of m to n is about 1:0.5 to about 1:0.3.In some embodiments, the ratio of m+n to z is about 40:60 to about 5:95, such as about 30:70 to about 10:90, such as about 20:80.
  • the ratio of m+n to z is about 40:60 to about 30:70, alternatively about 30:70 to about 20:80, alternatively about 20:80 to about 10:90, alternatively about 10:90 to about 5:95.
  • the halogenated poly(isobutylene-co-p-methylstyrene) is any one or more commercially available halogenated poly(isobutylene-co-p-methylstyrene), such as Exxpro® 3035, Exxpro® 3433, Exxpro® 3745, and combinations thereof, available from Exxon Mobil Corporation.
  • component A is halogenated butyl rubber or isomer thereof.
  • component A is present in the elastomeric composition at about 100 phr. In one or more embodiments, component A is present in the composition at about 80 phr to about 30 phr, such as about 70 phr to about 30 phr, such as about 60 phr to about 40 phr, such as about 55 phr to about 45 phr.
  • component B is selected from natural rubber, polyisoprene rubber, poly(styrene-co-butadiene) rubber (SBR), polybutadiene rubber (BR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene rubber (EPM), ethylene- propylene-diene rubber (EPDM), polysulfide, nitrile rubber, propylene oxide polymers, halobutyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, ionic butyl rubber, and combinations thereof.
  • SBR poly(styrene-co-butadiene) rubber
  • BR polybutadiene rubber
  • SIBR styrene-isoprene-butadiene rubber
  • EPM ethylene-propylene rubber
  • EPDM ethylene- propylene-diene rubber
  • polysulfide polysulfide
  • nitrile rubber propylene oxide
  • Natural rubbers can include Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20, SMR 50, and combinations thereof, wherein the natural rubbers have a Mooney viscosity at 100 °C (ML 1+4) of about 30 to about 120, such as about 40 to about 65.
  • the Mooney viscosity test referred to herein is in accordance with ASTM D1646-19.
  • Polybutadiene rubber (BR) can have a Mooney viscosity as measured at 100 °C (ML 1+4) of about 35 to about 70, such as about 40 to about 65, such as about 45 to about 60.
  • a desirable rubber is high cis-polybutadiene (cis-BR).
  • cis-polybutadiene or “high cis- polybutadiene,” it is meant that 1,4-cis polybutadiene is used, where the amount of cis component is at least 95%.
  • An example of a high cis-polybutadiene commercial product used in the composition is BUDENETM 1207 (available from Goodyear Chemical).
  • BUDENETM 1207 available from Goodyear Chemical.
  • Secondary rubbers of ethylene and propylene derived units such as EPM and EPDM are also suitable as polymers in component B of the present disclosure. Examples of suitable comonomers in making EPDM are ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene, as well as others.
  • the elastomeric polymer of component B has a number average molecular weight (M n ) of about 300,000 g/mol to about 500 g/mol, such as about 200,000 g/mol to about 7,000 g/mol, such as about 150,000 g/mol to about 10,000 g/mol, such as about 100,000 g/mol to about 15,000 g/mol, such as about 15,000 g/mol.
  • M n number average molecular weight
  • the elastomeric polymer of component B is treated with a peroxide to allow for vis-breaking of the polymer chain.
  • the elastomeric polymer of component B has an Mn of about 150,000 g/mol to about 7000 g/mol, such as about 100,000 g/mol to about 10,000 g/mol, such as about 50,000 g/mol to about 15,000 g/mol.
  • components B is present in the elastomeric composition at about 75 phr to about 30 phr, such as about 60 phr to about 40 phr, such as about 50 phr to about 40 phr.
  • the elastomeric composition includes one or more additives such as fillers, dyes, pigments, antioxidants, heat and light stabilizers, plasticizers, oils, and/or other ingredients.
  • additives include calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, aluminum oxide, starch, wood flour, carbon black (e.g., N110 to N990 per ASTM D1765-17, such as N330 and N660), or combinations thereof.
  • the fillers may be any suitable size, shape, and/or any aggregate size range thereof that is typical for use in the tire industry, such as about 1,000 nm to about 25 nm, such as about 700 nm to about 50 nm, such as about 500 nm to about 100 nm, such as about 300 nm to about 200 nm.
  • fillers can be present within the elastomeric composition at about 10 phr to about 100 phr, such as about 25 phr to about 80 phr, such as about 30 phr to about 70 phr.
  • fillers can be present within the elastomeric composition about 10 phr to about 30 phr.
  • 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.
  • the compositions of the present disclosure may also include clay as a filler.
  • 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.
  • components of the present disclosure include an extender oil.
  • the extender oil can be any suitable extender oil that is capable of extending or plasticizing elastomers.
  • the extender oil is chosen from the group consisting of polyolefin oils, paraffinic oils, naphthelnic oils, aromatic oils, mineral oils, and combinations thereof.
  • extender oil is present within the elastomeric composition at about 100 phr to about 1 phr, such as about 75 phr to about 5 phr, such as about 50 phr to about 10 phr, such as about 30 phr to about 20 phr.
  • the extender oil is a polybutene oil having an Mn of about 100,000 g/mol to about 1,000 g/mol, such as about 75,000 g/mol to about 5,000 g/mol, such as about 50,000 g/mol to about 10,000 g/mol, such as about 30,000 g/mol to about 20,000 g/mol.
  • Mn of about 100,000 g/mol to about 1,000 g/mol, such as about 75,000 g/mol to about 5,000 g/mol, such as about 50,000 g/mol to about 10,000 g/mol, such as about 30,000 g/mol to about 20,000 g/mol.
  • a curing system comprising a nucleophilic compound can be introduced to an elastomeric compostion consisting of a halogen functionalized monomer, such as a halogenated alkylstyrene or a halobutyl rubber, to cause ionic interactions thereby forming an ionomeric network.
  • a halogen functionalized monomer such as a halogenated alkylstyrene or a halobutyl rubber
  • the resulting elastomeric network is the result of ion-pair aggregation.
  • a curing system comprising a nucleophilic species is introduced to the elastomeric composition to induce ionomeric network formation with component A.
  • a nucleophilic compound introduced to an elastomeric composition to form an elastomeric network is one or more of a nitrogen or phosphorus nucleophile.
  • the nucleophilic compound can be represented by A is a nitrogen or phosphorus; and R 1 , R 2 , and R 3 are independently selected from the group consisting of an alkyl substituent, an aryl substituent, a heteroatom, and combinations thereof, wherein: the alkyl substituent is any one or more linear or branched C1-C18 alkyl substituents, the aryl substituent is monocyclic or composed of fused C4-C8 rings, and the heteroatom is selected from B, N, O, Si, P, and S.
  • the appropriate nucleophile will contain at least one neutral nitrogen or phosphorus center, both possessing a lone pair of electrons that are electronically and sterically accessible for participation in nucleophilic substitution reactions.
  • Suitable nucleophiles include trimethylamine, triethylamine, triisopropylamine, tri- n-butylamine, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n- butylphosphine, triphenylphosphine, and combinations thereof.
  • the nucleophilic compound is triphenyl phosphine.
  • nucleophiles include substituted azoles as disclosed in US 2012/0157579, such as N-butyl imidazole, N-(trimethylsilyl)imidazole, N-decyl-2- methylimidazole, N-hydroxyethylimidazole, N-(3-trimethoxysilylpropyl)imidazole, N- vinylimidazole, 2-(imidazol-1-yl)ethyl 2-methyl-2-propenoate, 1-butylbenzimidazole, and combinations thereof.
  • substituted azoles as disclosed in US 2012/0157579, such as N-butyl imidazole, N-(trimethylsilyl)imidazole, N-decyl-2- methylimidazole, N-hydroxyethylimidazole, N-(3-trimethoxysilylpropyl)imidazole, N- vinylimidazole, 2-(imidazol-1-yl)e
  • the amount of nucleophile added to the elastomeric composition is determined based upon the molar equivalence ratio relative to the halide content therein.
  • the nucleophile is added to the elastomeric composition in an molar equivalent ratio of about 2:1 to about 0.1:1, such as about 1.1:1 to about 0.2:1, such as about 0.8:1 to about 0.5:1.
  • the nuclephile is added to the elastomeric composition in a molar equivalent ratio of about 2:1 to about 1.1:1, alternatively about 1.1:1 to about 0.8:1, alternatively about 0.8:1 to about 0.5:1, alternatively about 0.5:1 to about 0.2:1, alternatively about 0.2:1 to about 0.1:1.
  • the nucleophilic composition is added to the elastomeric composition in an amount of about 2.77 phr to about 1.40.5 phr, such as about 5 phr to about 1 phr, such as about 3 phr to about 1.5 phr, such as about 2.1 phr.
  • Blending of component A, component B, fillers, additives, and curing system components may be carried out by combining the desired components and the elastomers of the present disclosure in any suitable mixing device such as a BANBURYTM mixer, BRABENDERTM mixer or an extruder and performed at temperatures of about 70 °C to 120 °C under conditions of shear sufficient to allow the components to become uniformly dispersed within the elastomer to form the elastomeric compositions thereof described herein.
  • any suitable mixing device such as a BANBURYTM mixer, BRABENDERTM mixer or an extruder and performed at temperatures of about 70 °C to 120 °C under conditions of shear sufficient to allow the components to become uniformly dispersed within the elastomer to form the elastomeric compositions thereof described herein.
  • mixing of the components may be carried out by combining the elastomers, 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 a mixer/extruder.
  • Mixing may be performed at temperatures up to the melting point of the elastomer(s) used in the composition in one embodiment, or 40 °C to 250 °C, or 100 °C to 200 °C.
  • Mixing should generally be conducted under conditions of shear sufficient to allow any clay to exfoliate and become uniformly dispersed within the elastomer(s).
  • elastomer or elastomers is first mixed for 20 to 90 seconds, or until the temperature reaches from 40 °C to 75 °C. Then, approximately 75% of the filler, and the remaining amount of elastomer, if any, can be added to the mixer, and mixing continues until the temperature reaches from 90 °C to 150 °C. Next, the remaining filler is added, as well as the processing aids, and mixing continues until the temperature reaches from 140 °C to 190 °C.
  • compositions of the present disclosure may be compounded blended by any conventional means known to those skilled in the art.
  • the mixing may occur in a single stage or in multiple stages.
  • the components are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mixing stage.
  • the curatives are typically mixed in the final stage, which is conventionally called 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 elastomers, secondary 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 resulting elastomeric composition forms a self- healing network via the breaking and reformation of the ion-pairs.
  • the resulting elastomeric network possesses dynamic mechanical properties that are comparable to thermoset vulcanizates. Additionally, both components of the interpenetrating elastomeric network can serve distinct purposes in the instance of the material being punctured or otherwise damaged.
  • the ionomeric network formed from the reaction between component A and the nucleophilic species provides the elastomeric composition a degree of structural integrity through the network structure thereof and gas impermeability, whilst also providing self-healing properties through the breaking and reformation of the ion-pairs.
  • component B provides the elastomeric composition with a degree of viscoelasticity, such that the elastomeric composition is able to form a gas impermeable barrier upon receiving damage and undergoing subsequent self-healing.
  • these and other physical, mechanical, rheological, and chemical properties are able to be provided through careful selection of each component and/or additive input into the composition.
  • the overall composition of the elastomeric network is able to be tuned so as to provide the final material having physical and mechanical properties, and retention thereof upon receiving damage, as a result of the self-healing and self-sealing abilities provided by the composition.
  • the virgin and retained material properties, as a result of self-healing and self-sealing, provide such elastomeric materials viability for implementation into any one or more intended commercial applications.
  • Such commercial applications can include implementation into tire and tire tread compositions, such as a tire innerliner, a tire sidewall, and the like.
  • Elastomeric compositions with two or more curable components [0072]
  • component B of the elastomeric composition comprises a partially crosslinked elastomer.
  • component B is partially crosslinked using any one or more conventional curing agents including sulfur and compounds comprising sulfur, metals, metal oxides such as zinc oxide, peroxides, organometallic compounds, radical initiators, fatty acids, accelerators, any other suitable curing agent and combinations thereof.
  • curing agent refers to the combination of any one or more curative agents.
  • the curing agent of component B is a bisthiosulfate compound.
  • a bisthiosulfate compound can be represented by the formula Z 1 -R 1 -Z 2 , where R 1 is substituted or unsubstituted C1 to C15 alkyl, substituted or unsubstituted C2 to C15 alkenyl, or substituted or unsubstituted C 6 to C 12 cyclic aromatic moiety; and Z 1 and Z 2 are independently a thiosulfate group.
  • R 1 is selected from methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and nonamethylene.
  • Thiosulfate groups can include any suitable countercation, such as an alkali metal countercation, such as sodium or potassium. So-called bisthiosulfate compounds are an example of a class of polyfunctional compounds included in the above formula. A non-limiting example of such polyfunctional curatives is hexamethylene bis(sodium thiosulfate). [0075] Curing systems for composition B can include one or more additional accelerators.
  • Additional accelerators may include mercaptobenzothiazole disulfide (MBTS), stearic acid, diphenyl guanidine (DPG), tetramethylthiuram disulfide (TMTD), N-t-butyl-2-benzothiazole sulfenamide (TBBS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), thioureas, and combinations thereof.
  • MBTS mercaptobenzothiazole disulfide
  • DPG diphenyl guanidine
  • TMTD tetramethylthiuram disulfide
  • TBBS N-t-butyl-2-benzothiazole sulfenamide
  • CBS N-cyclohexyl-2-benzothiazole-sulfenamide
  • thioureas thioureas, and combinations thereof.
  • Metal oxides can act as curing agents for compostion B. Examples of metal oxides
  • metal oxide can be used alone or in conjunction with its corresponding metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.).
  • the organic and fatty acids such as steric acid, may be used alone or optionally with other curatives such as sulfur or a sulfur compound, an alkylperoxide compound, diamines, derivatives thereof, and combinations thereof.
  • the curing system for component B is present in the elastomeric composition in an amount of about 0.1 phr to about 8 phr, such as about 0.5 phr to about 7.5 phr, such as about 1 phr to about 7 phr, such as about 2 phr to about 5.5 phr.
  • In-situ formation of low molecular weight resealing components it may be desired that the elastomeric composition posses a degree of flowability, such that the elastomeric composition exhibits impoved self-sealing properties.
  • oligomer refers to a material having molecular weight significantly lower than the original polymer/rubber.
  • Oligomers are tacky to touch and often are viscous liquids capable of flow.
  • the oligomeric ionomers have attached functional moieties, which can participate and/or facilitate ionic sealing.
  • the functional moiety is one or more of a bromine and chlorine.
  • Most rubbers like natural rubber (NR), nitrile rubber (NBR), styrene-butadiene rubber (SBR), bromobutyl rubber (BIIR), chlorobutyl rubber (CDR), butadiene rubber (BR), etc., crosslink when heated with suitable peroxide and storage modulus (G') increases after cure.
  • NR natural rubber
  • NBR nitrile rubber
  • SBR styrene-butadiene rubber
  • BIIR bromobutyl rubber
  • CDR chlorobutyl rubber
  • BR butadiene rubber
  • the elastomeric composition further comprises about 40 phr to about 10 phr of ionic butyl rubber, and about 3 phr to about 1 phr of peroxide catalyst, which may be incorporated within the composition via either component A or component B.
  • incorporating ionic butyl rubber within the elastomeric composition provides self-sealing and gas impermeable properties.
  • the elastomeric composition comprises at least one compound having at least one peroxide moieties.
  • the peroxide compound can be any one or more of an aliphatic compound, a cycloaliphatic compound, or an aromatic compound.
  • the peroxide compound is any one or more of 2,5- bis(t-butyl peroxy)-2,5-dimethyl hexane, 1,1-di-t-butyl peroxi-3,3,5-trimethyl cyclohexane, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexyne-3, p-chlorobenzyl peroxide, 2,4-dichlorobenzyl peroxide; 2,2-bis-(t-butyl peroxi)-butane, di-t-butyl peroxide; benzyl peroxide, 2,5-bis(t-butyl peroxy)-2,5-dimethyl hexane, dicumyl peroxide, and 2,5-dimethyl-2,5-di(t-)
  • the peroxide compound may be any appropriate commercially available peroxide compound, such as DI-CUP ® Dicumyl Peroxide and/or Luperox ® 101.
  • the elastomeric composition comprises an activating agent, such as 2,2,6,6-tetra alkyl piperidine based hindered amine, which will activate the organoperoxide, and in a sense, enable a reduction in the amount of the organoperoxide to more efficiently degrade the ionomeric network during the formation of the sealant layer.
  • an activating agent such as 2,2,6,6-tetra alkyl piperidine based hindered amine
  • the 2,2,6,6-tetra alkyl piperidine based hindered amine is, for example, a 50/50 mixture of poly[[6-[1,1,3,3,-tetramethylbutyl)amino ]-s-triazine-2,4- diyl][2,2,6,6,-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4- piperidyl)imino]] compound (referred to herein as "PTP") and bis(hydrogenated tallow alkyl), amines oxidized and sold as Irgastab ® FS410 FF from BASF.
  • PTP poly[[6-[1,1,3,3,-tetramethylbutyl)amino ]-s-triazine-2,4- diyl][2,2,6,6,-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4- piperidyl)i
  • peroxide activating agent is a mixture of PTP, bis(hydrogenated tallow alkyl) amines oxidized, and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate sold as Irgastab ® FS811 from BASF.
  • the peroxide activating agent is poly[[6-[1,1,3,3,- tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][2,2,6,6,-tetramethyl-4-piperidyl)imino]-1,6- hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] available as Chimassorb ® 944 FDL from BASF.
  • Physical properties [0088]
  • the elastomeric compositions of the present disclosure comprise a Shore A Hardness of about 5 to about 50, such as about 20 to about 38 such as about 27.5 to about 33.5.
  • the elastomeric compositions of the present disclosure comprise a Shore A Hardness of about 5 to about 35, alternatively about 20.9 to about 43.3, alternatively about 22.2 to about 46, alternatively about 10.38 to about 41.1, alternatively about 12.2 to about 47.7. [0089] In some embodiments, the elastomeric compositions of the present disclosure comprise a M100 value of about 0.1 MPa to about 3.6 MPa, such as about 0.3 MPa to about 2.2 MPa, such as about 0.5 MPa to about 1.6 MPa, such as about 0.8 MPa to about 1.3 MPa.
  • the elastomeric compositions of the present disclosure comprise a M100 value of about 0.5 MPa to about 0.9 MPa, alternatively about 0.6 MPa to about 3.5 MPa, alternatively about 0.2 MPa to about 3.6 MPa, alternatively about 0.5 MPa to about 2.5 MPa, alternatively about 0.2 MPa to about 1.8 MPa, alternatively about 0.1 MPa to about 2.7 MPa.
  • the elastomeric compositions of the present disclosure comprise a tensile strength at break of about 0.03 MPa to about 15.1 MPa, such as about 1.1 MPa to about 8.3 MPa, such as about 3.0 MPa to about 7.0 MPa, such as about 4.3 MPa to about 6.3 MPa.
  • the elastomeric compositions of the present disclosure comprise a tensile strength at break of about 2.7 MPa to about 12 MPa, alternatively about 1.5 MPa to about 15.1 MPa, alternatively about 0.9 MPa to about 8.3 MPa, alternatively about 1.9 MPa to about 10.2 MPa, alternatively about 0.3 MPa to about 6.3 MPa, alternatively about 0.02 MPa to about 5.7 MPa.
  • the elastomeric compositions of the present disclosure comprise a elongation at break of about 130 % to about 1380 %, such as about 350 % to about 1250 %, such as about 625 % to about 1150 %, such as about 800 % to about 1000 %.
  • the elastomeric compositions of the present disclosure comprise an elongation at break of about 930 % to about 1300 %, alternatively about 315 % to about 1300 %, alternatively about 130 % to about 1280 %, alternatively about 240 % to about 1180 %, alternatively about 255 % to about 1380 %, alternatively about 235 % to about 1290 %.
  • the elastomeric compositions of the present disclosure comprise an O2 permeability coefficient of about 0.1 (mm)•(cc)/ m2•day•mmHg to about 1.4 (mm)•(cc)/ m2•day•mmHg, such as about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.4 (mm)•(cc)/ m2•day•mmHg, such as about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.3 (mm)•(cc)/ m2•day•mmHg.
  • the elastomeric compositions of the present disclosure comprise an O2 permeability coefficient of about 0.1 (mm)•(cc)/ m2•day•mmHg to about 1.3 (mm)•(cc)/ m2•day•mmHg, alternatively about 0.1 (mm)•(cc)/ m2•day•mmHg to about 1 (mm)•(cc)/ m2•day•mmHg, alternatively about 0.1 (mm)•(cc)/ m2•day•mmHg to about 0.3 (mm)•(cc)/ m2•day•mmHg, alternatively about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.3 (mm)•(cc)/ m2•day•mmHg, alternatively about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.3 (mm)•(cc)/ m2•day•mmHg, alternatively about 0.2 (
  • the elastomeric compositions of the present disclosure may be damaged as a result of commercial use.
  • the elastomeric composition is capable of undergoing the self-healing and self-sealing behavior to produce a healed elastomeric composition.
  • the healed elastomeric compositions of the present disclosure comprise a M100 value of about 0.02 MPa to about 1.4 MPa, such as about 0.4 MPa to about 0.9 MPa, such as about 0.5 MPa to about 0.7 MPa.
  • the healed elastomeric compositions of the present disclosure comprise a M100 value of about 0.4 MPa to about 0.9 MPa, alternatively about 0.3 MPa to about 1.2 MPa, alternatively about 0.02 MPa to about 0.8 MPa, alternatively about 0.4 MPa to about 1.4 MPa, alternatively about 0.1 MPa to about 1 MPa, alternatively about 0.05 MPa to about 0.9 MPa.
  • the healed elastomeric compositions of the present disclosure comprise a tensile strength at break of about 0.2 MPa to about 1.8 MPa, such as about 0.4 MPa to about 1.3 MPa, such as about 0.5 MPa to about 1 MPa, such as about 0.6 MPa to about 0.9 MPa.
  • the healed elastomeric compositions of the present disclosure comprise a tensile strength at break of about 0.4 MPa to about 1.7 MPa, alternatively about 0.2 MPa to about 0.9 MPa, alternatively about 0.2 MPa to about 1.2 MPa, alternatively about 1 MPa to about 1.8 MPa, alternatively about 0.3 MPa to about 1.2 MPa, alternatively about 0.2 MPa to about 1.3 MPa.
  • the healed elastomeric compositions of the present disclosure comprise a elongation at break of about 35 % to about 1165 %, such as about 55 % to about 520 %, such as about 85 % to about 265 %, such as about 110 % to about 180 %.
  • the healed elastomeric compositions of the present disclosure comprise a elongation at break of about 120 % to about 1165 %, alternatively about 75 % to about 350 %, alternatively about 45 % to about 900 %, alternatively about 65 % to about 530 %, alternatively about 46 % to about 381 %, alternatively about 37 % to about 629 %.
  • the healed elastomeric compositions of the present disclosure comprise an O2 permeability coefficient of about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.4 (mm)•(cc)/ m2•day•mmHg, such as about 0.2 (mm)•(cc)/ m2•day•mmHg to about 0.3 (mm)•(cc)/ m2•day•mmHg, such as about 0.25 (mm)•(cc)/ m2•day•mmHg to about 0.26 (mm)•(cc)/ m2•day•mmHg.
  • elastomeric compositions of the present disclosure can be used as a component of a tire.
  • a tire also referred to as a “tire product” herein
  • a tire can be any suitable tire, such as a rubber tire having an outer (visible) rubber sidewall layer where the outer sidewall layer includes a composition of the present disclosure.
  • the tire can be built, shaped, molded to include the outer sidewall (rubber sidewall layer) and cured by various methods which will be readily apparent to those having skill in such art.
  • Blends of highly saturated specialty elastomers blended with highly unsaturated polymers can be desired to improve the performance window of the blend (e.g., oxygen & ozone resistance, thermal stability, tack, etc).
  • a tire comprises a supporting tire carcass comprised of one or more layers of ply, an outer circumferential tread, and a radially innermost innerliner layer, a pair of beads, sidewalls extending radially inward from the axial outer edges of the tread portion to join the respective beads, a sealant layer, and a cover layer, disposed on said tire carcass innermost layer.
  • the components of the interpenetrating networks described herein may be tuned and modified to provide high mechanical and physical properties desirable suitable for application within a tire composition, such as the liner layer, while also maintaining the viscoelastic properties necessary for the material to retain the desired self-healing and self-sealing capabilities.
  • a tire composition such as the liner layer
  • an appropriate balance of the parameters set forth for the elastomeric composition described herein, and implemented within a tire composition reduces the downtime and cost commonly associated with tire maintenance and replacement.
  • Elastomeric interpenetrating networks were formed by blending (one-step mixing) brominated poly(isobutylene-co-paramethylstyrene) and/or brominated poly(isobutylene-co- isoprene) with one or more of non-halogenated poly(isobutylene), butyl rubber, and/or poly(styrene-co-polyisobutylene), using a mixing bowl mixer at about 90 oC to 150 oC and mixed for approximately 2 minutes at about 40 rpm.
  • triphenyl phosphine is then added and allowed to blend for approximately 4 minutes. Subsequent the addition of the triphenyl phophine, stearic acid, ZnO, and other additives are added and allowed to blend for approximately 2 minutes. The resulting samples were then recovered for testing. Contents and amounts of the resulting elastomeric compositions are summarized in Table 3.
  • the temperature was then increased to a range of about 170 oC to about 190 oC, and allowed to mix for an additional 5 minutes.
  • samples may be produced in excess to be blended with other compositions at about 150 oC to form a mixture of blends.
  • the triphenyl phosphine was then added to the blend, and/or mixture of blends, and allowed to mix for 5 minutes.
  • the resulting samples were then recovered for testing. Contents and amounts of the resulting elastomeric compositions are summarized in Table 4.
  • the MB was first mixed at approximately 100 oC for about 5 minutes. The MB was then mixed for 5 min at a temperature range of about 160 oC to about 190 oC. An additional rubber component was then blended into the MB for approximately 2 minutes, followed by the addition of triphenyl phosphine. The resulting samples were then recovered for testing. Contents and amounts of the resulting elastomeric compositions are summarized in Table 5.
  • the MB was first mixed at approximately 100 oC for about 5 minutes. The MB was then mixed for 5 min at a temperature range of about 160 oC to about 190 oC. An additional rubber component was then blended into the MB for approximately 2 minutes, followed by the addition of triphenyl phosphine. The resulting samples were then recovered for testing. Contents and amounts of the resulting elastomeric compositions are summarized in Table 6.
  • Tensile testing [0106] Stress/Strain measurements were taken on test specimens using ASTM D412 die. Specimens were tested on an Instron 5565 with a long travel mechanical extensometer. The load cell and extensometer are calibrated before each day of testing with 20mm as the gauge length. Sample information, operator name, date, lab temperature, and humidity were all recorded. Specimen thickness was measured at three places in the test area and the average value was entered when prompted. The lab temperature and humidity were measured. Specimen was carefully loaded in the grips to ensure grips clamp on the specimen symmetrically. The extensometer grips was then attached to the sample in the test area. The test was prompted to start. A pre-load of 0.1N was applied.
  • Permeation rates of gases and permeation coefficients may be measured by a number of methods including coulometric (ASTM D 3895), manometric (ASTM D 1434), and carrier gas (ISO 15105-1). Instruments that measure permeation, and permeation testing services are provided by companies such as Mocon Inc., of Minneapolis, MN, USA. Oxygen transmission rate can be tested using ASTM D 3985-05 and an OX-TRAN® 2/61 MJ module (an oxygen transmission rate test system, available from Mocon, Inc.).
  • Elastomeric network self-healing and self-sealing [0108] Elastomeric network materials were cut and/or punctured, so as to mimic potential damage the material may receive during commercial use. For example, tensile test specimins were cut to form damaged components. After damaging the material, the damaged components were then compressed together under about 5 tons of pressure at about 50 oC for about 10 minutes, so as to self-heal the material. The pressure was then released from the sample, and the sample was allowed to cool for about 5 minutes on a cool platen.
  • the interpenetrating networks can include a first component, a second component, and a curing system.
  • the overall composition of the interpenetrating networks, as disclosed herein, can provide physical and mechanical properties for implementation within tire components. Additionally, the overall composition of the interpenetrating networks can provide the material with self-healing and self-sealing properties to extend the usable lifetime of the tire component.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente divulgation concerne des compositions élastomères imperméables aux gaz, auto-cicatrisantes et auto-obturantes et des procédés associés. Dans au moins un mode de réalisation, une composition d'élastomères comprend un premier élastomère et un second élastomère, le premier élastomère étant un copolymère comprenant des motifs répétés dérivés de p-méthlystyrène, de p-halogénométhylstyrène et d'isobutylène et constituant environ 30 phr à environ 100 phr de la composition élastomère. Dans au moins un mode de réalisation, un réseau élastomère renferme un premier élastomère, un second élastomère et un composé nucléophile, le composé nucléophile étant un agent de réticulation et constituant environ 1,4 phr à environ 2,7 phr de la composition élastomère. Dans certains modes de réalisation, un procédé comprend le mélange d'un premier élastomère et d'un second élastomère pour former une composition d'élastomères, la combinaison de la composition d'élastomères avec un composé nucléophile pour former un réseau élastomère et l'intégration du réseau élastomère dans une couche de flanc externe en caoutchouc d'un pneu.
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