Elastomer compositions and methods thereof

Abstract

The present disclosure relates to gas impermeable, self-healing, and self-sealing elastomeric compositions and methods thereof. In at least one embodiment, an elastomer composition comprises a first elastomer and a second elastomer, wherein 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. In at least one embodiment, an elastomeric network includes a first elastomer, a second elastomer, and a nucleophilic compound, wherein the nucleophilic compound is a crosslinking agent and comprises about 1.4 phr to about 2.7 phr of the elastomeric compostion. In some embodiments, a method comprises mixing a first elastomer and a second elastomer to form an elastomer composition, blending the elastomer composition with a nucleophilic compound to form an elastomeric network, and integrating the elastomeric network into an outer rubber sidewall layer of a tire.

Description

ELASTOMER COMPOSITIONS AND METHODS THEREOFINVENTORS: Sunny Jacob; Krishnan AnanthaNarayana IyerCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 520,120, filed August 17, 2023, entitled “Elastomer Compositions and Methods Thereof’, the entirety of which is incorporated by reference herein.FIELD

[0002] The present disclosure relates to elastomer compositions and methods thereof.BACKGROUND

[0003] The tire industry is interested in developing novel ways of extending the useful lifetime of tire products and materials, as such products and materials are ubiquitous in commercial and consumer applications. However, such high utilization inevitably means that a tire product may become punctured or damaged which can result in the substantial or total loss of air pressure of one or more tires. This unfortunately limits a vehicle’s ability to travel, and has been an issue dating back from the very start of the use of inflated tires.

[0004] For decades, the spare wheel was considered to be the only universal solution to sudden, irreversible loss of air pressure. However, recent technological advancements have arisen that could potentially dispense with the need for having a spare tire. Specifically, 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. However, in many cases, 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.

[0005] Thus, self-healing and / or self-sealing compositions for tires have become an active area of intrigue and research. The goal of such work is to produce a tire composition that is capable of automatically sealing a tire in the event of it being punctured by a foreign body, such as a nail. In addition, the automatic sealing properties should be able to proceed without any external intervention.

[0006] While there have been reports of elastomeric polymers being implemented in self- healing or self-sealing compositions, it is difficult to provide both of these properties within the same composition. In addition, many of these compositions and tires thereof lack physical and mechanical property retention once the material is damaged. In particular, retaining gasbarrier properties of the material once damaged is particularly troublesome, as poor retention in gas barrier properties can result in tire deflation.

[0007] There is a need to develop novel compositions to be used in tires, such that upon receiving damage, the tire can autonomously self-heal and self-seal to extend the usable lifetime of the tire. Specifically, there is a need to develop novel compositions that upon self- healing / sealing, the gas barrier properties retained will be comparable to that of the original material.

[0008] References for citing in an information disclosure statement (37 C.F.R. 1.97(h)): U.S. Patent Nos. 8,883,415; 11,312,094; 8,602,075; 10,919,242; 7,674,344; 8,703,832; U.S. Publication Nos. 2016 / 0068031; 2021 / 0354407.SUMMARY

[0009] The present disclosure relates to elastomer compositions and methods thereof.

[0010] In some embodiments, 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.

[0011] In some embodiments, 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, and the nucleophilic compound is a crosslinking agents, the nucleophilic compound comprising about 1.4 phr to about 2.7 phr of the elastomeric compostion.

[0012] In some embodiments, 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.DETAILED DESCRIPTION

[0013] Multiple pathways have been developed to produce highly impermeable self-healing and self-sealing compositions suitable for tire sealing applications. Those pathways include the implementation and crosslinking of elastomeric blends comprising one or more halogenated species. It was found that semi-interpenetrating elastomer network components with dual sealing mechanisms and in-situ formed low molecular weight ionomer containing compositions showed good resealing performances and retention of gas after puncture and reseal.

[0014] 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.

[0015] 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.

[0016] The second rubber component may also be partially crosslinked, so as to provide the interpenetrating elastomeric network with increased mechanical properties.

[0017] Additionally, in-situ low molecular weight ionomer formation was found to provide easier flow characteristics, prepared by chain breaking the halogenated elastomer with a peroxide. The network is then reformed via the ionomer forming reagent reacting with higher amounts of halobutyl elastomers or blends thereof, and a second elastomer.Definitions

[0018] 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.

[0019] As used herein, "polymer" may be used to refer to homopolymers, copolymers, terpolymers, etc. As used herein, the term “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 differentcomonomers. The mixing of comonomers may be done in one, two, or possible three different reactors in series and / or in parallel. As used herein, when a polymer is referred to as ‘'comprising” a monomer, the monomer is present in the polymer in the polymerized form of the monomer. Likewise, when 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.

[0020] As used herein, “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.

[0021] The term “composition” or “blend” as used herein 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.

[0022] 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”. Different monomers are discussed herein including C4-C7 isoolefm monomers, non-halogenated alkylstyrene monomers, halogenated sty rene monomers, and diolefin monomers.

[0023] As used herein, “phr” means “parts per hundred parts rubber,” where the “rubber” is the total rubber content of the composition. Herein, both the elastomers (such as BIMSM) of the present disclosure and additional rubbers, when present, are considered to contribute to the total rubber content. Thus, for example, 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.

[0024] “Mooney viscosity ” as used herein is the Mooney viscosity' of a polymer or polymer composition. The polymer composition analyzed for determining Mooney viscosity should be substantially devoid of solvent. For instance, 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, andthen, 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). Unless otherwise indicated, Mooney viscosity is measured using a Mooney viscometer according to ASTM DI 646- 19, but with the following modifications / clarifications of that procedure. First, 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. Further, although 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. Further, 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. The results are reported as Mooney Units (ML, 1+4 @ 125 °C or ML, 1+8 @ 125 °C), where M is the 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, and 125 °C is the test temperature. Thus, 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). Alternatively, 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. In some instances, 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.Elastomers and compositions thereof

[0025] In one or more embodiments, the compositions can be comprised of at least one elastomeric network and can exhibit self-healing and self-sealing behavior. In some embodiments, 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. Without being bound by theory, the at least one elastomeric network participates predominantly in the self-healing behavior of the composition, while the additional elastomeric component participates predominantly in theself-sealing behavior. In addition, in some embodiments, 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.

[0026] In at least one embodiment, 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. 2- methylbutadiene, 2,3-dimethyl-l,3-butadiene, 2,4-dimethyl-l,3-butadiene, 1,3-pentadiene, 2- methyl-l,3-pentadiene, 3-methyl-l,3-pentadiene, 4-methyl- 1,3-pentadiene, 2, 3-dimethyl- 1,3- pentadiene, 1,3-hexadiene, 2-methyl-l,3-hexadiene, 3-methyl-l,3-hexadiene, 4-methyl-l,3- hexadiene, 5-methyl- 1,3-hexadiene, 2, 3-dimethyl- 1,3-hexadiene, 2, 4-dimethyl- 1,3-hexadiene, 2, 5-dimethyl- 1 ,3-hexadiene, 2-neopentylbutadiene, 1,3-cyclopentadiene, 1 ,3-cyclohexadiene, l-vinyl-l,3-cyclohexadiene, isobutylene, isobutene, 2-methyl-l -butene, 3 -methyl- 1 -butene, 2- methyl-2-butene, 4-methyl- 1 -pentene, and combinations thereof. In at least one embodiment, an elastomer is butyl rubber.

[0027] In at least one embodiment, an elastomer comprises halogenated butyl rubber. As used herein, '‘halogenated butyl rubber” refers to both butyl rubber and so-called “star- branched” butyl rubber. In some embodiments, the halogenated rubber component is a halogenated copolymer of a C4-C14 isoolefin and a C4-C14 multiolefin. In another embodiment, 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. In one embodiment, the halogenated butyl rubber is brominated butyl rubber, and in another embodiment is chlorinated butyl rubber.

[0028] In some embodiments, 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. Thus, in some embodiments, 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 thetotal 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.

[0029] 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). Its Mooney viscosity is 41 to 51 (ML 1+8 at 125° C., ASTM 1646-17), and the bromine content is 1.8 to 2.2 weight percent. Further, cure characteristics of Bromobutyl 2255 are as follows: MH is from 34 to 48 dN m, ML is from 11 to 21 dN m (ASTM D2084-17).

[0030] Examples of isobutylene-isoprene copolymers, include EXXON™ BUTYL 065, EXXON™ BUTYL 065 S, EXXON™ BUTYL 365, EXXON™ BUTYL 068, EXXON™ BUTYL 068S, EXXON™ BUTYL 268. EXXON™ 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.

[0031] In at least one embodiment, an elastomer comprises a polymer made up of at least one non-halogenated sty rene monomer and / or halogenated styrene monomer. In at least one embodiment, 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. In some embodiments, 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. In one or more embodiments, 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 %.

[0032] In one or more embodiments, 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.

[0033] In one or more embodiments, 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). In some embodiments, non-halogenated alkydstyrene and halogenated alkylstyrene monomers each contain at least 80 wt%, such as at least 90 wt% para-isomer. In some embodiments, 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 %.

[0034] In some embodiments, elastomers of the present disclosure may contain the following monomer units randomly spaced along the polymer chain:wherein R10and R11are 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, R10and R11are 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 %.

[0036] 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.

[0037] In at least one embodiment, 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 %. These halogenated elastomers are commercially available as EXXPRO™ 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.

[0038] In some embodiments, 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. In one or more embodiments, 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. Expressed another way, 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. In at least one embodiment, the elastomer is a copolymer of C4to C14isoolefin 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 %. In at least one embodiment, the p-halomethylstyrene is p-bromomethylstyrene.

[0039] In at least one alternative embodiment, the elastomers can further include one or more diolefin monomers, where the C4to C14isoolefin is not the same as the diolefin. Examples of 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%.

[0040] In one or more embodiments, an elastomer includes at least one C4to C14isoolefin- 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. In at least one embodiment, 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 %.

[0041] In one or more embodiments, 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.

[0042] In some embodiments, 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.

[0043] In some embodiments, 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. In some embodiments, it may be advantageous to utilize two or more elastomers each having a similar polymer backbone composition but different molecular weight profiles, for example, a low molecular weight elastomer having a weight average molecular weight less than about 150,000 g / mol being blended with a high molecular weight elastomer having a weight average molecular weight greater than about 250,000 g / mol.Elastomeric and interpentrating networks

[0044] 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.

[0045] In some embodiments, one or more halogenated elastomers (denoted hereinafter as “component A”) 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. Furthermore, 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.

[0046] In one or more embodiments, component A can be represented by pendently a numerical value representingthe number of respective repeat units along the polymer backbone. In at least one embodiment, each X is independently either bromine or chlorine. In some embodiments, the elastomeric polymer of component A has a number average molecular weight (Mn) 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. In some emodiments, 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. In at least one alternative embodiment the ratio of m+n to z is about 40:60 to about 30:70, alternatively about 30:70 to about 20:80, alternatively about20:80 to about 10:90, alternatively about 10:90 to about 5:95.In at least one embodiment, 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.

[0047] In at least one embodiment, component A is halogenated butyl rubber or isomer thereof.

[0048] In at least one embodiments, 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.

[0049] In one or more embodiments, 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. Many of these rubbers are described by Subramaniam in RUBBER TECHNOLOGY 179-208 (M. Morton, Chapman & Hall 1995), THE VANDERBILT RUBBER HANDBOOK 105-122 (R. F. Ohm ed., R.T. Vanderbilt Co., Inc. 1990), or E. Kresge and H. C. Wang in 8 KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY 934-955 (John Wiley & Sons, Inc.4th ed.1993).

[0050] 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.

[0051] 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). By “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 BUDENE™ 1207 (available from Goodyear Chemical).

[0052] 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. A suitable ethylene-propylene rubber is commercially available as VISTALON™ (ExxonMobil Chemical Company).

[0053] In some embodiments, the elastomeric polymer of component B has a number average molecular weight (Mn) 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.

[0054] In at least one embodiment, the elastomeric polymer of component B is treated with a peroxide to allow for vis-breaking of the polymer chain. Once vis-broken, 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.

[0055] In one or more embodiments, 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.

[0056] In some embodiments, the elastomeric composition includes one or more additives such as fillers, dyes, pigments, antioxidants, heat and light stabilizers, plasticizers, oils, and / or other ingredients.

[0057] Examples of fillers 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. In some embodiments, 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. In at least one alternative embodiments, fillers can be present within the elastomeric composition about 10 phr to about 30 phr.

[0058] As used herein, 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.

[0059] 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. Alternatively, 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.

[0060] In some embodiments, 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. In some embodiments, the extender oil is chosen from the group consisting of polyolefin oils, paraffinic oils, naphthelnic oils, aromatic oils, mineral oils, and combinations thereof. In some embodiments, 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. In at least one embodiment, 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.

[0061] In some embodiments, it is desirable to incorporate crosslinks into the elastomer composition. In such instances, 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. Without being bound by theory, the resulting elastomeric network is the result of ion-pair aggregation.

[0062] When forming the interpenetrating network, a curing system comprising a nucleophilic species is introduced to the elastomeric composition to induce ionomeric network formation with component A. In some embodiments, it is important that components A and B be adequately blended such that upon the introduction of the nucleophilic species to the elastomeric composition, the newly formed ion pairs and ion-pair aggregates form substantially throughout the elastomeric composition. Further, since component B is incapable of interacting with the nucleophilic species, component B remains dispersed within the ionomeric network formed by component A.

[0063] In at least one embodiment, a nucleophilic compound introduced to an elastomeric composition to form an elastomeric network is one or more of a nitrogen or phosphorus nucleophile. In one or more embodiments, the nucleophilic compound can be represented byA is a nitrogen or phosphorus; and R1, R2, and R3are 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.

[0064] In general and without being bound by theory, 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. In at least one embodiment, the nucleophilic compound is triphenyl phosphine.

[0065] Other suitable 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.

[0066] The amount of nucleophile added to the elastomeric composition is determined based upon the molar equivalence ratio relative to the halide content therein. In one or more embodiments, 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. In at least one alternative embodiment 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.Alterantively, 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.

[0067] 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 BANBURY™ mixer, BRABENDER™ 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.

[0068] In another embodiment, 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, BRABENDER™ internal mixer, BANBURY™ 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).

[0069] Typically, from 70% to 100% of the 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. The masterbatch mixture is then finished by sheeting on an open mill and allowed to cool, for example, to from 60 °C to 100 °C when the remaining components of the curing system may be added to produce a final batch mix.

[0070] The 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. For example, 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. In 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.

[0071] Without being bound by theory, 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. Without being bound by theory, 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. Furthermore, 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. Without being bound by theory, 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. As such, 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] In one or more embodiments, component B of the elastomeric composition comprises a partially crosslinked elastomer. Without being bound by theory, implementing a partially crosslinked elastomer as component B provides additional strength to the ionomeric network without significantly affecting the resealing characteristics and properties of the overall elastomeric composition.

[0073] In some embodiments, 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. As used herein, the term “curing system” refers to the combination of any one or more curative agents.

[0074] In at least one embodiment, the curing agent of component B is a bisthiosulfate compound. A bisthiosulfate compound can be represented by the formula Z1-R1-Z2, where R1is substituted or unsubstituted C1 to C15 alkyl, substituted or unsubstituted C2 to C15 alkenyl, or substituted or unsubstituted C6to C12cyclic aromatic moiety; and Z1and Z2are independently a thiosulfate group. In some embodiments, R1is 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.

[0076] Metal oxides can act as curing agents for compostion B. Examples of metal oxides include zinc oxide, calcium oxide, lead oxide, magnesium oxide, and combinations thereof.

[0077] In one or more embodiments, metal oxide can be used alone or in conjunction with its corresponding metal fatty acid complex (e.g., zinc stearate, calcium stearate, etc.). In some embodiments, 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.

[0078] In some embodiments, 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

[0079] In some embodiments, it may be desired that the elastomeric composition posses a degree of flowability, such that the elastomeric composition exhibits impoved self-sealing properties. For instance, when the elastomeric composition is punctured or damaged, the material would have the ability easily flow over the damaged area to thereby provide a sealant layer thereto. In the context of the present disclosure, this can be accomplished through the chain cessation of one or more components of the interpenetrating network via the introduction of one or more peroxide catalysts.

[0080] Chain scission can occur in ionic butyl rubber, thereby producing low molecular weight ionomers. Such low molecular weight ionomers can also be called ionomeric oligomer. As used herein, "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. In some embodiments, the oligomeric ionomers have attached functional moieties, which can participate and / or facilitate ionic sealing. In some embodiments, the functional moiety is one or more of a bromine and chlorine.

[0081] 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. In contrast, halobutyl rubber undergoes chain scission, resulting in decreased viscosity or G’ after heating to a cure temperature.

[0082] In some embodiments, 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. Without being bound by theory, incorporating ionic butyl rubber within the elastomeric composition provides self-sealing and gas impermeable properties.

[0083] In some embodiments, the elastomeric composition comprises at least one compound having at least one peroxide moieties. In one or more embodiments, the peroxide compound can be any one or more of an aliphatic compound, a cycloaliphatic compound, or an aromatic compound. In at least one embodiment, 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-butyl peroxy) hexane. In one or more embodiments, the peroxide compound may be any appropriate commercially available peroxide compound, such as DI-CUP®Dicumyl Peroxide and / or Luperox®101.

[0084] In some embodiments, 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. Such activating agents are described in U.S. Pat. No.7,674,344 to D'Sidocky et al., the disclosure of which is incorporated by reference for that purpose.

[0085] In one or more embodiments, 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.

[0086] In at least one embodiment, 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.

[0087] In at least one embodiment, 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] In some embodiments, 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. In one or more alternative embodiments, 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. In one or more alternative embodiments, 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.

[0090] In some embodiments, 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. In one or more alternative embodiments, 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.

[0091] In some embodiments, 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 %. In one or more alternative embodiments, 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 %.

[0092] In some embodiments, 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. In one or more alternative embodiments, 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 0.4 (mm)•(cc) / m²•day•mmHg.

[0093] In some embodiments, 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.

[0094] In some embodiments, 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. In one or more alternative embodiments, 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.

[0095] In some embodiments, 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 0.9MPa. In one or more alternative embodiments, 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.

[0096] In some embodiments, 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 %. In one or more alternative embodiments, 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 %.

[0097] In some embodiments, 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. Tires

[0098] In some embodiments, 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) 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.

[0099] 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). For tire tread in particular, tire tread compounds in a tire dictate properties of the tire, such as wear, traction, and rolling resistance. It is a technical challenge to deliver excellent traction, low rolling resistance while providing good tread wear. The challenge lies in the trade-off between wet traction and rolling resistance / tread wear.

[0100] Generally, 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 therespective 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. As such, 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. Examples Formation of elastomeric interpenetrating networks:

[0101] 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. The triphenyl phosphine, ZnO, salt mix, and / or any other additive was then added to the blend and allowed to mix for 5 minutes. Optionally, stearic acid was then added to the mixture, and the mixture was continuously blended for about 3 minutes to about 6 minutes. The resulting samples were then recovered for testing. Contents and amounts of the resulting elastomeric compositions are summarized in Tables 1A and 2A.Table 1 Mix at Mix at Mix at Mix at 150 C 150 C 150 C 150 C Exam 9 10 11 12 Exxpro Exxpro Exxpro Exxpro 30351:1 30351:1 30351:1 30351:1 Meq Meq Meq Meq ateria TPP; TPP; TPP; TPP; 30 30 XP 30 XP 30068 SIBSTA 50 and 50 and and R more more, more, BaO BaO phr phr phr phrExxpr 70.0 70.0 54.0 54.0 Triph phosp 2.1 2.1 2.1 2.1 XP 30.0 30.0 30.0stanex RB RB SIBS 02TU 30.0 Steari 1.0 1.0 1.0 Barium 5.0 5.0 5.0 N660 ( Carbon SCOR 10.0 Indo 20.0 20.0 pro 30 60ph 26.0 26.0 T ta 102.1 108.1 138.1 148.1Ta Mix at Mix at Mix at Mix at 150 150 150 150 C C C C 18 19 20 21 Exxpro Exxpro Exxpro Exxpro 3745 3745 3745 3745 1:1 1:1 1:1 1:1 Meq Meq Meq Meq TPP; TPP; TPP; TPP; 50 30 30 30 365 365 068 SIBS TAR phr phr phr phr 50.0 70.0 70.0 70.0 2.1 2.1 2.1 2.1 V 50.0 30.0 30.0 30.0 102.1 102.1 102.1 102.1Ta Mix at Mix at Mix at Mix at 150 C 150 C 150 C 160 C 331 32 33 34 Exxpro Exxpro o 3035 3035 Exxpro 1:1 1:1 3035 Meq Meq 1:1.3 Exxpro TPP; TPP; Meq 3035; 30365; 15 NR, TPP; NR, ; 20 CB 15 30365; SBR, 660; SBR; 20 CB ZnO 1102 & 20 CB 660 Indopol 660 phr phr phr phr 70.0 70.0 70.0 30.0 B A i 2.1 2.1 2.7 - 15.0 15.0 30.0 15.0 15.0 40.0 30.0 t T S20.0 20.0 20.0 20.0 20.0 10.0 10.0 5.0 02.1 102.1 122.1 142.1 122.1 122.7 125.0Mix at Mix at Mix at Mix at 150 C 150 C 150 C 150 C 44 45 46 47Exxpro Exxpro Exxpro 3745 3745 3745 1:1 1:1 1:1.3 Meq Meq Meq Exxpro TPP; TPP; TPP; 3745; 30365; 15 NR, 15 NR, NR, 20 CB 15 15 SBR, 660; SBR; SBR; ZnO 1102 & 20 CB 20 CB Indopol 660 660 phr phr phr phr 70.0 70.0 70.0 30.0 2.1 2.1 2.7 15.0 15.0 30.0 15.0 15.0 40.030.0 20.0 20.0 20.0 20.0ESC 10.0 10.05.0T 102.1 102.7 102.1 102.1 122.1 142.1 122.1 122.7 125.0 31Formation of elastomeric components having two of more curable components:

[0102] Elastomeric networks wherein both components A and B are, and / or could be, crosslinked, were formed by blending (one-step mixing) brominated poly(isobutylene-co- paramethylstyrene) and / or poly(isobutylene-co-isoprene) with a second elastomer that is curable via any introducing any one or more conventional cure agents, using a mixing bowl at about 90 ºC to 150 ºC and mixed for approximately 2 minutes at about 40 rpm. The 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.at Mix at Mix at Mix at Mix at C 150 C 150 C 150 C 160 C 6 57 58 59 60xpro Exxpro Exxpro Exxpro Exxpro 35 3035 3035 3035 30351.3 1:1.3 1:1 Meq 1:1.3 1:1.3 eq Meq TPP; Meq MeqPP; TPP; 30365; TPP; TPP; 0 50 20 CB 25 SBR, 50R; S SBR;C 660; 25 NR, 2502,BTS B, S 1102 & S Hst, MBTS Indopol MBTS Znohr phr phr phr phr0.0 50.0 70.0 50.0 50.0 .7 2.7 2.1 2.7 2.7 25.0 0.0 50.0 25.0 30.0 50.0 .0 2.0 2.0 2.0 10.0 20.0 10.0 10.0 .0 3.0 3.0 3.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5 0.5 0.5 0.5 5.0 2 112.7 130.2 140.2 107.7 110.2 120.2 142.1 110.2 109.7Mix at Mix at Mix at 150 C 150 C 150 C 68 69 70 Exxpro 37451:1.3 Exxpro Exxpro Meq TPP; 37451:1.3 37451:1.3 50068; Meq TPP; Meq TPP; HSt, ZnO; 50068; 50068; S 101 HSt, ZnO cure phr phr phr 50.0 50.0 50.0 2.7 2.7 2.7 50.0 50.0 50.0 2.0 2.0 2.0 3.0 3.0 1.0 1.0 0.5 1.0 105.7 107.7 110.2Formation of elastomeric networks comprising peroxides:

[0103] Elastomeric interpenetrating networks were formed by blending (one-step mixing) brominated poly(isobutylene-co-paramethylstyrene) and / or poly(isobutylene-co-isoprene) with DICUP®, and optionally a halogenated and / or non-halogenated butyl rubber, using a mixing bowl at about 100 ºC and mixed for approximately 5 minutes at about 40 rpm. 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. Optionally, 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.T Exam 7 78 79 80 81 2222 BB 2222 BB 22 BB 2255 BB 2255 Meq 1:1 Meq 55 1:1 Meq 1:1 ; + TPP; + 1: Meq P 1 Meq TPP; TPP; + TPP; + up 3 Dicup 4 Dicup 2 Dicup 3 hr phr phr phr phr B0.0 100.0x T 2 4.2 4.2 4.2 4.2 z - x D - x D - B D -042 ( 100.0 100.0 100.0 ' 2.0 3.0 4.0 0.0 2.0 3.0 M 106.2 107.2 108.2 104.2 106.2 107.2T Exam 89 90 91 92 BB 2255 BB 2255 Exxpro Exxpro 1:1 Meq 1:1 Meq 37451:1 37451:1 TPP; 'BB TPP; 'BB Meq TPP; Meq TPP; a 2255 + 2255 + 'BB 2255 'BB 2255 Dicup 2 Dicup 3 + Dicup 2 + Dicup 2 (50%) (50%) (50%) (50%) phr phr phr phr x 50.0 50.0 m T p 4.2 4.2 4.2 5.0 n 2 x 2 x 2 50.0 2 50.0 50.050.0 .0 50.0 50.0 4.2 104.2 104.2 104.2 104.2 104.2 105.0Effect of visbreaking halobutyl using peroxide before ionomer reaction:

[0104] A master batch (MB) was first formed comprising a rubber component and DICUP®, wherein the rubber component was selected from Exxpro 3745, Exxpro 3035, BB 2222, or a blend of Exxpro 3745:RB068. 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.T Mix Mix at TPP at TPP at Mix TPP Mix TPP C 150 C 150 C at 150 C at 150 C 99 100 101 102 BB BB Exxpro Exxpro 2 6222 6222 3745:068 3035:068 1:1 1:1 blend 1:1 blend 1:1 Meq Meq Meq Meq ; TPP; TPP; TPP; TPP; p Dicup Dicup Dicup Dicup 0.5 1.0 1.0 1.0 phr phr phr phr 0 50.0 50.0 50.0 50.0 T 4.2 4.2 5.0 5.0 100.0 100.00.5 1.0 0.5 1.0 0.5 1.0 1.0 1.00 102.6 103.1 104.7 105.2 104.7 105.2 106.0 106.0T T Mix Mix P at Mix TPP Mix TPP TPP at TPP at Mix TPP C at 150 C at 150 C 150 C 150 C at 150 C 2 113 114 115 116 117 B BB BB 22 Exxpro 2222 2222 Exxpro 1 37451:1 BB 2222 1:1 1:1 37451:1 eq Meq 1:1 Meq Meq Meq Meq P; TPP; TPP; TPP; TPP; TPP; 45 'Exxpro 'Exxpro 'Exxpro 'Exxpro 'Exxpro 3745:068 3745:068 3745 + 3035 + 3745:068 up + Dicup + Dicup Dicup Dicup + Dicup 1 (50%) 1 (50%) 1 1 1 (50%), %) (50%), (50%), H100 H100 H100 hr phr phr phr phr phr 50.0 50.0 50.0 .0 50.0 50.0 2 5.0 4.2 4.2 2.1 5.0 50.0 50.0 50.050.0 50.0 50.0 50.0 50.0 10.0 10.0 10.004.2 104.2 105.0 154.2 114.2 112.1 115.0

[0105] A master batch (MB) was first formed comprising a rubber component and Luperox 101, wherein the rubber component was selected from Exxpro 3745, Exxpro 3035, BB 2222, or a blend of Exxpro 3745:RB068. 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.Mix Mix Mix TPP at TPP at Mix TPP Mix TPP Mix TPP TPP at 150 C 150 C at 150 C at 150 C at 150 C 150 C 122 123 124 125 126 127 BB BB Exxpro Exxpro BB 2222 3745: CB 2222 068 3035:068 2222:068 blend 1:1 blend 1: 1066 1:1 Meq 1:1 Meq 1 blend 1:1 Meq Meq Me 1:1 Meq TPP; TPP; q erox TPP; TPP; TP TPP; Luperox Lup P; Luperox Luper Luperox 101 0.5 101 1.0 ox Luperox 101 1.0 101 1.0 101 1.0 101 0.5 phr phr phr phr phr phr 100.0 100.0 50.0 50.0 50.0 50.0 50.0 50.0 4.2 4.2 5.0 5.0 4.2 5.02 Lu 10 7 u 0 Z n H u 0.5 1.0 1.0 1.0 1.0 0.5 o 1 104.7 105.2 106.0 106.0 105.2 5.5Tab Mix Mix PP TPP at TPP at Mix TPP C 150 C 150 C at 150 C 6 137 138 139xam BB B Exxpro 222 B 22 37451:1 eq 22 2222 1:1 Meq 1 Meq ; :1 Meq TPP; TPP TPP; ro ; Ma 'Exxpro ' 'Exxpro 068 Exxpro 3745 + 30 3745:068 Na 35 + Luperox Luper + ox ox 1011 10 Luperox 1 11 (50%), (50%) 1011 %) , H100 H100 (50%), H100 phr phr phr BB 0 50.0 50.0 Ex 37 50.0 Ex 30 RB 4.2 2.1 5.0 0 50.03 Lup 101 M 50.0 2 Lup 101 M 74 Lup 101 M 50.0 50.0 50.0 Z Ind H 10.0 10.0 10.0 Lup 1 ot 105.0 154.2 114.2 112.1 115.0Hardness testing: Hardness measurements were taken on test specimens in accordance with ASTM D2240, which is incorporated herein as reference. 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. Testing began with the crosshead at 20 inches / minute until a break is detected. 3 specimens from each sample were tested and the median values were reported. O2permeability:

[0107] 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.). The specimen for Mocon testing was a circular disk having a diameter of about 0.2 mm to about 0.3 mm. 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. Samples were then retested, via any one or more of the previously described material testing methods, and compared to their original undamaged counterpart to determine the degree of mechanical and physical property retention. To determine the self-sealing properties of the elastomeric network materials, select samples were studied using Mocon instrument after puncture and reseal to illustrate the air retention capabilities after puncture and reseal formation. Mocon testspecimens were punctured using a nail, then resealed similar to the cut tensile specimen preparation. The resealed samples were then used for impermeability testing, using Mocon instrument. The results are summarized in Tables 1B through 6B, wherein Tables denoted with B represent the corresponding properties of each of the respective formulations as summarized in Tables denoted with A.6 7 8 9 10 11 12 Exxpro Exxpro Exxpro Exxpro Exxpro 3035 3035 3035 3035 3035 Exxpro 1:1 1:1 1:1 1:1 1:1 Exxpro 30351:1 Meq Meq Meq 3035 Meq TP Meq Meq P; TPP; TPP; TPP; 1:1 30 TPP; TPP; 30 XP 30068 50365 30365 Meq SIBSTAR 30 XP 50 50 and and TPP; and more, m 8 mo ore, 3006 re BaO BaO too soft too soft too soft 18.7 24.3 25.8 31.6 9.2 5.1 5.7 0.44 0.55 0.56 0.74 NA NA NA 4.21 7.675 6.46 13.41 NA NA NA 1291 1256 1235 1165 NA NA NA NA NA 0.47 0.57 0.59 0.72 NA NA NA 0.61 0.66 1.61 1.03 NA NA NA 358 202 791.4 141 NA NA NA15 16 17 18 19 20 21 xxpro 3745 Exxpro Exxpro Exxpro Exxpro Exxpro Exxpro 1:0.7 37451:1 37451:1 37451:1 37451:1 37451:1 37451:1 Meq Meq Meq Meq Meq Meq Meq TPP;PP; 30 TPP; TPP; TPP; TPP; TPP; 30 XP 50 50 XP 50 30 PIB 50365 30365 30068 SIBSTAR 23.7 29.1 32.1 28.1 29.6 32.4 36.4 0.52 0.69 0.66 0.61 0.76 0.78 0.93 6.01 4.135 3.72 4.55 7.18 5.58 11.94 1291 1181 929 998 1136 1070 1221 0.53 0.88 0.75 0.76 0.69 0.75 0.87 0.78 1.07 0.98 1.13 0.83 1 0.91 234 142 182 185 139 165 12129 30 31 32 33 34 Exxpro Exxpro Exxpro Exxpro Exxpro 3035 3035 3035 1:1 3035 30351:1 1:1 1:1 M 1:1.3 Exxpro ; Meq TPP; Meq eq Meq T Meq 3035; 30 TPP; PP; TPP; 30365 TPP; NR,R SIBSTAR 30 ; 15 NR, 20 C 30 SBR, 072 365; B 15 660; SBR; 365; ZnO 20 CB 1102 & 20 CB 660 20 CB Indopol 660 660 33.2 35.2 24.8 34.5 32.7 20.9 0.72 0.88 0.58 1.04 1.68 0.99 15.1 5.5 3.7 4.7 5.3 1.5 1190 854 993 884 837 599 0.67 0.91 0.56 1.04 0.84 0.54 0.61 0.66 0.45 0.60 0.55 0.52 250 171 191 117 130 304 0.236 0.208 0.255 NA 0.460 1.3292 43 44 45 46 47Exxpro Exxpro Exxpro Exxpr 3745 3745 3745 xpro o 3745 1:1 1:1 1:1.3 45 1:1 Meq Meq Meq :1 Meq TPP; TPP; TPP; eq TPP; 30365; 15 NR, 15 NR, ExxproPP; 30 20 CB 15 15 3745; 0 365; 660; SBR; SBR; NR,BST 20 CB 1102 & 20 CB 20 CB SBR, 072 660 Indopol 660 660 ZnO .08 43.32 34.54 41.64 40.40 33.82 91 3.53 2.11 2.46 2.38 1.95 .10 6.84 4.76 5.21 4.31 4.94 72 654 737 580 315 530 0.91 1.15 1.21 66 0.85 0.57 0.65 0.51 0.68 8 78 99 109 78 99212 0.199 0.274 0.420 NA 1.13556 57 58 59 60 Exxp Exxpro xpro ro 3035 30351:1 Exxpro 30 Exxpro 035 1:1.3 Meq 35 1:1. 3035 1.3 TPP; 3 1:1 q Meq .3 Me 30365; Meq Meq PP; TPP; TPP; 50 20 CB TPP; SBR; SBR; 660; 110 25 SBR, CB 2 502502, MBTS , 25 NR, S S MBTS & Hst, Zno Indopol MBTS 9.50 13.90 25.60 39.10 30.50 .58 2.22 2.37 1.74 0.78 .11 2.31 5.58 4.31 1.86 47 130 914 337 281 .00 0.00 0.52 0.00 0.00 .54 0.38 0.60 0.90 0.57 47 47 191 67 83 .551 NA 0.189 NA 1.0966 67 68 69 70ro Exxpro Exxpro Exxpro Exxpro Exxpro5 3035 3035 3745 3745 37453 1:1.3 1:1.3 1:1.3 1:1.3 1:1.3q Meq Meq Meq Meq Meq ; TPP; TPP; TPP; TPP; TPP; 8; 50068; 50068; S 50068; 50068; 50068; S, HSt, ZnO cure HSt, HSt, ZnO cure 101 ZnO; 101 0 24.90 24.10 18.10 31.80 31.403 1.29 1.32 0.69 1.20 1.648 1.94 1.61 1.05 1.41 2.88 244 137 203 152 194 1 0.49 0.02 0.31 0.62 0.094 0.71 0.31 0.33 0.76 0.26 208 60 282 115 111 NA NA 0.357 NA NA77 78 79 80 81B 2222 BB 2222 BB 2255 BB 2255 BB 2255 1 Meq 1:1 Meq 1:1 Meq 1:1 Meq 1:1 Meq TPP; + TPP; + TPP; TPP; + TPP; + icup 3 Dicup 4 Dicup 2 Dicup 3 23.0 22.5 25.6 25.8 23.3 0.5 0.6 0.5 0.7 0.6 3.1 2.1 7.2 3.4 2.7 1153 891 1138 764 848 0.4 0.7 0.5 0.5 0.6 1.2 1.4 1.3 1.2 1.2 472 220 533 279 192 0.247 0.276 0.272 0.290 0.252 NA 0.268 0.235 NA NA89 90 91 92 1:1 BB 2255 BB 2255 Exxpro Exxpro PP; 1:1 Meq 1:1 Meq 37451:1 37451:1 2 + TPP; 'BB TPP; 'BB Meq TPP; Meq 3 2255 + 2255 + 'BB 2255 TPP; 'BB ) Dicup 2 Dicup 3 + Dicup 2 2255 + (50%) (50%) (50%) Dicup 2 (50%) 26.6 25.0 40.5 0.6 0.7 NA 2.5 6.3 4.8 NA 6.5 1103 1081 NA 666 0.7 0.7 1.5 1.5 1.300 264 236 83.800 0.209 0.241 NA NANA 0.216 NA NA 0.255 NA 0.218 NA NA NA8 99 100 101 102 B BB BB Exxpro Exxpro22 6222 6222 3745:068 3035:0681 1:1 1:1 blend 1:1 blend 1:1eq Meq Meq Meq MeqP; TPP; TPP; TPP; TPP;up Dicup Dicup Dicup Dicup0 0.5 1.0 1.0 1.0 A 22.64 10.38 12.32 N / A 0.37 0.16 0.37 1.15 0.35 1.15 727 983 727 0.163 0.285 0.338 0.426 0.267 0.506 92 289 183.394 0.274 NA 0.383 NA114 115 116 117o BB BB BB Exxpro 2222 2222 2222 3745 1:1 1:1 1:1 1:1 Meq Meq Meq Meq TPP; TPP; TPP; TPP;r 'Exxpr 'Exxp 'Exxp 'Exxpr o ro ro o0 3745:0 3745 3035 3745:0 68 + + + 68 + Dicup Dicup Dicup Dicup 1 1 1 1 (50%) (50% (50% (50%), ), ), H100 H100 H100 36.14 1.42 2.94 301 -0.010 0.441107.0 117.0 98.00 66.20 74.8 132.0 68.000 60.900 00 00 0 0 00 00 0.231 0.248 0.271 0.245 0.23 0.24 0.325 0.308 NA 0 9124 125 126 127 Exxpro Exxpro BB CB 3745:068 3035:068 2222:068 1066 blend 1:1 blend 1:1 blend 1:1 1:1 Meq Meq Meq Meq TPP; TPP; TPP; TPP; Luperox Luperox Luperox Luperox 101 0.5 101 1.0 101 1.0 101 1.0 15.300 N / A 12.200 N / A 0.355 0.122 0.243 0.168 0.833 0.025 0.826 0.373 388 758 807 283 0.055 0.410 0.269 N / A 0.305 0.226 0.361 182 629 271 0.307 NA 0.438 NAF 135 136 137 138 139 xxpro BB 2222 BB BB Exxpro 7451:1 1:1 Meq 2222 2222 37451:1 Meq TPP; 1:1 Meq 1:1 Meq Meq TPP; 'Exxpro TPP; TPP; TPP; Exxpro 3745:068 'Exxpro 'Exxpro 'Exxpro 45:068 + 3745 + 3035 + 3745:068 + Luperox Luperox Luperox + uperox 1011 1011 1011 Luperox 1011 (50%) (50%), (50%), 1011 50%) H100 H100 (50%), H100 3.300 27.700 31.000 19.700 29.600 1.610 0.696 0.702 0.486 0.786 5.380 1.840 2.880 2.530 3.280 429 500 725 1290 770 0.603 0.804 0.577 0.966 0.641 0.868 0.588 0.718 56 100 120 106 37 NA 0.273 0.314 0.325 0.260

[0109] Overall, the present disclosure provides compositions of self-healing and self-sealing interpenetrating networks and methods thereof. 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.

[0110] The phrases, unless otherwise specified, "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0111] Numerical ranges used herein include the numbers recited in the range. For example, the numerical range “from 1 wt % to 10 wt %” includes 1 wt % and 10 wt % within the recited range.

[0112] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, 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. Additionally, 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.

[0113] All numerical values within the detailed description herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0114] All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including” for purposes of UnitedStates law. Likewise whenever a composition, an element or a group of elements is 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.

[0115] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS 1. An elastomer composition, comprising: a first elastomer, a second elastomer, and a nucleophile, wherein; the first elastomer is a copolymer comprising p-methlystyrene, p-halomethylstyrene, and isobutylene derived units, the first elastomer comprising about 30 phr to about 100 phr of the elastomeric composition; and the second elastomer comprises isobutylene derived repeat units and comprises about 30 phr to about 75 phr of the elastomeric composition.

2. The elastomer composition claim 1, wherein the first elastomer is a halogenated poly(isobutylene-co-p-methylstyrene) that can be represented byeach of m, n, and z is independently a numerical value representing the number of respective repeat units along the polymer backbone.

3. The elastomer composition of claim 2, wherein X is selected from bromine and chlorine.

4. The elastomer composition of claim 3, wherein X comprises about 0.3 wt % to about 4.5 wt % of the first elastomer.

5. The elastomer composition of claim 2, wherein the first elastomer comprises about 0.1 mol % to about 7.5 mol % p-halomethylstyrene units, relative to total of p-methylstyrene and p- halomethylstyrene derived units.

6. The elastomer composition of claim 2, wherein the combination of the p-halomethylstyrene units and the p-methylstyrene units comprise about 0.5 wt % to about 30 wt % of the first elastomer.

7. The elastomer composition of claim 1, wherein the second elastomer is partially crosslinked.

8. The elastomer composition of claim 1, wherein the second elastomer is a vis-broken polymer capable of ionomer formation.

9. The elastomer composition of claim 1, wherein the composition further comprises one or more additives selected from the group consisting of fillers, dyes, pigments, antioxidants, heat and light stabilizers, plasticizers, oils, and combinations thereof.

10. An elastomeric composition, comprising: a first elastomer, a second elastomer, and a nucleophilic compound, wherein; the first elastomer is a copolymer comprising p-methylstyrene, p-halomethylstyrene, and isobutylene derived repeat units; the first elastomer 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 agent, the nucleophilic compound comprising about 1 phr to about 5 phr of the elastomeric compostion.

11. The elastomeric network of claim 10, wherein the nucleophilic compound is represented byA is a nitrogen or phosphorus; and R1, R2, and R3are 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,12. The elastomeric network of claim 11, wherein the nucleophilic compound is selected from the group consisting of trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, and combinations thereof.

13. The elastomeric network of claim 10, wherein the nucleophilic compound is triphenylphosphine.

14. The elastomeric network of claim 10, wherein a molar ratio of the nucleophilic compound to halide of the first elastomer is about 0.2:1 to about 1.2:

1.

15. The elastomeric network of claim 10, wherein the second elastomer is selected from the group consisting of 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.

16. The elastomeric network of claim 10, wherein the second elastomer is crosslinked.

17. A method of making a tire component, the method comprising: mixing a first elastomer and a second elastomer to form an elastomer composition in a mixer, wherein: the first elastomer is a copolymer comprising p-methlystyrene, p-halomethylstyrene, and isobutylene derived repeat units; the first elastomer comprises about 30 phr to about 100 phr of the elastomeric composition; the second elastomer is butyl rubber; and the second elastomer comprises about 30 phr to about 75 phr of the elastomeric composition; blending the elastomer composition with a nucleophilic compound to form an elastomeric network, wherein: the nucleophilic compound comprises about 1.4 phr to about 2.7 phr of the elastomeric network, anda molar ratio of the nucleophilic compound to halide of the first elastomer is about 0.2:1 to about 1.2:1; and integrating the elastomeric network into one or more components of a tire.

18. The method of claim 17, wherein the elastomeric network has a M100 value of about 0.1 MPa to about 3.6 MPa.

19. The method of claim 17, wherein the elastomeric network has a tensile strength at break of about 0.03 MPa to about 15.1 MPa.

20. The method of claim 17, wherein the elastomeric network has an elongation at break of about 130 % to about 1380%.

21. The method of claim 17, wherein the elastomeric network has an O2 permeability coefficient of about 0.1 (mm)•(cc) / m²•day•mmHg to about 1.4 (mm)•(cc) / m²•day•mmHg.

22. The method of claim 17, wherein the elastomeric network has a Shore A Hardness value of about 5 to about 50.

23. The method of claim 17, wherein the nucleophilic compound is triphenylphosphine.

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