Rubber compositions and articles thereof

Abstract

To provide improved post-cure sealants for tires.SOLUTION: In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to uncured compositions that include an elastomer, a curing agent, a co-curative, and a diluent, where the diluent comprises a highly reactive polyisobutene with at least about 60 mol% of terminal vinylidene groups. In certain aspect, the diluent can include a second diluent comprising a second polyisobutene comprising at most about 20 mol% terminal vinylidene groups, a hydrocarbon oil, or a combination thereof. There are also disclosed vulcanized rubber compositions including the uncured compositions that have been vulcanized and articles, including tires and / or components of tires, comprising the vulcanized rubber compositions.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a rubber composition and an article thereof. [Background technology]

[0002]

[0001] The demand for improved tire performance has led to the development and evaluation of new materials that, when incorporated into rubber compositions, exhibit desirable properties, such as good stiffness and elasticity. For elastomeric compositions used in tire construction, such as sealants, developing compositions with improved, tunable viscoelastic properties without compromising processability can be challenging. A sealant layer applied directly to a tire after the curing process is referred to as a post-cure sealant. In some cases, such sealants are adhesively secured to exposed surfaces of the tire, such as the innermost innerliner. These post-cure sealants may not provide adequate long-term sealing against punctures. Therefore, in addition to the general need for improved elastomeric compositions used in tire construction, there is a need for improved post-cure sealants for tires. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 8,821,982 [Patent Document 2] U.S. Patent Application Publication No. 2017 / 0151740 [Non-patent literature]

[0004] [Non-Patent Document 1] The Vanderbilt Rubber Handbook (1978), pp. 344-346 Summary of the Invention [Means for solving the problem]

[0005] In accordance with the purposes of this disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to an uncured composition comprising an elastomer, a curative, a co-curative, and a diluent, wherein the diluent comprises a highly reactive polyisobutene having at least about 60 mol % terminal vinylidene groups. In certain aspects, the diluent can comprise a second diluent comprising a second polyisobutene having at most about 20 mol % terminal vinylidene groups, a hydrocarbon oil, or a combination thereof. Also disclosed are vulcanized rubber compositions comprising the vulcanized uncured composition, and articles comprising tires and / or tire components comprising the vulcanized rubber compositions.

[0006]

[0003] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one of ordinary skill in the art upon examination of the following drawings and detailed description. All such additional systems, methods, features, and advantages are intended to be included within this specification, be within the scope of this disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments can be used in all aspects of the present disclosure taught herein. Furthermore, the individual features of the dependent claims, and all optional and preferred features and modifications of the described embodiments, are combinable and interchangeable with each other.

[0007] Many aspects of the present disclosure can be better understood by reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals indicate corresponding parts throughout the several views. [Brief explanation of the drawings]

[0008] [Figure 1]

[0005] Figure 1 shows that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutene (HR-PIB) and 70% conventional polyisobutene (C-PIB) exhibits a 26% increase or 1.25 times higher elastic modulus G' according to ASTM D5289 when compared to a cured composition without HR-PIB. [Figure 2]

[0006] Figure 1 shows that cured compositions prepared from a diluent composed of 100% highly reactive polyisobutene (HR-PIB) exhibit a 140% increase or 2.4 times higher elastic modulus G' according to ASTM D5289 when compared to cured compositions without HR-PIB. [Figure 3]

[0007] Figure 1 shows that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutene (HR-PIB) and 70% conventional polyisobutene (C-PIB) exhibits a 33% increase or 1.55 times higher elastic modulus G' according to ASTM D4440 when compared to a cured composition without HR-PIB. [Figure 4]

[0008] Figure 1 shows that cured compositions prepared from a diluent composed of 100% highly reactive polyisobutene (HR-PIB) exhibit a 350% increase or 4.5 times higher elastic modulus G' according to ASTM D5289 when compared to cured compositions without HR-PIB. [Figure 5]

[0009] FIG. 1 shows that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutene (HR-PIB) and 70% conventional polyisobutene (C-PIB) exhibits a 30% reduction in loss factor tan delta according to ASTM D4440 when compared to a cured composition without HR-PIB. [Figure 6]

[0010] FIG. 1 shows that a cured composition prepared from a diluent composed of 100% highly reactive polyisobutene (HR-PIB) exhibits a 97.5% reduction in loss factor tan delta according to ASTM D4440 when compared to a cured composition without HR-PIB. DETAILED DESCRIPTION OF THE INVENTION

[0009]

[0011] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

[0010]

[0012] Numerous modifications and other embodiments of what is disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. It is therefore to be understood that the disclosure is not limited to the particular embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Those skilled in the art will recognize many variations and adaptations of the aspects described herein. These variations and adaptations are within the teachings of the present disclosure and are intended to be encompassed by the claims herein.

[0011]

[0013] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0012]

[0014] As will be apparent to one of ordinary skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has individual components and features that may be readily separated from or readily combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0013]

[0015] Any recited method may be carried out in the order of events recited or in any other order which is logically possible. That is, unless expressly stated otherwise, it is in no way intended that the methods or aspects described herein be construed as requiring that its steps be performed in a specific order. Thus, unless a method claim specifically recites in the claim or description that the steps are limited to a particular order, no order is intended to be inferred in any respect. This also applies to all possible implicit bases for interpretation, including matters of logic regarding the arrangement of steps or operational flow, the plain meaning derived from grammatical construction or punctuation, or the number or type of aspects described in the specification.

[0014]

[0016] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the publication dates provided herein may be different from the actual publication dates, which may require independent confirmation.

[0015]

[0017] Although aspects of the present disclosure may be described and claimed in particular statutory classes, such as a systems statutory class, this is for convenience only, and those skilled in the art will understand that each aspect of the present disclosure may be described and claimed in any statutory class.

[0016]

[0018] It should also be understood that the terms used herein are intended to describe only specific embodiments and are not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the disclosed compositions and methods belong. Furthermore, terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of this specification and related art, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0017]

[0019] Prior to describing the various aspects of this disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in this disclosure.

[0018] definition

[0020] As used herein, "comprising" is interpreted as specifying the presence of the stated features, integers, steps, or components as referenced, but does not exclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Furthermore, each of the terms "by," "comprising," "comprises," "comprised of," "including," "includes," "included," "involving," "involves," "involved," and "such as" are used in their open, non-limiting sense and may be used interchangeably. Furthermore, the term "comprising" is intended to include examples and embodiments encompassed by the terms "consisting essentially of" and "consisting of." Similarly, the term "consisting essentially of" is intended to include examples encompassed by the term "consisting of."

[0019]

[0021] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an "elastomer," "pre-silanized silica," or "vulcanizing agent" includes, but is not limited to, mixtures or combinations of two or more such elastomers, pre-silanized silicas, or vulcanizing agents, etc.

[0020]

[0022] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in range format. It is further understood that each endpoint of a range is significant relative to the other endpoint, and independently of the other endpoint. It is also understood that there are numerous values ​​disclosed herein, and that each value is herein disclosed as "about" a particular value in addition to the value itself. For example, if the value "10" is disclosed, "about 10" is also disclosed. Ranges can be expressed herein as "about" one particular value and / or "about" another particular value. Similarly, when values ​​are expressed as approximations, the use of the antecedent "about" will understand that the particular value forms a further aspect. For example, if the value "about 10" is disclosed, "10" is also disclosed.

[0021]

[0023] When a range is expressed, a further embodiment includes from one particular value and / or to the other particular value. For example, when the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure; for example, the phrase "from x to y" includes ranges from "x" to "y," as well as ranges greater than "x" and less than "y." Ranges may also be expressed as upper limits, e.g., "about x, y, z, or less," and should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "less than x," "less than y," and "less than z." Similarly, the phrase "about x, y, z, or more" should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "greater than x," "greater than y," and "greater than z." Furthermore, the phrase "about 'x' to 'y'," where "x" and "y" are numerical values, includes "about 'x' to about 'y'."

[0022]

[0024] It should be understood that such range formats are used for convenience and brevity and should thus be interpreted flexibly to include not only the numerical values ​​expressly recited as range limits, but also all individual numerical values ​​or subranges subsumed within that range, as if each numerical value and subrange were expressly recited. As an example, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicitly recited values ​​of about 0.1% to about 5%, but also individual values ​​within the indicated range (e.g., about 1%, about 2%, about 3%, and about 4%), and subranges (e.g., about 0.5% to about 1.1%, about 5% to about 2.4%, about 0.5% to about 3.2%, and about 0.5% to about 4.4%, as well as other possible subranges).

[0023]

[0025] As used herein, the terms "about," "approximately," "just or about," and "substantially" mean that the quantity or value in question may be an exact value or a value that provides an equivalent result or effect as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximated and / or larger or smaller, as desired, to reflect tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art to achieve an equivalent result or effect. In some circumstances, a value that will achieve an equivalent result or effect may not be reasonably determined. In such cases, as used herein, "about" and "just or about" are generally understood to mean a ±10% variation from the stated nominal value, unless otherwise indicated or inferred. In general, a quantity, size, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "just or about," whether or not expressly stated as such. When "about," "approximately," or "just or about" is used before a quantitative value, unless specifically stated otherwise, it is understood that the parameter also includes the particular quantitative value itself.

[0024]

[0026] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which said event or circumstance occurs and instances in which it does not occur.

[0025]

[0027] As used herein, the term "phr" refers to parts by weight of a respective material per 100 parts by weight of rubber or elastomer. Generally, using this convention, an elastomeric composition is composed of 100 parts by weight of rubber / elastomer. A claimed composition may contain rubbers / elastomers other than those explicitly recited in the claims, provided that the phr values ​​of the claimed rubbers / elastomers comply with the claimed phr ranges and the amounts of all rubbers / elastomers in the composition total 100 parts rubber.

[0026]

[0028] The terms "rubber" and "elastomer" may be used interchangeably herein unless otherwise indicated.

[0027]

[0029] As used herein, the term "uncured composition" refers to an unvulcanized composition comprising at least one natural or synthetic rubber component, and optionally one or more fillers, processing aids, or additional compounds. Uncured rubber is sensitive to temperature changes and tends to undergo "cold flow" (slow movement or deformation under stress) over time. In one embodiment, the uncured rubber composition is a masterbatch.

[0028]

[0030] As used herein, the term "vulcanized rubber composition" refers to a rubber composition obtained by curing or vulcanizing an uncured composition described herein, often accomplished in the presence of heat using sulfur compounds and / or other curing additives. Vulcanized or cured rubber does not undergo cold flow and is less sensitive to temperature changes compared to uncured rubber. In another aspect, the rubber composition can be cured in a mold to form a finished article, including, but not limited to, a tire.

[0029]

[0031] As used herein, the term "repeating units" referred to in the partially saturated elastomers described herein are derived from the monomers used to produce the partially saturated elastomer. For example, polybutadiene has the repeating units provided below.

[0030] [ka] In certain embodiments, when the partially saturated elastomer is the polymerization product of two different monomers (eg, A and B), the repeat unit can be represented by -AB-.

[0031]

[0032] Unless otherwise specified, pressures referred to herein are based on atmospheric pressure (ie, 1 atmosphere).

[0032] rubber composition

[0033] Disclosed herein are uncured sealant compositions, including post-cure sealant compositions comprising an elastomer, a curing agent, a co-curing agent, and a diluent, where the diluent comprises a highly reactive polyisobutene (HR-PIB). It has been unexpectedly discovered that in sealant compositions, HR-PIB interacts with the curing agent to actively contribute to crosslink formation, increasing the stiffness and elasticity of the cured composition with increasing HR-PIB content. Therefore, by varying the relative amount of HR-PIB, the crosslink density and other properties of the resulting composition can be adjusted. In certain embodiments, blending HR-PIB with other materials, such as oil or conventional PIB (C-PIB), to form a diluent can improve and cost-effectively adjust the properties of the resulting composition.

[0033]

[0034] The diluent in the sealant composition includes a highly reactive polyisobutene (HR-PIB). The HR-PIB is characterized by having at least about 60 mol% terminal vinylidene groups. Terminal functional groups, such as terminal vinylidene groups, are functional groups located at the end of the carbon chain (i.e., at a terminal position). In a further embodiment, the HR-PIB may contain at least 75 mol% terminal vinylidene groups. In another embodiment, the HR-PIB may contain at least about 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, or 95 mol% terminal vinylidene groups, with any value representing the lower or upper limit of a range (e.g., 70 mol% to 85 mol%). In one embodiment, the HR-PIB has a number average molecular weight ranging from about 500 Da to about 5,000 Da, or about 500 Da, 1,000 Da, 2,000 Da, 3,000 Da, 4,000 Da, or 5,000 Da, any value may be the lower or upper limit of the range (e.g., 500 Da to 1,000 Da).

[0034]

[0035] The diluent can further comprise a second diluent. In one embodiment, the second diluent comprises a second polyisobutene characterized by having at most about 20 mol% terminal vinylidene groups. In a further embodiment, the second polyisobutene may comprise at most about 10 mol% terminal vinylidene groups. In another embodiment, the second polyisobutene may comprise at most about 5 mol%, 10 mol%, 15 mol%, or 20 mol% terminal vinylidene groups, any value being the lower or upper limit of a range (e.g., 5 mol% to 20 mol%). In one embodiment, the second polyisobutene has a number average molecular weight in the range of about 500 Da to about 5,000 Da, or about 500 Da, 1,000 Da, 2,000 Da, 3,000 Da, 4,000 Da, or 5,000 Da, any value may be the lower or upper limit of the range (e.g., 500 Da to 1,000 Da).

[0035]

[0036] In other embodiments, the second diluent may comprise a hydrocarbon oil. Examples of hydrocarbon oils include, but are not limited to, mineral oil, vegetable oil, or a combination thereof. Mineral oils may include, but are not limited to, aromatic oil, naphthenic oil, paraffinic oil, MES oil, TDAE oil, RAE oil, and SRAE oil. Vegetable oils may include, but are not limited to, sunflower oil, soybean oil, corn oil, castor oil, and canola oil. In other embodiments, the second diluent may comprise a combination of a second polyisobutene and a hydrocarbon oil.

[0036]

[0037] In one embodiment, the weight ratio of HR-PIB to the second diluent (HR-PIB:second diluent) can be about 1:20 to about 20:1, or about 1:20, 1:15, 1:10, 1:5, 1:4, 1:2, 1:1, 2:1, 4:0, 5:1, 10:1, 15:1, or 20:1, with any value representing the lower or upper limit of the range (e.g., 1:20 to 1:5). In one embodiment, the diluent (including HR-PIB and the second diluent) is present in the sealant composition in an amount of about 10 wt% to about 80 wt%, or about 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, with any value representing the lower or upper limit of the range (e.g., 50 wt% to 80 wt%). In another embodiment, the diluent (including the HR-PIB and the second diluent) is present in the sealant composition in an amount of about 100 phr to about 600 phr, or 100 phr, 150 phr, 200 phr, 250 phr, 300 phr, 350 phr, 400 phr, 450 phr, 500 phr, 550 phr, or 600 phr, any value being a lower or upper limit of a range (e.g., 200 phr to 500 phr). In other embodiments, the diluent consists of HR-PIB (i.e., the diluent is 100% HR-PIB).

[0037]

[0038] In one embodiment, the elastomer can be present in the sealant composition in an amount of about 10 wt% to about 50 wt%, or 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, any value may be the lower or upper limit of the range (e.g., 20 wt% to 40 wt%). In one embodiment, the elastomer includes repeat units formed by residues of monomers selected from one or more of ethylene, propylene, isobutene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

[0038]

[0039] In other embodiments, the elastomer may be selected from isoprene-isobutylene rubber (butyl rubber, IIR), halogenated isoprene-isobutylene rubber (HIIR), ethylene-propylene-diene-terpolymer (EPDM), styrene-butadiene copolymer (SBR), acrylonitrile-butadiene copolymer (AB), acrylonitrile-butadiene-styrene copolymer (ABS), polybutadiene, natural rubber, cis polyisoprene, and any combination thereof. In further embodiments, the elastomer generally has a number average molecular weight (M) of 100,000 Da to 500,000 Da. n ) Elastomer with molecular weight M n may be determined by methods known in the art, such as gel permeation chromatography according to ASTM D3536 or equivalent.

[0039]

[0040] In one embodiment, the elastomer is a butyl rubber containing repeating units of isobutene and a conjugated diene. In one embodiment, about 85 wt% to about 99.5 wt%, or about 85 wt%, 90 wt%, 95 wt%, or 99 wt% of the butyl rubber is isobutene repeating units, with any value representing the lower and upper limits of the range (e.g., 90 wt% to 99 wt%). In one embodiment, about 0.1 wt% to about 15.0 wt%, or about 0.1 wt%, 3 wt%, 6 wt%, 9 wt%, 12 wt%, or 15 wt% of the butyl rubber is conjugated diene repeating units, with any value representing the lower and upper limits of the range (e.g., 3 wt% to 6 wt%). In a further embodiment, the conjugated diene has 4 to 8 carbon atoms, such as butadiene, isoprene, and hexadiene. In another embodiment, the conjugated diene is isoprene.

[0040]

[0041] In one embodiment, the curing agent can be present in the sealant composition in an amount of about 0.5 wt % to about 5.0 wt %, or 0.5 wt %, 1.0 wt %, 2.0 wt %, 3.0 wt %, 4.0 wt %, or 5.0 wt %, where any value may be the lower or upper limit of a range (e.g., 2.0 wt % to 4.0 wt %). In one embodiment, the curing agent present in the sealant composition is a quinoid curing agent. In a further embodiment, the curing agent can be selected from benzoquinone dioxime (BQD), dibenzoyl-p-quinone dioxime, p,p-dibenzoylquinone dioxime, p-dinitrosobenzene, N-methyl-N,4-dinitrosaniline, or any combination thereof. In another embodiment, the curing agent is BQD.

[0041]

[0042] In one embodiment, the co-curing agent can be present in the sealant composition in an amount of about 1 wt % to about 15 wt %, or about 1 wt %, 3 wt %, 6 wt %, 9 wt %, 12 wt %, or 15 wt %, with any value being the lower or upper limit of a range (e.g., 9 wt % to 12 wt %). In one embodiment, the co-curing agent is an oxidizing agent. In a further embodiment, the co-curing agent is an organic peroxide. In one embodiment, the organic peroxide may be selected from diaroyl peroxides, diacyl peroxides, and peroxyesters. In a further embodiment, the co-curing agent is dibenzoyl peroxide. In another embodiment, the co-curing agent is selected from ZnO, MgO, CaO, or any combination thereof. In one embodiment, the sealant composition comprises a dibenzoyl peroxide co-curing agent and a BQD curing agent.

[0042]

[0043] In one embodiment, a resin is also present in the sealant composition. Suitable resins include, but are not limited to, hydrocarbon resins, phenolic / acetylene resins, rosin-derived resins, and mixtures thereof. Hydrocarbon resins can include coumarone-indene resins, petroleum resins, terpene polymers, and mixtures thereof.

[0043] Preparation and application of rubber compositions

[0044] The compositions disclosed herein may be compounded by methods generally known in the rubber compounding art. In one aspect, these methods include mixing the aforementioned components of the sealant composition with other conventional compounding ingredients, including fillers such as carbon black and silica, antidegradants such as antioxidants and antiozonants, colorants, processing aids, cure accelerators, cure retarders, and the like. In one aspect, the cure accelerator may be selected from dithiocarbamate accelerators, thiuram accelerators, diphenylguanidine accelerators, benzothiazole sulfenamide accelerators, or any combination thereof. The cure accelerator may include derivatives; for example, benzothiazole sulfenamide accelerators include benzothiazole sulfenamides, which may also include derivatives of benzothiazole sulfenamides. In other aspects, the cure accelerator may include amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthates. In one aspect, the cure retarder may be selected from ethylene glycol, alkyl-substituted ethylene glycols, ethylenediamines, and alkyl-substituted ethylenediamines. In a further embodiment, the cure retarder may be selected from ethylene glycol, propylene glycol (i.e., α-propylene glycol), ethylenediamine, methylethylenediamine, N,N-dimethylethylenediamine, and 1,2-dimethylethylenediamine. In one embodiment, the antioxidant and antioxidant may each be included individually in an amount of about 1 phr to about 5 phr. In one embodiment, the antioxidant may be selected from diphenyl-p-phenylenediamine and others, such as those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. In another embodiment, the antiozonant may be selected from N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD) and N,N'-dixylene-p-phenylenediamine (DTPD). In another embodiment, basic oxides, such as zinc oxide, magnesium oxide, and calcium oxide, may be included in an amount of about 1 phr to about 5 phr.Mixing of the sealant composition may be accomplished by combining the elastomer and other components in a rubber mixer, such as, for example, a Brabender internal mixer, an extruder, a conical mixer, etc. Suitable processes for mixing and applying sealants to tire innerliners are as disclosed, for example, in U.S. Patent No. 8,821,982, which is incorporated herein by reference.

[0044]

[0045] Also disclosed herein are rubber compositions comprising any of the sealant compositions disclosed herein that have been vulcanized, and articles comprising the vulcanized sealant compositions. In one aspect, the article comprises a tire, such as a pneumatic tire, or a tire component. The tire may be a race tire, passenger tire, aircraft tire, agricultural, earthmoving, off-road, truck tire, or the like. In one embodiment, the tire is a passenger or truck tire. The tire may also be radial or bias. Such tires may be built, shaped, molded, and cured by various methods known and readily apparent to those skilled in such art. The tire component may be a tread, base, sidewall, apex, chafer, sidewall insert, wire coat, innerliner, or any combination thereof. In a further aspect, the sealant composition can be applied to a cured tire. In a further aspect, the sealant composition can be applied to the innerliner of a cured tire. Prior to applying the sealant, the tire surface can be cleaned of impurities to improve adhesion of the sealant to the tire surface. In one embodiment, the surface of the tire innerliner is cleaned using the laser technology described in U.S. Patent Application Publication No. 2017 / 0151740, which is incorporated herein by reference.

[0045]

[0046] The use of high-reactivity polyisobutene (HR-PIB), with or without a second diluent, can modify the physical properties of the cured rubber compositions described herein. In one embodiment, the modulus of elasticity of the cured rubber composition can be modified. In one embodiment, the cured rubber composition has a modulus of elasticity G' at 6.1% strain, 70°C, and a frequency of 1.672 Hz, based on ASTM D5289, that is at least 20%, 30%, 40%, 50%, 75%, or up to 100% greater than the modulus of elasticity G' of a cured composition without the high-reactivity polyisobutene. In another embodiment, the cured rubber composition has a modulus of elasticity G' at 0.5% strain, 60°C, and a frequency of 0.005 Hz, based on ASTM D4440, that is at least 30%, 40%, 50%, 75%, or up to 100% less than the loss factor tan delta of a cured composition without the high-reactivity polyisobutene.

[0046]

[0047] In another embodiment, the cured rubber composition has a loss factor tan delta based on ASTM D4440 at 0.5% strain, 60°C, and a frequency of 0.005 Hz that is at least 30% lower, 40% lower, 50% lower, 75% lower, or up to 100% lower than the loss factor tan delta of the cured composition without the highly reactive polyisobutene.

[0047]

[0048] Having generally described aspects of the present disclosure above, the following examples describe some additional aspects of the disclosure. Aspects of the present disclosure will be described in conjunction with the following examples and corresponding documents and figures, but there is no intent to limit the aspects of the disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.

[0048] Aspects

[0049] The present disclosure can be described according to the following numbered aspects, which should not be confused with the claims.

[0049]

[0050] Embodiment 1. An uncured composition comprising an elastomer, a curing agent, a co-curative, and a diluent, wherein the diluent comprises a highly reactive polyisobutene containing at least about 60 mol % terminal vinylidene groups.

[0051] Aspect 2. The composition of Aspect 1, wherein the diluent comprises highly reactive polyisobutene.

[0052] Embodiment 3. The composition of embodiment 1, wherein the diluent comprises a second diluent comprising a second polyisobutene comprising at most about 20 mol % terminal vinylidene groups, a hydrocarbon oil, or a combination thereof.

[0053] Aspect 4. The composition of Aspect 3, wherein the weight ratio of the highly reactive polyisobutene to the second diluent is from about 1:20 to about 20:1.

[0054] Aspect 5. The composition of Aspect 3, wherein the weight ratio of the highly reactive polyisobutene to the second diluent is from about 1:20 to about 1:2.

[0055] Embodiment 6. The composition of any one of embodiments 3-5, wherein the second diluent comprises a second polyisobutene comprising at most about 10 mol % terminal vinylidene groups.

[0056] Aspect 7. The composition of any one of Aspects 3-5, wherein the second diluent comprises a second polyisobutene comprising from about 5 mol % to at most 20 mol % terminal vinylidene groups.

[0057] Aspect 8. The composition of any one of Aspects 3-7, wherein the second polyisobutene has an average molecular weight of from about 500 Daltons to about 5,000 Daltons.

[0058] Embodiment 9. The composition of any one of embodiments 3-5, wherein the second diluent comprises a hydrocarbon oil.

[0059] Embodiment 10. The composition of any one of embodiments 3-5, wherein the hydrocarbon oil comprises a mineral oil, a vegetable oil, or a combination thereof.

[0060] Aspect 11. The composition of any one of Aspects 1-10, wherein the highly reactive polyisobutene comprises at least 75 mol % terminal vinylidene groups.

[0061] Aspect 12. The composition of any one of Aspects 1-10, wherein the highly reactive polyisobutene comprises from about 60 mol % to less than 95 mol % terminal vinylidene groups.

[0062] Aspect 13. The composition of any one of Aspects 1 to 12, wherein the highly reactive polyisobutene has an average molecular weight of from about 500 daltons to about 5,000 daltons.

[0063] Embodiment 14. The composition of any one of embodiments 1-13, wherein the elastomer comprises repeat units formed by residues of monomers selected from one or more of ethylene, propylene, isobutene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

[0064] Embodiment 15. The composition of any one of embodiments 1-14, wherein the curing agent is a quinoid.

[0065] Embodiment 16. The composition of any one of embodiments 1-14, wherein the curing agent is selected from the group consisting of benzoquinone dioxime, p,p-dibenzoylquinone dioxime, dibenzoyl-p-quinone dioxime, p-dinitrosobenzene, N-methyl-N,4-dinitrosaniline, and any combination thereof.

[0066] Embodiment 17. The composition of any one of embodiments 1-16, wherein the co-curing agent is an oxidizing agent.

[0067] Embodiment 18. The composition of any one of embodiments 1-16, wherein the co-curing agent is an organic peroxide.

[0068] Embodiment 19. The composition of any one of embodiments 1 to 16, wherein the co-curing agent is a diaroyl peroxide, a diacyl peroxide, or a peroxyester.

[0069] Embodiment 20. The composition of any one of embodiments 1-16, wherein the curing agent is benzoquinone dioxime and the co-curing agent is dibenzoyl peroxide.

[0070] Embodiment 21. The composition of any one of embodiments 1 to 20, wherein the diluent is about 50 weight percent to about 80 weight percent of the composition.

[0071] Aspect 22. A vulcanized rubber composition comprising the uncured composition of any one of Aspects 1 to 21 that has been vulcanized.

[0072] Embodiment 23. The composition of embodiment 22, wherein the composition after curing has an elastic modulus G' at 6.1% strain, 70°C, and a frequency of 1.672 Hz, based on ASTM D5289, that is at least 20% greater than the elastic modulus G' of the cured composition that does not contain the highly reactive polyisobutene.

[0073] Embodiment 24. The composition of embodiment 22, wherein the composition after curing has an elastic modulus G' based on ASTM D4440 at 0.5% strain, 60°C, and a frequency of 0.005 Hz that is at least 30% lower than the loss factor tan delta of the cured composition that does not contain the highly reactive polyisobutene.

[0074] Embodiment 25. The composition of embodiment 22, wherein the composition after curing has a loss factor tan delta according to ASTM D4440 at 0.5% strain, 60°C, and a frequency of 0.005 Hz that is at least 30% lower than the loss factor tan delta of a cured composition that does not contain the highly reactive polyisobutene.

[0075] Embodiment 26. An article comprising the vulcanized rubber composition of any one of embodiments 22-25.

[0076] Embodiment 27. The article of embodiment 26, wherein the article comprises a tire or a tire component.

[0077] Embodiment 28. The article of embodiment 27, wherein the tire component comprises a tread, a sidewall, an apex, a chafer, a sidewall insert, a wire coat, an inner liner, or any combination thereof. [Example]

[0050]

[0078] The following examples are provided to provide those skilled in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed herein are made and evaluated. These examples are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is ° C. or is ambient temperature, and pressure is at or near atmospheric pressure.

[0051] [Example 1] Evaluation of rubber composition

[0079] The rheological properties of the cured rubber compositions described herein were evaluated. The test methods used to evaluate the cured compositions are shown in Table 1. The test results are shown in Table 2 and Figures 1-6.

[0052] [Table 1]

[0053] [Table 2]

[0054]

[0080] As shown in the data above, rubber compositions prepared with a diluent consisting of 100% high-reactivity polyisobutene (HR-PIB) or a mixture of high-reactivity polyisobutene (HR-PIB) and conventional polyisobutene (C-PIB) had significantly higher elastic moduli (G') when compared to cured rubber compositions not prepared with HR-PIB. Furthermore, rubber compositions prepared with a diluent consisting of 100% high-reactivity polyisobutene (HR-PIB) or a mixture of high-reactivity polyisobutene (HR-PIB) and conventional polyisobutene (C-PIB) also had significantly reduced loss factor (tan delta) when compared to cured rubber compositions not prepared with HR-PIB.

[0081] It should be emphasized that the above-described embodiments of the present disclosure are merely possible implementations, set forth for a clear understanding of the principles of the present disclosure. Many variations and modifications may be made to the above-described embodiments without substantially departing from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims

1. An uncured composition comprising an elastomer, a curing agent, a co-curing agent, and a diluent, wherein the diluent comprises a highly reactive polyisobutene containing at least about 60 mol % terminal vinylidene groups.

2. 2. The composition of claim 1, wherein said diluent comprises said highly reactive polyisobutene.

3. 10. The composition of claim 1, wherein the diluent comprises a second diluent comprising a second polyisobutene containing at most about 20 mol% terminal vinylidene groups, a hydrocarbon oil, or a combination thereof.

4. 4. The composition of claim 3, wherein the weight ratio of said highly reactive polyisobutene to said second diluent is from about 1:20 to about 20:

1.

5. 4. The composition of claim 3, wherein the weight ratio of the highly reactive polyisobutene to the second diluent is from about 1:20 to about 1:

2.

6. 4. The composition of claim 3, wherein the second diluent comprises a second polyisobutene containing at most about 10 mol % terminal vinylidene groups.

7. 4. The composition of claim 3, wherein the second diluent comprises a second polyisobutene containing from about 5 mol % to at most 20 mol % terminal vinylidene groups.

8. 4. The composition of claim 3, wherein the second polyisobutene has an average molecular weight of from about 500 Daltons to about 5,000 Daltons.

9. The composition of claim 3 , wherein the second diluent comprises a hydrocarbon oil.

10. The composition of claim 3 , wherein the hydrocarbon oil comprises a mineral oil, a vegetable oil, or a combination thereof.

11. 10. The composition of claim 1, wherein the highly reactive polyisobutene contains from about 60 mol % to less than 95 mol % terminal vinylidene groups.

12. 10. The composition of claim 1, wherein the highly reactive polyisobutene has an average molecular weight of from about 500 Daltons to about 5,000 Daltons.

13. 10. The composition of claim 1, wherein the elastomer comprises repeat units formed by residues of monomers selected from one or more of ethylene, propylene, isobutene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

14. 2. The composition of claim 1, wherein the curing agent is a quinoid selected from the group consisting of benzoquinone dioxime, p,p-dibenzoylquinone dioxime, dibenzoyl-p-quinone dioxime, p-dinitrosobenzene, N-methyl-N,4-dinitrosaniline, and any combination thereof.

15. 10. The composition of claim 1, wherein the co-curing agent is an organic peroxide selected from the group consisting of diaroyl peroxides, diacyl peroxides, and peroxyesters.

16. The composition of claim 1, wherein the diluent is from about 50 percent to about 80 percent by weight of the composition.

17. A vulcanized rubber composition comprising the uncured composition of claim 1 which has been vulcanized.

18. the composition after curing has an elastic modulus G' at 6.1% strain, 70°C, and a frequency of 1.672 Hz according to ASTM D5289 that is at least 20% greater than the elastic modulus G' of a cured composition that does not contain the highly reactive polyisobutene; or the composition after curing has a modulus of elasticity G' at 0.5% strain, 60°C, and a frequency of 0.005 Hz according to ASTM D4440 that is at least 30% less than the loss factor tan delta of a cured composition that does not contain the highly reactive polyisobutene; or 18. The vulcanized rubber composition of claim 17, wherein the composition after curing has a loss factor tan delta according to ASTM D4440 at 0.5% strain, 60°C, and a frequency of 0.005 Hz that is at least 30% lower than the loss factor tan delta of a cured composition that does not contain the high-reactivity polyisobutene.

19. 18. An article comprising the vulcanized rubber composition of claim 17.

20. 20. The article of claim 19, wherein the article comprises a tire or tire component.

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