Rubber composition and product thereof

Abstract

The invention relates to a rubber composition and a product thereof. According to object (s) of the present disclosure, as implemented and broadly described herein, the present disclosure, in one aspect, relates to an uncured composition comprising an elastomer, a curing agent, a co-curing agent, and a diluent, where the diluent comprises a highly reactive polyisobutylene having at least about 60 mol% of a terminal vinylidene group. In certain aspects, the diluent may include a second diluent comprising a second polyisobutylene having up to about 20 mol% terminal vinylidene, a hydrocarbon oil, or a combination thereof. Vulcanized rubber compositions comprising a vulcanized uncured composition, and articles comprising tires and / or tire components comprising the vulcanized rubber compositions are also disclosed.

Description

Technical Field

[0001] The present invention relates to an uncured composition, and more particularly to a vulcanized rubber composition and articles made therefrom. Background Art

[0002] The demand for improved tire performance has led to the development and evaluation of new materials that exhibit desirable properties, such as good stiffness and elasticity, when incorporated into rubber compositions. For elastomeric compositions used to manufacture tires, such as sealants, it can be challenging to develop compositions with improved and adjustable viscoelastic properties without compromising processability. The sealant layer applied directly to the tire after the curing process is referred to as a post-cure sealant. In some cases, such sealants are bonded to exposed surfaces of the tire, such as the innermost liner. These post-cure sealants may not provide sufficient long-term sealing to prevent punctures. Therefore, in addition to the general demand for improved elastomeric compositions used to manufacture tires, there is also a need for improvements in post-cure sealants for tires. Summary of the Invention

[0003] In accordance with one or more purposes of the present disclosure, as embodied and broadly described herein, the present disclosure relates in one aspect to an uncured composition comprising an elastomer, a curing agent, a co-curing agent, and a diluent, wherein the diluent comprises a highly reactive polyisobutylene having at least about 60 mole % of terminal vinylidene groups. In certain aspects, the diluent may comprise a second diluent, a hydrocarbon oil, or a combination thereof, the second diluent comprising a second polyisobutylene comprising up to about 20 mole % of terminal vinylidene groups. Also disclosed are vulcanized rubber compositions comprising the vulcanized uncured composition, and articles comprising tires and / or tire components comprising the vulcanized rubber compositions.

[0004] Other systems, methods, features, and advantages of the present disclosure will be or will become apparent to those skilled in the art upon examination of the following figures and detailed description. All such additional systems, methods, features, and advantages are intended to be included within this specification, be within the scope of the present disclosure, and be protected by the appended claims. Furthermore, all optional and preferred features and modifications of the described embodiments may be applied to all aspects of the disclosure taught herein. Furthermore, the various features of the dependent claims and all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with each other.

[0005] The present invention discloses the following solutions:

[0006] Option 1. An uncured composition comprising:

[0007] An elastomer, a curing agent, a co-curing agent, and a diluent, wherein the diluent comprises a highly reactive polyisobutylene comprising at least about 60 mole percent terminal vinylidene groups.

[0008] Option 2. The composition of Option 1, wherein the diluent consists of highly reactive polyisobutylene.

[0009] Item 3. The composition of item 1, wherein the diluent comprises a second diluent, a hydrocarbon oil, or a combination thereof, the second diluent comprising a second polyisobutylene comprising up to about 20 mol % of terminal vinylidene groups.

[0010] Item 4. The composition of item 3, wherein the weight ratio of the highly reactive polyisobutylene to the second diluent is from about 1:20 to about 20:1.

[0011] Item 5. The composition of item 3, wherein the weight ratio of the highly reactive polyisobutylene to the second diluent is from about 1:20 to about 1:2.

[0012] Item 6. The composition of item 3, wherein the second diluent comprises a second polyisobutylene comprising up to about 10 mol % of terminal vinylidene groups.

[0013] Item 7. The composition of item 3, wherein the second diluent comprises a second polyisobutylene comprising from about 5 mol% to at most 20 mol% of terminal vinylidene groups.

[0014] Item 8. The composition of item 3, wherein the second polyisobutylene has an average molecular weight of about 500 Daltons to about 5,000 Daltons.

[0015] 9. The composition of claim 3, wherein the second diluent comprises a hydrocarbon oil.

[0016] 10. The composition of claim 3, wherein the hydrocarbon oil comprises mineral oil, vegetable oil, or a combination thereof.

[0017] Item 11. The composition of item 1, wherein the highly reactive polyisobutylene comprises from about 60 mol% to less than 95 mol% of terminal vinylidene groups.

[0018] Item 12. The composition of item 1, wherein the highly reactive polyisobutylene has an average molecular weight of about 500 Daltons to about 5,000 Daltons.

[0019] 13. The composition of claim 1, wherein the elastomer comprises repeating units formed from residues of one or more monomers selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

[0020] 14. The composition of claim 1 , wherein the curing agent is a quinone-type compound selected from the group consisting of benzoquinone dioxime, p-,p-dibenzoylquinone dioxime, dibenzoyl-p-quinone dioxime, p-dinitrosobenzene, N-methyl-N,4-dinitrosoaniline, and any combination thereof.

[0021] 15. 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.

[0022] 16. The composition of claim 1, wherein the diluent comprises from about 50% to about 80% by weight of the composition.

[0023] A vulcanized rubber composition comprising the vulcanized uncured composition according to claim 1.

[0024] 18. The composition of claim 17, wherein the cured composition 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% higher than the elastic modulus G' of a cured composition that does not contain the highly reactive polyisobutylene, or

[0025] The cured composition has an elastic modulus G' at 0.5% strain, 60° C., and a frequency of 0.005 Hz based on ASTM D4440 that is at least 30% lower than the loss factor tan δ of a cured composition that does not contain the highly reactive polyisobutylene, or

[0026] The cured composition has a loss factor tan δ at 0.5% strain, 60° C., and a frequency of 0.005 Hz based on ASTM D4440 that is at least 30% lower than the loss factor tan δ of a cured composition that does not include the high-reactivity polyisobutylene.

[0027] Option 19. An article comprising the vulcanized rubber composition according to Option 17.

[0028] Item 20. The article of item 19, wherein the article comprises a tire or a component of a tire. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Many aspects of the present disclosure may be better understood with reference to the following drawings. The components in the drawings are not necessarily drawn to scale, but emphasis is placed on clearly illustrating the principles of the present disclosure. Additionally, in the drawings, like reference numerals indicate corresponding parts throughout the various views.

[0030] Figure 1 It is shown that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutylene (HR-PIB) and 70% conventional polyisobutylene (C-PIB) results in an elastic modulus G' based on ASTM D5289 that is 26% higher or 1.25 times higher when compared to a cured composition that does not contain HR-PIB.

[0031] Figure 2 It is shown that a cured composition prepared with a diluent composed of 100% highly reactive polyisobutylene (HR-PIB) results in an elastic modulus G' that is increased by 140% or 2.4 times higher based on ASTM D5289 when compared to a cured composition that does not contain HR-PIB.

[0032] Figure 3 It is shown that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutylene (HR-PIB) and 70% conventional polyisobutylene (C-PIB) results in an elastic modulus G' that is increased by 33% or 1.55 times higher based on ASTM D4440 when compared to a cured composition that does not contain HR-PIB.

[0033] Figure 4 It is shown that a cured composition prepared with a diluent composed of 100% highly reactive polyisobutylene (HR-PIB) results in a 350% increase in elastic modulus G' based on ASTM D5289, or 4.5 times higher, when compared to a cured composition not containing HR-PIB.

[0034] Figure 5 It is shown that a cured composition prepared from a diluent mixture of 30% highly reactive polyisobutylene (HR-PIB) and 70% conventional polyisobutylene (C-PIB) results in a 30% reduction in loss factor tan δ based on ASTM D4440 when compared to a cured composition that does not contain HR-PIB.

[0035] Figure 6 It is shown that a cured composition prepared with a diluent composed of 100% highly reactive polyisobutylene (HR-PIB) results in a 97.5% reduction in the loss factor, tan δ, based on ASTM D4440, when compared to a cured composition that does not contain HR-PIB.

[0036] Other advantages of the present invention will be set forth in part in the description that follows and in part will be obvious from the description, or may be learned by practice of the present invention. The advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the invention as claimed. DETAILED DESCRIPTION

[0037] Having benefited from the teachings presented in the foregoing description and the associated drawings, those skilled in the art of the disclosed compositions and methods will recognize many modifications and other embodiments disclosed herein. Therefore, it should be understood that the present disclosure is not limited to the specific embodiments disclosed, and 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 adjustments of the aspects described herein. These variations and adjustments are intended to be included in the teachings of the present disclosure and to be covered by the claims herein.

[0038] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0039] As will be apparent to those skilled in the art after reading this disclosure, each individual embodiment described and illustrated herein has discrete components and features that may be readily separated or combined with the features of any of the other several embodiments without departing from the scope or spirit of the disclosure.

[0040] Any enumerated method may be performed in the order of the enumerated events or in any other order that is logically possible. That is, unless otherwise expressly stated, it is not intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a particular order. Therefore, in the absence of a method claim in the claims or specification that the steps are to be limited to a particular order, no order is intended to be inferred in any respect. This applies to any possible non-explicit basis for interpretation, including logical content regarding the arrangement of steps or operational flows, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0041] All publications mentioned herein are incorporated herein by reference to disclose and describe the method and / or material relevant to the cited publications. The publications discussed herein only provide the disclosures prior to the application's filing date. This paper should not be construed as admitting that the present invention has no right to be earlier than these publications by virtue of prior inventions. In addition, the publication date provided herein may be different from the actual publication date, which may require independent confirmation.

[0042] While aspects of the present disclosure may be described and claimed in certain legal categories, such as the system legal category, this is merely for convenience, and those skilled in the art will understand that each aspect of the present disclosure may be described and claimed in any legal category.

[0043] It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will also be understood that those terms as defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the specification and the relevant art, and should not be interpreted in an idealized or overly formal sense, unless explicitly defined herein.

[0044] Before describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in this disclosure.

[0045] definition

[0046] As used herein, "comprising" should be interpreted as specifying the presence of the features, integers, steps or components mentioned, but not excluding 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-restrictive sense and are used interchangeably. Furthermore, the term "comprising" is intended to include instances and aspects encompassed by the terms "consisting essentially of" and "consisting of." Similarly, the term "consisting essentially of is intended to include instances encompassed by the term "consisting of."

[0047] As used in the 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.

[0048] It should be noted that ratios, concentrations, amounts and other numerical data can be expressed in range form in this article. It will also be understood that the endpoints of each range are meaningful relative to and independent of the other endpoint. It will also be understood that many values ​​are disclosed herein, and in addition to the value itself, each value is also disclosed herein as "about" this particular value. For example, if the value "10" is disclosed, "about 10" is also disclosed. In this article, ranges can be expressed as from "about" a particular value and / or to "about" another particular value. Similarly, when a value is expressed as an approximation by using the antecedent "about", it will be understood that the particular value forms another aspect. For example, if the value "about 10" is disclosed, "10" is also disclosed.

[0049] When expressing a range, on the other hand, it includes from a specific value and / or to another specific value. For example, when the range includes one or two limits, the scope of any one or two of the limits included is also included in the present disclosure, such as the phrase "x to y" includes the scope from "x" to "y" and the scope greater than "x" and less than "y". Scope can also be expressed as an upper limit, such as "about x, y, z or less", and should be interpreted as including the specific scope of "about x", "about y" and "about z" and the scope of "less than x", "less than y" and "less than z". Similarly, the phrase "about x, y, z or more" should be interpreted as including the specific scope of "about x", "about y" and "about z" and the scope of "greater than x", "greater than y" and "greater than z". In addition, the phrase "about "x" to "y" (wherein "x" and "y" are numerical values) includes "about "x" to about "y".

[0050] It should be understood that this range format is used for convenience and brevity and should, therefore, be interpreted in a flexible manner to include not only the values ​​explicitly recited as the limits of the range, but also all individual values ​​or subranges contained within the range, as if each value and subrange were explicitly recited. For illustration, 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 ​​(e.g., about 1%, about 2%, about 3%, and about 4%) and subranges within the indicated range (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).

[0051] As used herein, the terms "about," "approximately," "at or about," and "substantially" mean that the amount or value in question can be the exact value or value that provides an equivalent result or effect as described in the claims or taught herein. That is, it should be understood that amounts, dimensions, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as necessary to reflect tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, so that an equivalent result or effect is achieved. In some cases, a value that provides an equivalent result or effect cannot be reasonably determined. In such cases, it is generally understood that, as used herein, "about" and "at or about" refer to a ±10% variation of the nominal value shown, unless otherwise indicated or inferred. In general, an amount, dimension, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "at or about," regardless of whether it is explicitly stated as such. It should be understood that when "about," "approximately," or "at or about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless otherwise specifically stated.

[0052] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0053] As used herein, the term "phr" refers to parts by weight of the respective material per 100 parts by weight of rubber or elastomer. Typically, using this convention, an elastomeric composition comprises 100 parts by weight of rubber / elastomer. The claimed compositions may contain other rubbers / elastomers in addition to those explicitly mentioned in the claims, provided that the phr value of the claimed rubber elastomer falls within the claimed phr range and the amount of all rubbers / elastomers in the composition results in a total of 100 parts rubber.

[0054] Unless otherwise indicated, the terms "rubber" and "elastomer" are used interchangeably herein.

[0055] As used herein, term " uncured composition " refers to the composition comprising at least one natural or synthetic rubber component and optional one or more fillers, processing aids or other compounds, which is not vulcanized. Uncured rubber is sensitive to temperature changes and has a trend of experiencing " cold flow " (slowly moving or deforming under stress) over time. In one aspect, uncured rubber composition is a masterbatch.

[0056] As used herein, term " vulcanized rubber composition " refers to the rubber composition obtained by obtaining uncured composition as described herein and solidifying or vulcanizing, usually using sulfur compound and / or other curing additives and completing under the existence of heat. The rubber of vulcanization or solidification does not experience cold flow, and is less sensitive to temperature changes with respect to uncured rubber. On the other hand, rubber composition can be solidified in a mold to form the finished products (finished articles) including but not limited to tire.

[0057] As used herein, the term "repeating units" as referenced in the partially saturated elastomers described herein are derived from the monomers used to prepare the partially saturated elastomer. For example, polybutadiene has repeating units as provided below.

[0058]

[0059] In certain aspects, when the partially saturated elastomer is the polymerization product of two different monomers (eg, A and B), the repeating unit can be represented by -AB-.

[0060] Unless otherwise indicated, pressures referred to herein are based on atmospheric pressure (ie, one atmosphere).

[0061] Rubber composition

[0062] Disclosed herein are uncured sealant compositions, including post-cured sealant compositions, comprising an elastomer, a curing agent, a co-curing agent, and a diluent, wherein the diluent comprises a highly reactive polyisobutylene (HR-PIB). In the sealant compositions, it was unexpectedly discovered that the HR-PIB interacts with the curing agent and actively promotes crosslink formation, with the stiffness and elasticity of the cured composition increasing with increasing HR-PIB content. This allows the crosslink density and other properties of the resulting composition to be adjusted by varying the relative amount of HR-PIB. In certain aspects, blending other materials with the HR-PIB to form the diluent, such as oil or conventional PIB (C-PIB), can allow the properties of the resulting composition to be adjusted to improve and be cost-effective.

[0063] The diluent in the sealant composition includes a highly reactive polyisobutylene (HR-PIB) characterized by comprising at least about 60 mol% terminal vinylidene groups. A terminal functional group, such as a terminal vinylidene group, is a functional group located at the end (i.e., terminal position) of a carbon chain. In a further aspect, the HR-PIB may comprise at least 75 mol% terminal vinylidene groups. In another aspect, the HR-PIB may comprise at least about 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, or 95 mol% terminal vinylidene groups, wherein any value may be the lower and upper limits of a range (e.g., 70 mol% to 85 mol%). In one aspect, 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, where any value can be the lower and upper limits of the range (e.g., 500 Da to 1,000 Da).

[0064] In one aspect, the second polyisobutylene comprises a second diluent, characterized in that it comprises at most about 20 mole % of terminal vinylidene groups. In a further aspect, the second polyisobutylene comprises at most about 10 mole % of terminal vinylidene groups. In another aspect, the second polyisobutylene comprises at most about 5 mole %, 10 mole %, 15 mole % or 20 mole % of terminal vinylidene groups, wherein any value can be the lower limit and upper limit of scope (for example, 5 mole % to 20 mole %). In one aspect, the second polyisobutylene has a number average molecular weight of about 500Da to about 5,000Da or about 500Da, 1,000Da, 2,000Da, 3,000Da, 4,000Da or 5,000Da scope, wherein any value can be the lower limit and upper limit of scope (for example, 500Da to 1,000Da).

[0065] In other aspects, 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 oils, naphthenic oils, paraffin oils, MES oils, TDAE oils, RAE oils, and SRAE oils. Vegetable oils may include, but are not limited to, sunflower oil, soybean oil, corn oil, castor oil, and rapeseed oil. In other aspects, the second diluent may comprise a combination of the second polyisobutylene and a hydrocarbon oil.

[0066] In one aspect, the weight ratio of HR-PIB to the second diluent (HR-PIB:second diluent) can be from 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, any of which can be the lower or upper limit of a range (e.g., 1:20 to 1:5). In one aspect, the diluent (including HR-PIB and the second diluent) is present in the sealant composition in an amount of from 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 %, any of which can be the lower or upper limit of a range (e.g., 50 wt % to 80 wt %). In another aspect, the diluent (including HR-PIB and a second diluent) is present in the sealant composition in an amount of from 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, wherein any value can be the lower and upper limits of the range (e.g., 200 phr to 500 phr). In another aspect, the diluent consists of HR-PIB (i.e., the diluent is 100% HR-PIB).

[0067] In one aspect, the elastomer can be present in the sealant composition in an amount from about 10% to about 50% by weight, or 10%, 20%, 30%, 40%, or 50% by weight, where any value can be the lower and upper limits of the range (e.g., 20% to 40% by weight). In one aspect, the elastomer comprises repeating units formed from monomer residues of one or more selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

[0068] In other aspects, the elastomer can be selected from isoprene-isobutylene rubber (butyl rubber, IIR), halogenated isoprene-isobutylene rubber (HIIR), ethylene propylene diene monomer (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 aspects, the number average molecular weight (M) of the elastomer is selected from the group consisting of: n ) is usually between 100,000 Da and 500,000 Da. Molecular weight M n It can be determined by methods known in the art, such as by gel permeation chromatography according to ASTM D3536 or equivalent.

[0069] In one aspect, elastomer is butyl rubber, and it comprises the repeating unit of isobutylene and conjugated diene.In one aspect, about 85 % by weight to about 99.5 % by weight of butyl rubber is the repeating unit of isobutylene, or about 85 % by weight, 90 % by weight, 95 % by weight or 99 % by weight is the repeating unit of isobutylene, and wherein any value can be the lower limit and the upper limit (for example, 90 % by weight to 99 % by weight) of scope.In one aspect, about 0.1 % by weight to about 15.0 % by weight of butyl rubber is the repeating unit of conjugated diene, or about 0.1 % by weight, 3 % by weight, 6 % by weight, 9 % by weight, 12 % by weight or 15 % by weight is the repeating unit of conjugated diene, and wherein any value can be the lower limit and the upper limit (for example, 3 % by weight to 6 % by weight) of scope.In further aspect, conjugated diene has 4 to 8 carbon atoms, as divinyl, isoprene and hexadiene.In other aspects, conjugated diene is isoprene.

[0070] In one aspect, 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 %, wherein any value can be the lower and upper limits of the range (e.g., 2.0 wt % to 4.0 wt %). In one aspect, the curing agent present in the sealant composition is a quinone-type curing agent. In a further aspect, the curing agent can be selected from benzoquinone dioxime (BQD), dibenzoyl-p-quinone dioxime, p-dibenzoylquinone dioxime, p-dinitrosobenzene, N-methyl-N, 4-dinitrosoaniline, or any combination thereof. In other aspects, the curing agent is BQD.

[0071] In one aspect, 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 %, wherein any value can be the lower and upper limits of the range (e.g., 9 wt % to 12 wt %). In one aspect, the co-curing agent is an oxidizing agent. In a further aspect, the co-curing agent is an organic peroxide. In one aspect, the organic peroxide can be selected from diaroyl peroxide, diacyl peroxide and peroxyester. In a further aspect, the co-curing agent is dibenzoyl peroxide. In other aspects, the co-curing agent is selected from ZnO, MgO, CaO or any combination thereof. In one aspect, the sealant composition includes dibenzoyl peroxide co-curing agent and BQD curing agent.

[0072] In one aspect, a resin is also present in the sealant composition. Suitable resins include, but are not limited to, hydrocarbon resins, phenol / acetylene resins, rosin-derived resins, and mixtures thereof. Hydrocarbon resins can include coumarone-indene resins, petroleum resins, terpene polymers, and mixtures thereof.

[0073] Preparation and application of rubber composition

[0074] The compositions disclosed herein can be compounded by methods commonly known in the art of rubber compounding. In one aspect, these methods include mixing the components of the sealant composition described above with other conventional compounding ingredients, including fillers such as carbon black and silica; antidegradants such as antioxidants and antiozonants; colorants; processing aids; curing accelerators; curing retardants, etc. In one aspect, the curing accelerator can be selected from dithiocarbamate accelerators, thiuram accelerators, diphenylguanidine accelerators, benzothiazolesulfenamide accelerators, or any combination thereof. The curing accelerator can include derivatives: for example, benzothiazolesulfenamide accelerators include benzothiazolesulfenamide, and can also include derivatives of benzothiazolesulfenamide. In other aspects, the curing accelerator can include amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthates. In one aspect, the curing retardant can be selected from ethylene glycol, alkyl-substituted ethylene glycols, ethylenediamine, and alkyl-substituted ethylenediamine. On the other hand, curing retarder can be selected from ethylene glycol, propylene glycol (i.e. α-propylene glycol), ethylenediamine, methylethylenediamine, N,N-dimethylethylenediamine and 1,2-dimethylethylenediamine. In one aspect, antioxidant and antioxidant can be separately included in an amount of about 1phr to 5phr. In one aspect, antioxidant can be selected from diphenyl-p-phenylenediamine and other antioxidants, such as The Vanderbilt RubberHandbook (1978), antioxidants disclosed in pages 344 to 346. In other aspects, antiozonant can be selected from N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD) and N,N'-xylene-p-phenylenediamine (DTPD). In other aspects, basic oxides such as zinc oxide, magnesium oxide and calcium oxide can be included in an amount of about 1phr to about 5phr. Mixing of the sealant composition can be accomplished, for example, by combining the elastomer and other components in a rubber mixer, such as a Brabender internal mixer, an extruder, a cone mixer, etc. Suitable methods for mixing the sealant and applying it to the tire innerliner are disclosed, for example, in U.S. Patent No. 8,821,982, which is incorporated herein by reference.

[0075] Also disclosed herein are rubber compositions comprising the vulcanized sealant compositions disclosed herein and articles comprising the vulcanized sealant compositions. In one aspect, the article comprises a tire, such as a pneumatic tire, or a component of a tire. The tire can be a racing tire, a passenger car tire, an aircraft tire, an agricultural tire, a bulldozer tire, an off-road tire, a truck tire, or the like. In one embodiment, the tire is a passenger car tire or a truck tire. The tire can also be a radial tire or a bias tire. Such tires can be constructed, shaped, molded, and cured by various methods that are known and will be apparent to those skilled in the art. The components of the tire can be a tread, a base, a sidewall, an apex, a bead filler, a sidewall insert, a wire rubber coating, an inner liner, 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 inner liner of a cured tire. Before applying the sealant, impurities can be removed from the tire surface to improve the sealant's adhesion to the tire surface. In one embodiment, the tire innerliner surface is cleaned using laser technology, as described in US 20171 0151740, and the technology is incorporated herein by reference.

[0076] The use of highly reactive polyisobutylene (HR-PIB) in the presence or absence of a second diluent can change the physical properties of the vulcanized rubber composition described herein. In one aspect, the elastic modulus of the vulcanized rubber composition can be changed. In one aspect, the vulcanized rubber composition has an elastic modulus G' based on ASTM D5289 at 6.1% strain, 70°C and a frequency of 1.672Hz that is at least 20%, 30%, 40%, 50%, 75% and up to 100% higher than the elastic modulus G' of the vulcanized composition not comprising highly reactive polyisobutylene. On the other hand, the vulcanized rubber composition has an elastic modulus G' based on ASTM D4440 at 0.5% strain, 60°C and a frequency of 0.005Hz that is at least 30%, 40%, 50%, 75% and up to 100% lower than the loss factor tan δ of the vulcanized composition not comprising highly reactive polyisobutylene.

[0077] In another aspect, the cured rubber composition has a loss factor, tan δ, at 0.5% strain, 60° C., and a frequency of 0.005 Hz based on ASTM D4440 that is at least 30% lower, 40% lower, 50% lower, 75% lower, and up to 100% lower than the loss factor, tan δ of a cured composition that does not include the high-reactivity polyisobutylene.

[0078] Now that aspects of the present disclosure have been described, generally speaking, the following examples describe some additional aspects of the present disclosure. Although various aspects of the present disclosure are described in conjunction with the following examples and corresponding text and drawings, it is not intended to limit the various aspects of the present disclosure to this specification. On the contrary, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.

[0079] aspect

[0080] The disclosure may be described in terms of the following numbered aspects, which should not be confused with the claims.

[0081] Aspect 1. An uncured composition comprising:

[0082] An elastomer, a curing agent, a co-curing agent, and a diluent, wherein the diluent comprises a highly reactive polyisobutylene containing at least about 60 mole percent terminal vinylidene groups.

[0083] Aspect 2. The composition according to aspect 1, wherein the diluent consists of the highly reactive polyisobutylene.

[0084] Aspect 3. The composition of aspect 1, wherein the diluent comprises a second diluent comprising a second polyisobutylene, a hydrocarbon oil, or a combination thereof, the second polyisobutylene comprising up to about 20 mole % of terminal vinylidene groups.

[0085] Aspect 4. The composition of aspect 3, wherein the weight ratio of the highly reactive polyisobutylene to the second diluent is from about 1:20 to about 20:1.

[0086] Aspect 5. The composition of aspect 3, wherein the weight ratio of the highly reactive polyisobutylene to the second diluent is from about 1:20 to about 1:2.

[0087] Aspect 6. The composition of any one of aspects 3-5, wherein the second diluent comprises a second polyisobutylene comprising up to about 10 mol % of terminal vinylidene groups.

[0088] Aspect 7. The composition of any one of aspects 3-5, wherein the second diluent comprises a second polyisobutylene comprising from about 5 mol% to up to 20 mol% terminal vinylidene groups.

[0089] Aspect 8. The composition of any one of aspects 3-7, wherein the second polyisobutylene has an average molecular weight of about 500 Daltons to about 5,000 Daltons.

[0090] Aspect 9. The composition of any one of aspects 3-5, wherein the second diluent comprises a hydrocarbon oil.

[0091] Aspect 10. The composition according to any one of aspects 3-5, wherein the hydrocarbon oil comprises mineral oil, vegetable oil, or a combination thereof.

[0092] Aspect 11. The composition of any one of aspects 1 to 10, wherein the highly reactive polyisobutylene comprises at least 75 mol% terminal vinylidene groups.

[0093] Aspect 12. The composition of any one of aspects 1-10, wherein the highly reactive polyisobutylene comprises from about 60 mol% to less than 95 mol% terminal vinylidene groups.

[0094] Aspect 13. The composition of any one of aspects 1-12, wherein the highly reactive polyisobutylene has an average molecular weight of about 500 Daltons to about 5,000 Daltons.

[0095] Aspect 14. The composition of any one of aspects 1-13, wherein the elastomer comprises repeating units formed from residues of one or more monomers selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, and any combination thereof.

[0096] Aspect 15. The composition of any one of aspects 1-14, wherein the curing agent is a quinoid compound.

[0097] Aspect 16. The composition according to any one of aspects 1 to 14, wherein the curing agent is selected from benzoquinone dioxime, p,p-dibenzoylbenzoquinone dioxime, dibenzoyl-p-benzoquinone dioxime, p-dinitrosobenzene, N-methyl-N,4-dinitrosoaniline, and any combination thereof.

[0098] Aspect 17. The composition according to any one of aspects 1 to 16, wherein the co-curing agent is an oxidizing agent.

[0099] Aspect 18. The composition of any one of aspects 1-16, wherein the co-curing agent is an organic peroxide.

[0100] Aspect 19. The composition of any one of aspects 1 to 16, wherein the co-curing agent is a diaroyl peroxide, a diacyl peroxide, or a peroxyester.

[0101] Aspect 20. The composition of any one of aspects 1-16, wherein the curing agent is benzoquinone dioxime and the co-curing agent is dibenzoyl peroxide.

[0102] Aspect 21. The composition of any one of aspects 1-20, wherein the diluent comprises from about 50% to about 80% by weight of the composition.

[0103] Aspect 22. A vulcanized rubber composition comprising the vulcanized uncured composition according to any one of aspects 1 to 21.

[0104] Aspect 23. The composition of aspect 22, wherein the cured composition 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% higher than the elastic modulus G' of a cured composition that does not contain high-reactivity polyisobutylene.

[0105] Aspect 24. The composition of aspect 22, wherein the cured composition has an elastic modulus G′ at 0.5% strain, 60° C., and a frequency of 0.005 Hz based on ASTM D4440 that is at least 30% lower than the loss factor tan δ of a cured composition that does not include high-reactivity polyisobutylene.

[0106] Aspect 25. The composition of aspect 22, wherein the cured composition has a loss factor tan δ at 0.5% strain, 60° C., and a frequency of 0.005 Hz based on ASTM D4440 that is at least 30% lower than the loss factor tan δ of a cured composition that does not include the high-reactivity polyisobutylene.

[0107] Aspect 26. An article comprising the vulcanized rubber composition of any one of aspects 22-25.

[0108] Aspect 27. The article of aspect 26, wherein the article comprises a tire or a component of a tire.

[0109] Aspect 28. The article of aspect 27, wherein the components of the tire include a tread, a sidewall, an apex, a chafer, a sidewall insert, a wire lagging, an innerliner, or any combination thereof.

[0110] Example

[0111] The following examples are presented so as to provide one of ordinary skill in the art with a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, apparatus and / or methods claimed herein. These examples are intended only as illustrations of the present 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, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C. or at ambient temperature, and pressures are at or near atmospheric.

[0112] Example 1: Evaluation of rubber compositions

[0113] The rheological properties of the cured rubber compositions described herein were evaluated. The test methods for evaluating the cured compositions are provided in Table 1. The test results are provided in Tables 2 and Figure 1-6 middle.

[0114] Table 1

[0115]

[0116] Table 2

[0117]

[0118] As shown in the above data, rubber compositions prepared with a diluent consisting of 100% highly reactive polyisobutylene (HR-PIB) or a mixture of highly reactive polyisobutylene (HR-PIB) and conventional polyisobutylene (C-PIB) exhibited significantly higher elastic modulus G' than cured rubber compositions prepared without HR-PIB. Furthermore, rubber compositions prepared with a diluent consisting of 100% highly reactive polyisobutylene (HR-PIB) or a mixture of highly reactive polyisobutylene (HR-PIB) and conventional polyisobutylene (C-PIB) also exhibited significantly lower loss coefficient tan δ than cured rubber compositions prepared without HR-PIB.

[0119] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementation methods set forth for a clear understanding of the principles of the present disclosure. Many variations and modifications may be made to one or more of the above-described embodiments without departing substantially from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included within the scope of the present disclosure and to be protected by the appended 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 polyisobutylene comprising at least about 60 mole percent terminal vinylidene groups.

2. The composition according to claim 1, wherein the diluent consists of highly reactive polyisobutylene.

3. The composition of claim 1, wherein the diluent comprises a second diluent comprising a second polyisobutylene, a hydrocarbon oil, or a combination thereof, the second diluent comprising up to about 20 mole percent terminal vinylidene groups.

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

1.

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

2.

6. The composition of claim 3, wherein the second diluent comprises a second polyisobutylene comprising up to about 10 mole percent terminal vinylidene groups.

7. The composition of claim 3, wherein the second diluent comprises a second polyisobutylene comprising from about 5 mole % up to 20 mole % terminal vinylidene groups.

8. The composition of claim 3, wherein the second polyisobutylene has an average molecular weight of 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 mineral oil, vegetable oil, or a combination thereof.

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