Rubber compositions and articles thereof

Abstract

This invention relates to rubber compositions and articles thereof. In one aspect, this disclosure relates to a composition comprising an elastomer comprising about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; an accelerator comprising about 0.1 phr to about 5 phr of a first accelerator and about 0.1 phr to about 5 phr of a second accelerator; and about 0.1 phr to about 10 phr of hydrogenated rosin. This disclosure also relates to articles comprising the disclosed compositions, such as tires and / or tire assemblies. Methods for blending rubbers are also disclosed herein. This abstract is intended as a scanning tool for searching in a particular field and is not intended to limit this disclosure.

Description

Technical Field

[0001] This invention relates to rubber compositions and articles thereof, and to a method for mixing rubber. Background Technology

[0002] The need for improved tire performance has led to the development and evaluation of new materials with desirable properties. Improving tire properties such as ozone resistance while maintaining a balanced approach can be challenging. For example, tires with good ozone resistance, at least in part due to wax additive migration to the surface of the tire sidewall and / or bead wrapping, may also exhibit visible wax blooming on the tire surface. Visible wax blooming on the tire surface can be perceived negatively by tire sellers, buyers, and / or users. There is a need for rubber formulations with good properties such as ozone resistance while maintaining the visual appeal of products made from them. This disclosure addresses these and other needs. Summary of the Invention

[0003] For the purposes of this disclosure, as specifically embodied and broadly described herein, this disclosure relates in one aspect to a composition comprising: an elastomer comprising about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; an accelerator comprising about 0.1 phr to about 5 phr of a first accelerator and about 0.1 phr to about 5 phr of a second accelerator; and about 0.1 phr to about 10 phr of hydrogenated rosin. In one aspect, the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 200 mg KOH / g. In another aspect, the hydrogenated rosin has a softening point of about 70°C to about 125°C. Articles comprising the disclosed compositions, such as tires and / or tire assemblies, are also disclosed herein.

[0004] This document also discloses a method for blending rubber, comprising combining an elastomer with hydrogenated rosin of about 0.1 phr to about 10 phr to form an initial mixture; mixing the initial mixture at a temperature of about 130°C to about 180°C to form a first-stage mixture; combining the first-stage mixture with a first accelerator of about 0.1 phr to about 5 phr and a second accelerator of about 0.1 phr to about 5 phr to form an intermediate mixture; and mixing the intermediate mixture at a temperature of about 90°C to about 110°C to form a second-stage mixture. In one aspect, the elastomer comprises natural rubber of about 25 phr to about 75 phr and a synthetic elastomer of about 25 phr to about 75 phr. In another aspect, the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 200 mg KOH / g. In yet another aspect, the hydrogenated rosin has a softening point of about 70°C to about 125°C.

[0005] Other systems, methods, features, and advantages of this disclosure will be apparent to those skilled in the art after studying the following specific embodiments. All such additional systems, methods, features, and advantages are intended to be included within this specification, within the scope of this disclosure, and protected by the appended claims. Furthermore, all optional and preferred features and modifications of the stated aspects are applicable to all aspects of the disclosure taught herein. Moreover, the various features of the dependent claims, as well as all optional and preferred features and modifications of the stated aspects, are combinable and interchangeable with each other.

[0006] The present invention discloses the following solutions: Option 1. A composition comprising: An elastomer comprising about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; An accelerator comprising about 0.1 phr to about 5 phr of a first accelerator and about 0.1 phr to about 5 phr of a second accelerator; and Hydrogenated rosin from approximately 0.1 phr to approximately 10 phr; The hydrogenated rosin described therein has an acid value of about 140 mg KOH / g to about 200 mg KOH / g and a softening point of about 70°C to about 125°C.

[0007] Option 2. The composition according to Option 1, wherein the synthetic elastomer comprises repeating units formed from residues of monomers selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, and combinations thereof.

[0008] Option 3. The composition according to Option 1, wherein the first accelerator is selected from dithiocarbamates, thiuram compounds, guanidine compounds, and combinations thereof.

[0009] Option 4. The composition according to Option 1, wherein the first accelerator is selected from zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; zinc N-ethyl-N-phenyldithiocarbamate; zinc dibenzyldithiocarbamate; tetrabenzylthiuram disulfide; diphenylguanidine; 1,3-di-o-tolueneguanidine; triphenylguanidine; and combinations thereof.

[0010] Option 5. The composition according to Option 1, wherein the second accelerator is selected from amines, imines, sulfenamides, guanidines, dithiocarbamates, thiadiazoles, thiazoles, thiourea, thiurams, dithiophosphates, xanthates, and combinations thereof.

[0011] Option 6. The composition according to Option 1, wherein the second accelerator is selected from cyclohexylethylamine; hexamethylenetetramine; ethylidene aniline; butyraldehyde diphenylamine condensate; N-cyclohexyl-2-benzothiazole sulfenamide; N-tert-butyl-2-benzothiazole sulfenamide; N,N-dicyclohexyl-2-benzothiazole sulfenamide; 2-(2,4'-dinitrophenylmercapto)benzothiazole; 1,3-di-o-tolueneguanidine; triphenylguanidine; zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; N-ethyl-N-phenyldithiocarbamate. Zinc carbamate; zinc dibenzyl dithiocarbamate; N-cyclohexyl-S-(1,3,4-thiadiazol-2-yl)thiohydroxylamine; 2-mercaptobenzothiazole; 2,2'-dithiobenzothiazole; zinc 2-mercaptobenzothiazole; 2-(morpholinothio)benzothiazole; ethylidene thiourea; N-N'-diphenylthiourea; tetramethylthiuram disulfide; tetraethylthiuram disulfide; tetramethylthiuram monosulfide; dipentamethylthiuram tetrasulfide; zinc dithiophosphate; zinc butyl xanthate; sodium isopropyl xanthate; and combinations thereof.

[0012] Option 7. The composition according to Option 1, wherein the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 180 mg KOH / g.

[0013] Option 8. The composition according to Option 1, wherein the hydrogenated rosin has a softening point of about 70°C to about 100°C.

[0014] Option 9. The composition according to Option 1, wherein the composition further comprises filler, wax, anti-degradation agent, fatty acid, processing oil, zinc oxide, curing agent or a combination thereof.

[0015] Option 10. The composition according to Option 9, wherein the composition comprises a filler, the filler comprising carbon black.

[0016] Scheme 11. An article comprising the composition described in Scheme 1.

[0017] Option 12. The article of claim 11, wherein the article of claim 11 comprises a tire or a tire assembly.

[0018] Option 13. The method according to Option 12, wherein the tire assembly includes a sidewall or bead wrapping.

[0019] Option 14. The article according to Option 11, wherein, compared with an equivalent article not containing hydrogenated rosin, the article exhibits a visually reduced wax bloom on the surface of the article.

[0020] Option 15. The article according to Option 11, wherein the article does not crack after a dynamic ozone test, wherein the dynamic ozone test is performed in accordance with at least one of the methods detailed in ASTM D1149 or DIN 53509.

[0021] Option 16. The article according to Option 11, wherein the article did not crack after a static ozone test, wherein the static ozone test was performed in accordance with the method detailed in ASTM D1149 or DIN 53509.

[0022] Option 17. A method for mixing rubber, comprising: The elastomer is mixed with hydrogenated rosin at a rate of about 0.1 phr to about 10 phr to form an initial mixture; The initial mixture is mixed at a temperature of about 130°C to about 180°C to form a first-stage mixture; The first-stage mixture is combined with a first accelerator of 0.1 phr to about 5 phr and a second accelerator of about 0.1 phr to about 5 phr to form an intermediate mixture; and The intermediate mixture is mixed at a temperature of about 90°C to about 110°C to form a second-stage mixture; The elastomer comprises about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; and The hydrogenated rosin described therein has an acid value of about 140 mg KOH / g to about 200 mg KOH / g and a softening point of about 70°C to about 125°C.

[0023] Option 18. The method according to Option 17, wherein forming the initial mixture further comprises combining at least one of filler, wax, anti-degradation agent, fatty acid or processing oil.

[0024] Option 19. The method according to Option 18, wherein the filler comprises carbon black.

[0025] Option 20. The method according to Option 17, wherein forming the intermediate mixture further comprises combining at least one of a retarder, a curing activator, or a curing agent to form the intermediate mixture. Attached Figure Description

[0026] Many aspects of this disclosure can be better understood by referring to the following accompanying drawings. The components in the drawings are not necessarily drawn to scale, but rather the emphasis is on clearly illustrating the principles of this disclosure. Furthermore, in the drawings, the same reference numerals indicate corresponding parts throughout multiple views.

[0027] Figure 1A-1G This image shows a representative picture of a tire sidewall rubber sample that has undergone dynamic ozone resistance testing.

[0028] Figure 2A-2G This image shows a representative picture of a tire sidewall rubber sample that has undergone a static ozone resistance test.

[0029] Figures 3A-3B This image shows a representative picture of a tire sidewall rubber sample that has undergone ozone resistance testing.

[0030] Additional advantages of this disclosure will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of this disclosure. The advantages of this disclosure will be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and do not limit the disclosure as claimed. Detailed Implementation

[0031] Those skilled in the art, benefiting from the teachings presented in the foregoing specification, will conceive of numerous modifications and other aspects disclosed herein. Therefore, it should be understood that this disclosure is not limited to the specific aspects disclosed, and that modifications and other aspects are intended to be included within the scope of the appended claims. Those skilled in the art will recognize many variations and modifications to the aspects described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0032] As will be apparent to those skilled in the art upon reading this disclosure, each individual aspect described and illustrated herein has discrete components and features that can be readily separated from or combined with features of any of the other aspects without departing from the scope or spirit of this disclosure.

[0033] Any enumerated method may be performed in the order of the enumerated events or in any other logically possible order. That is, unless otherwise expressly stated, it is never intended to interpret any method or aspect described herein as requiring its steps to be performed in a particular order. Therefore, unless a method claim in the claim or specification specifically states that the steps will be limited to a particular order, no inference is made in any respect of the order. This applies to any possible non-explicit basis of interpretation, including the logical content of the arrangement of steps or procedures, the simple meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0034] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials relating to the cited publications. The publications discussed herein provide only their disclosure prior to the filing date of this application. This document should not be construed as an admission that this disclosure is not authorized to predate these publications by virtue of prior disclosure. Furthermore, the publication dates provided herein may differ from the actual publication dates, which may require independent verification.

[0035] While aspects of this disclosure may be described and claimed in specific statutory categories such as composition statutory categories, this is merely for convenience, and those skilled in the art will understand that each aspect of this disclosure may be described and claimed in any statutory category.

[0036] Although specific terms are used herein, they are used only in a general and descriptive sense, and not for limiting purposes. It should also be understood that the terms used herein are for describing specific aspects only 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 one of ordinary skill in the art to which the disclosed compositions and methods pertain. It will be further understood that terms as defined in common dictionaries should be interpreted as having meanings consistent with their meanings in the context of the specification and the relevant field, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0037] Before describing various aspects of this disclosure, the following definitions are provided and should be used unless otherwise specified. Additional terms may be defined elsewhere in this disclosure.

[0038] A. Definition As used herein, “comprising” should be interpreted as specifying the presence of the mentioned feature, integer, step, or component, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Furthermore, each of the terms “through,” “comprising,” “comprises,” “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” is used in its open, non-limiting sense and is interchangeable. Additionally, the term “comprising” is intended to include instances and aspects covered by the terms “substantially constitutes” and “consistent with.” Similarly, the term “substantially constitutes” is intended to include instances covered by the term “consistent with.”

[0039] As used herein, the term "and / or" includes any and all combinations of one or more related listed items. Expressions such as "at least one…" when placed before a list of elements modify the entire list, not a single element within it.

[0040] As used herein, the nomenclature of compounds (including organic compounds) may be provided using common names, IUPAC, IUBMB, or CAS nomenclature recommendations. When one or more stereochemical features are present, the Cahn-Ingold-Prelog stereochemical rules may be used to specify stereochemical priority, E / Z configuration, etc. Given a name, those skilled in the art can systematically reduce the compound structure using nomenclature conventions or commercially available software such as CHEMDRAW. TM (Cambridgesoft Corporation, USA) The structure of the compound was easily determined.

[0041] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly indicates otherwise. Thus, for example, references to “elastomer,” “accelerator,” or “wax” include, but are not limited to, two or more such elastomers, accelerators, or waxes. A reference to “a chemical compound” means one or more molecules of the compound, not just a single molecule. Furthermore, the one or more molecules may be the same or different, as long as they fall within the category of compounds. Thus, for example, “a chemical compound” is interpreted as including one or more molecules of the compound, wherein the molecules may be the same or different (e.g., different isotope ratios, enantiomers, etc.).

[0042] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed in ranges herein. It will be further understood that each endpoint of a range is meaningful both relative to and independent of another endpoint. It should also be understood that many values ​​are disclosed herein, and each value is also disclosed herein as “about” that particular value, in addition to being the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. In this document, a range may be expressed as from “about” one particular value and / or to “about” another particular value. Similarly, when a value is expressed as an approximation using the antecedent “about”, it will be understood that the particular value is formed in another respect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0043] When a range is indicated, it in another respect includes from one specific value and / or to another specific value. For example, where the range includes one or two limits, the range excluding any one or both of those included limits is also included in this disclosure; for example, the phrase "x to y" includes the range from "x" to "y" as well as the range greater than "x" and less than "y". A range can also be indicated as an upper limit, such as "about x, y, z or less", and should be interpreted as including the specific ranges of "about x", "about y", and "about z" as well as the ranges of "less than x", "less than y", and "less than z". Similarly, the phrase "about x, y, z or greater" should be interpreted as including the specific ranges of "about x", "about y", and "about z" as well as the 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".

[0044] It should be understood that this range form is used for convenience and brevity, and therefore should be interpreted flexibly to include not only the values ​​explicitly listed as the boundaries of the range, but also all individual values ​​or subranges contained within that range, as if each value and subrange were explicitly listed. For example, the range of values ​​“about 0.1% to 5%” should be interpreted to include not only the explicitly stated 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%, and other possible subranges).

[0045] As used herein, the terms “about,” “approximately,” “in or about,” and “substantially” mean that the quantity or value in question can be an 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 quantities, 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 needed, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art, resulting in an equivalent result or effect. In some cases, it is not reasonable to determine a value that provides an equivalent result or effect. In such cases, it is generally understood that, as used herein, “about” and “in or about” mean a variation of ±10% of the indicated nominal value, unless otherwise indicated or inferred. Generally, quantities, dimensions, formulations, parameters, or other quantities or characteristics are “about,” “approximately,” or “in or about,” whether or not explicitly stated so. It should be understood that, unless otherwise specifically stated, when “about,” “approximately,” or “in or about” is used before a quantity value, the parameter also includes the specific quantity value itself.

[0046] As used herein, the terms “optional” or “optionally” mean that the event or situation described below may or may not occur, and the description includes both the possibility that the event or situation occurs and the possibility that it does not occur.

[0047] Unless otherwise specified, the terms “rubber” and “elastomer” are used interchangeably in this document.

[0048] As used herein, the term "phr" refers to the weight parts of each material in 100 parts by weight of rubber or elastomer. Typically, using this convention, an elastomer composition comprises 100 parts by weight of rubber / elastomer. The claimed composition may contain other rubbers / elastomers besides those expressly mentioned in the claims, provided that the phr value of the claimed rubber elastomer falls within the claimed phr range and the total amount of all rubbers / elastomers in the composition results in a total of 100 parts of rubber.

[0049] As used herein, the term "uncured composition" refers to a composition comprising at least one natural or synthetic rubber component and optionally one or more fillers, processing aids, or other compounds, which has not been vulcanized. Uncured rubber is sensitive to temperature changes and tends to undergo "cold flow" (slow movement or deformation under stress) over time. In one respect, the uncured rubber composition is a masterbatch.

[0050] As used herein, the term "vulcanized rubber composition" refers to a rubber composition obtained by taking an uncured composition as described herein and curing or vulcanizing it, typically using sulfur compounds and / or other curing additives and done in the presence of heat. Vulcanized or cured rubber does not undergo a cold flow and is less sensitive to temperature changes compared to uncured rubber. In one aspect, the rubber composition can be cured in a mold to form finished articles such as tires.

[0051] As used herein, the term "repeating unit" in the context of elastomers is derived from monomers used to prepare partially saturated elastomers. For example, polybutadiene has repeating units as provided below.

[0052] In some respects, when the elastomer is a polymer of two different monomers (e.g., A and B), the repeating unit can be represented by -AB-.

[0053] As used herein, a chemical class "residue" refers to a moiety of the product resulting from that chemical class in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether that moiety is actually obtained from that chemical class. Therefore, an isoprene residue in an elastomer refers to one or more –CH2CH=C(CH3)CH2– units in the elastomer, regardless of whether isoprene is used to prepare the elastomer. Similarly, a butadiene residue in an elastomer refers to one or more –CH2CH=CHCH2– portions in the elastomer, regardless of whether the residue is obtained by reacting sebacic acid or its esters to obtain a polyester.

[0054] Unless otherwise stated, the temperatures mentioned in this article are based on atmospheric pressure (i.e., one atmosphere).

[0055] B. Rubber composition In one aspect, this disclosure relates to a composition, such as an uncured or cured rubber composition, comprising an elastomer, an accelerator, and hydrogenated rosin of about 0.1 phr to about 10 phr. In one aspect, the elastomer may comprise natural rubber of about 25 phr to about 75 phr and synthetic elastomer of about 25 phr to about 75 phr. In one aspect, the accelerator may comprise a first accelerator of about 0.1 phr to about 5 phr and a second accelerator of about 0.1 phr to about 5 phr. In another aspect, the total amount of accelerator present in the composition may be about 0.5 phr to about 5 phr, about 0.5 phr to about 4 phr, about 0.5 phr to about 3 phr, about 0.5 phr to about 2 phr, about 1 phr to about 5 phr, about 1 phr to about 4 phr, or about 1 phr to about 3 phr. The compositions disclosed herein exhibit good ozone resistance, while also exhibiting reduced visible wax bloom on their surfaces. This disclosure also relates to methods of manufacturing the disclosed compositions and articles comprising the compositions, such as tires and / or tire assemblies.

[0056] In another aspect, the elastomer may comprise natural rubber of about 25 phr to about 75 phr, about 30 phr to about 75 phr, about 35 phr to about 75 phr, about 40 phr to about 75 phr, about 25 phr to about 70 phr, about 25 phr to about 65 phr, about 25 phr to about 60 phr, about 30 phr to about 70 phr, or about 40 phr to about 60 phr. In another aspect, the elastomer may comprise synthetic elastomer of about 25 phr to about 75 phr, about 30 phr to about 75 phr, about 35 phr to about 75 phr, about 40 phr to about 75 phr, about 25 phr to about 70 phr, about 25 phr to about 65 phr, about 25 phr to about 60 phr, about 30 phr to about 70 phr, or about 40 phr to about 60 phr. In one aspect, the total phr of the natural rubber and synthetic elastomer present in the composition is 100 phr. Synthetic elastomers may comprise repeating units formed from monomer residues selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, and acrylonitrile, and combinations thereof. In another aspect, the elastomer may have a number-average molecular weight (Mn) between 100,000 Da and 500,000 Da. n M n It can be determined by methods known in the art, such as gel permeation chromatography following ASTM D3536 or an equivalent method.

[0057] In another aspect, the composition may comprise hydrogenated rosin at concentrations of about 0.1 phr to about 10 phr, about 0.1 phr to about 8 phr, about 0.1 phr to about 5 phr, about 0.1 phr to about 3 phr, about 1 phr to about 10 phr, about 3 phr to about 10 phr, about 5 phr to about 10 phr, or about 7 phr to about 10 phr, about 0.5 phr to about 5 phr, or about 0.5 phr to about 3 phr. Rosin is a resinous material that can be extracted from pine trees. Rosin consists of a mixture of organic compounds, including acids such as rosin acid, piratic acid, and their derivatives. Raw rosin can be refined or processed (e.g., hydrogenated) to prepare various rosin derivatives. An example of hydrogenated rosin is white or aquamarine rosin, which can be prepared from raw rosin through processes such as hydrogenation, disproportionation, and other treatments. Hydrogenated rosin can be characterized by a variety of physical properties, including acid value and softening point. Acid value refers to the amount of base required to neutralize acidic groups contained in a sample. In one aspect, acid value is the amount of KOH (mg) required to neutralize the acidic groups contained in one gram of hydrogenated rosin. In another aspect, the acid value of hydrogenated rosin can be about 140 mg KOH / g to about 200 mg KOH / g, about 150 mg KOH / g to about 200 mg KOH / g, about 160 mg KOH / g to about 200 mg KOH / g, about 170 mg KOH / g to about 200 mg KOH / g, about 140 mg KOH / g to about 190 mg KOH / g, about 140 mg KOH / g to about 180 mg KOH / g, about 140 mg KOH / g to about 170 mg KOH / g, about 150 mg KOH / g to about 190 mg KOH / g, or about 160 mg KOH / g to about 180 mg KOH / g. In one aspect, the softening point of hydrogenated rosin may be about 70°C to about 125°C, about 70°C to about 115°C, about 70°C to about 105°C, about 70°C to about 100°C, about 70°C to about 90°C, about 80°C to about 125°C, about 90°C to about 125°C, about 100°C to about 125°C, about 80°C to about 115°C, or about 90°C to about 105°C. In another aspect, the softening point may be determined according to ASTM E28 or an equivalent method.

[0058] In another aspect, the accelerator may comprise a first accelerator in amounts of about 0.1 phr to about 5 phr, about 0.1 phr to about 4 phr, about 0.1 phr to about 3 phr, or about 0.1 phr to about 2 phr. The first accelerator may be selected from dithiocarbamate compounds, thiuram compounds, guanidine compounds, and combinations thereof. In another aspect, the first accelerator may be selected from zinc diethyldithiuram, N-dibutyldithiuram, N-ethyl-N-phenyldithiuram, zinc dibenzyldithiuram, tetrabenzylthiuram disulfide, diphenylguanidine, 1,3-di-o-toluidine, triphenylguanidine, and combinations thereof. In another aspect, the first accelerator may be selected from thiuram compounds, guanidine compounds, and combinations thereof. In another aspect, the first accelerator may be selected from tetrabenzylthiuram disulfide, diphenylguanidine, 1,3-di-o-toluidine, triphenylguanidine, and combinations thereof. In another aspect, the first accelerator may be selected from tetrabenzylthiuram disulfide, diphenylguanidine, and combinations thereof.

[0059] In another aspect, the accelerator may comprise a second accelerator at a concentration of about 0.1 phr to about 5 phr, about 0.1 phr to about 4 phr, about 0.1 phr to about 3 phr, about 0.1 phr to about 2 phr, or about 0.1 phr to about 1 phr. The second accelerator may be selected from amines, imines, sulfenamides, guanidines, dithiocarbamates, thiadiazoles, thiazoles, thioureas, thiurams, dithiophosphates, xanthates, and combinations thereof. In another aspect, the second accelerator may be selected from cyclohexylethylamine, hexamethylenetetramine, ethyldiphenylamine, and ethylbenzylamine. aniline), butyraldehyde diphenylamine condensate, N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide; N,N-dicyclohexyl-2-benzothiazole sulfenamide; 2-(2,4'-dinitrophenylmercapto)benzothiazole; 1,3-di-o-tolueneguanidine; triphenylguanidine; zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; zinc N-ethyl-N-phenyldithiocarbamate; zinc dibenzyldithiocarbamate; N-cyclohexyl-S-(1,3,4-thiazole) Diazol-2-yl)thiohydroxylamine; 2-mercaptobenzothiazole; 2,2'-dithiobenzothiazole; zinc 2-mercaptobenzothiazole; 2-(morpholinothio)benzothiazole; ethylidene thiourea; N-N'-diphenylthiurea; tetramethylthiuram disulfide; tetraethylthiuram disulfide; tetramethylthiuram monosulfide; dipentamethylenethiuramtetrasulfide; zinc dithiophosphate; zinc butyl xanthate; sodium isopropyl xanthate; and combinations thereof.

[0060] In another aspect, the composition may further comprise fillers, waxes, anti-degradation agents, fatty acids, processing oils, curing activators, curing agents, or combinations thereof. In another aspect, the composition may comprise fillers of about 0.5 phr to about 150 phr, about 0.5 phr to about 100 phr, about 0.5 phr to about 75 phr, about 0.5 phr to about 50 phr, or about 0.5 phr to about 25 phr. In another aspect, the composition may comprise anti-degradation agents of about 1 phr to about 10 phr, about 1 phr to about 5 phr, or about 5 phr to about 10 phr. In another aspect, the composition may comprise processing oils of about 1 phr to about 50 phr, about 1 phr to about 40 phr, about 1 phr to about 30 phr, or about 1 phr to about 20 phr.

[0061] In another aspect, the wax may be included in an amount from about 1 phr to about 5 phr. Examples of waxes include microcrystalline waxes, paraffin waxes, and isoparaffin waxes. Fatty acids may be included in an amount from about 0.5 phr to about 3 phr. Examples of fatty acids include, but are not limited to, stearic acid, palmitic acid, oleic acid, and mixtures thereof. Activators may be included in an amount from about 1 phr to about 10 phr or from about 1 phr to about 5 phr. Activators may include, but are not limited to, magnesium oxide, zinc oxide, calcium oxide, and polyethylene glycol. Curing agents or vulcanizing agents may be included in an amount from about 0.1 phr to about 8.0 phr or from about 0.1 phr to about 5.0 phr. Curing agents or vulcanizing agents may include, but are not limited to, elemental sulfur, sulfur-containing silanes, or combinations thereof. In another aspect, the composition may additionally include a retarder from about 1 phr to about 10 phr. Retarder may include, but is not limited to, phthalic anhydride, phthalimide (e.g., N-(cyclohexylthio)phthalimide), sulfenamide compounds and acids (e.g., benzoic acid and salicylic acid).

[0062] In one aspect, the filler may include carbon black. In another aspect, the carbon black may be N-type carbon black. Examples of N-type carbon black include carbon blacks with ASTM names N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, and N991, as specified in ASTM D1765-21 “Standard Classification System for Carbon Blacks Used in Rubber Products”. According to ASTM D1510-21, these carbon blacks are characterized by an iodine absorption of approximately 9 g / kg to 145 g / kg. According to ASTM D2414, these carbon blacks are also characterized by an iodine absorption of approximately 34 cm⁻¹. 3 / 100 g to 150 cm 3 Absorption value of dibutyl phthalate (DBP) per 100 g.

[0063] Anti-degradation agents can include antioxidants and anti-ozone agents. Representative antioxidants include, but are not limited to, phenylenediamine compounds (e.g., diphenyl-p-phenylenediamine), hydrogenated quinoline compounds (e.g., 2,2,4-trimethyl-1,2-dihydroquinoline), amine compounds, dithiocarbamate compounds, phenolic compounds, phosphite compounds, mebendazole compounds, and other compounds such as those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. Representative anti-ozone agents include, but are not limited to, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD) and N,N'-xylene-p-phenylenediamine (DTPD).

[0064] Processing oils can be included in the composition as incrementing oils commonly used in incremental elastomers. Processing oils can also be included in the elastomer composition by adding the oil directly during rubber compounding. The processing oils used can include both the incrementing oils present in the elastomer and the process oils added during compounding. Suitable processing oils include, but are not limited to, a variety of oils known in the art, including aromatic oils, paraffinic oils, naphthenic oils, vegetable oils, and low polycyclic aromatic hydrocarbon (PCA) oils, such as MES, TDAE, SRAE, and heavy naphthenic oils. In one aspect, the PCA content of low PCA oils can be less than about 5% by weight or less than about 3% by weight. Suitable vegetable oils include, for example, soybean oil, sunflower oil, and low erucic acid rapeseed oil, which are in the form of esters containing a certain degree of unsaturation.

[0065] C. Preparation and application of rubber compositions Rubber compositions can be compounded using methods generally known in the field of rubber compounding. In one aspect, a method for compounding rubber may include mixing an elastomer, an accelerator, and hydrogenated rosin with optionally various vulcanizable component rubbers and optionally various commonly used additive materials such as fillers, waxes, degradation inhibitors, fatty acids, processing oils, curing activators, and curing or vulcanizing agents. More specifically, a method for rubber compounding is disclosed herein, comprising: combining an elastomer with about 0.1 phr to about 10 phr of hydrogenated rosin to form an initial mixture; mixing the initial mixture at a temperature of about 130°C to about 180°C to form a first-stage mixture; combining the first-stage mixture with 0.1 phr to about 5 phr of a first accelerator and about 0.1 phr to about 5 phr of a second accelerator to form an intermediate mixture; and mixing the intermediate mixture at a temperature of about 90°C to about 110°C to form a second-stage mixture. In another aspect, the initial mixture can be mixed at temperatures ranging from about 130°C to about 180°C, from about 140°C to about 180°C, from about 150°C to about 180°C, from about 130°C to about 170°C, from about 130°C to about 160°C, or from about 140°C to about 170°C. In yet another aspect, the intermediate mixture can be mixed at temperatures ranging from about 90°C to about 110°C, from about 100°C to about 110°C, or from about 90°C to about 100°C.

[0066] In one aspect, the rubber composition may undergo a thermomechanical mixing step. The mixing stage may include thermomechanical mixing, typically characterized by mechanical processing for a period of time in a mixer (e.g., an internal batch mixer) or extruder at a high temperature suitable for producing rubber. The appropriate duration of thermomechanical mixing varies with operating conditions and variations in the volume and properties of the components. For example, thermomechanical mixing may be from about 0.5 to 10 minutes.

[0067] In another aspect, the elastomer may comprise natural rubber of about 25 phr to about 75 phr, about 30 phr to about 75 phr, about 35 phr to about 75 phr, about 40 phr to about 75 phr, about 25 phr to about 70 phr, about 25 phr to about 65 phr, about 25 phr to about 60 phr, about 30 phr to about 70 phr, or about 40 phr to about 60 phr. In another aspect, the elastomer may comprise synthetic elastomer of about 25 phr to about 75 phr, about 30 phr to about 75 phr, about 35 phr to about 75 phr, about 40 phr to about 75 phr, about 25 phr to about 70 phr, about 25 phr to about 65 phr, about 25 phr to about 60 phr, about 30 phr to about 70 phr, or about 40 phr to about 60 phr. In one aspect, the total phr of the natural rubber and synthetic elastomer present in the composition is 100 phr. Synthetic elastomers may comprise repeating units formed from monomer residues selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, and acrylonitrile, and combinations thereof. In another aspect, the elastomer may have a number-average molecular weight (Mn) between 100,000 Da and 500,000 Da. n M n It can be determined by methods known in the art, such as by gel permeation chromatography according to ASTM D3536 or an equivalent method.

[0068] In another aspect, the composition may comprise hydrogenated rosin in amounts of about 0.1 phr to about 10 phr, about 0.1 phr to about 8 phr, about 0.1 phr to about 5 phr, about 0.1 phr to about 3 phr, about 1 phr to about 10 phr, about 3 phr to about 10 phr, about 5 phr to about 10 phr, about 7 phr to about 10 phr, about 0.5 phr to about 5 phr, or about 0.5 phr to about 3 phr. An example of hydrogenated rosin is a white or aquamarine rosin, which can be prepared from virgin rosin by processes such as hydrogenation, disproportionation, and other treatments. Hydrogenated rosin can be characterized by a variety of physical properties, including acid value and softening point. In one respect, the acid value of hydrogenated rosin can be about 140 mg KOH / g to about 200 mg KOH / g, about 150 mg KOH / g to about 200 mg KOH / g, about 160 mg KOH / g to about 200 mg KOH / g, about 170 mg KOH / g to about 200 mg KOH / g, about 140 mg KOH / g to about 190 mg KOH / g, about 140 mg KOH / g to about 180 mg KOH / g, about 140 mg KOH / g to about 170 mg KOH / g, about 150 mg KOH / g to about 190 mg KOH / g, or about 160 mg KOH / g to about 180 mg KOH / g. In one aspect, the hydrogenated resin may have a softening point of about 70°C to about 125°C, about 70°C to about 115°C, about 70°C to about 105°C, about 70°C to about 100°C, about 70°C to about 90°C, about 80°C to about 125°C, about 90°C to about 125°C, about 100°C to about 125°C, about 80°C to about 115°C, or about 90°C to about 105°C.

[0069] In another aspect, the accelerator may comprise a first accelerator in the form of about 0.1 phr to about 5 phr, about 0.1 phr to about 4 phr, about 0.1 phr to about 3 phr, or about 0.1 phr to about 2 phr. The first accelerator may be selected from dithiocarbamate compounds, thiuram compounds, guanidine compounds, and combinations thereof. In another aspect, the first accelerator may be selected from zinc diethyldithiuram, N-dibutyldithiuram, N-ethyl-N-phenyldithiuram, zinc dibenzyldithiuram, tetrabenzylthiuram disulfide, diphenylguanidine, 1,3-di-o-toluidine, triphenylguanidine, and combinations thereof. In another aspect, the first accelerator may be selected from thiuram compounds, guanidine compounds, and combinations thereof. In another aspect, the first accelerator may be selected from tetrabenzylthiuram disulfide, diphenylguanidine, 1,3-di-o-toluidine, triphenylguanidine, and combinations thereof. In another aspect, the first accelerator may be selected from tetrabenzylthiuram disulfide, diphenylguanidine, and combinations thereof.

[0070] In another aspect, the accelerator may comprise a second accelerator in amounts of about 0.1 phr to about 5 phr, about 0.1 phr to about 4 phr, about 0.1 phr to about 3 phr, or about 0.1 phr to about 2 phr. The second accelerator may be selected from amines, imines, sulfenamides, guanidines, dithiocarbamates, thiadiazoles, thiazoles, thiourea, thiurams, dithiophosphates, xanthates, and combinations thereof. In another aspect, the second accelerator may be selected from cyclohexylethylamine, hexamethylenetetramine, ethylidene aniline, butyraldehyde diphenylamine condensate, N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide; N,N-dicyclohexyl-2-benzothiazole sulfenamide; 2-(2,4'-dinitrophenylmercapto)benzothiazole; 1,3-di-o-tolueneguanidine; triphenylguanidine; zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; N-ethyl-N-phenyldithiocarbamate. Zinc dibenzyl dithiocarbamate; N-cyclohexyl-S-(1,3,4-thiadiazol-2-yl)thiohydroxylamine; 2-mercaptobenzothiazole; 2,2'-dithiobenzothiazole; zinc 2-mercaptobenzothiazole; 2-(morpholinylthio)benzothiazole; ethylidene thiourea; N-N'-diphenylthiourea; tetramethylthiuram disulfide; tetraethylthiuram disulfide; tetramethylthiuram monosulfide; dipentamethylthiuram tetrasulfide; zinc dithiophosphate; zinc butyl xanthate; sodium isopropyl xanthate; and combinations thereof.

[0071] In another aspect, forming the initial mixture may further include combining at least one of filler, wax, anti-degradation agent, fatty acid, or processing oil. The filler may be carbon black. In one aspect, the filler may be used in an amount of about 0.5 phr to about 150 phr, about 0.5 phr to about 100 phr, about 0.5 phr to about 75 phr, about 0.5 phr to about 50 phr, or about 0.5 phr to about 25 phr. In another aspect, the wax may be used in an amount of about 1 phr to about 5 phr. In another aspect, the anti-degradation agent may be used in an amount of about 1 phr to about 10 phr, about 1 phr to about 5 phr, or about 5 phr to about 10 phr. In another aspect, the fatty acid may be used in an amount of about 0.5 phr to about 3 phr. In another aspect, the processing oil may be used in an amount of about 1 phr to about 50 phr, about 1 phr to about 40 phr, about 1 phr to about 30 phr, or about 1 phr to about 20 phr. Examples of various additives (such as fillers, waxes, etc.) include those listed above.

[0072] In another aspect, forming the intermediate mixture further includes combining at least one of a retarder, a curing activator, or a curing agent to form the intermediate mixture. In another aspect, the retarder may be used in an amount from about 1 phr to about 10 phr. In another aspect, the curing activator may be used in an amount from about 1 phr to about 10 phr or from about 1 phr to about 5 phr. In another aspect, the curing agent may be used in an amount from about 0.1 phr to about 8.0 phr or from about 0.1 phr to about 5.0 phr. Examples of various additives (e.g., retarders, curing activators, etc.) include those listed above.

[0073] D. Rubber products This document also discloses articles incorporating any compositions disclosed herein and / or compositions prepared by any methods disclosed herein. In one aspect, the article comprises a tire (such as a pneumatic tire) or a tire assembly. The tire may be a racing tire, passenger car tire, aircraft tire, agricultural tire, off-road tire, truck or bus tire, etc. The tire may also be a radial tire or a bias-ply tire. The tire assembly may be a tread, base, sidewall, gusset, bead wrap, sidewall insert, steel wire wrap, inner liner, or any combination thereof. In another aspect, the tire assembly may be a bead wrap, sidewall, or any combination thereof. The vulcanization of the disclosed tires is typically carried out at conventional temperatures, for example, from about 100°C to about 200°C or from about 110°C to about 180°C. Such tires can be constructed, shaped, molded, and cured by a variety of methods known to and obvious to those skilled in the art.

[0074] In one respect, the product exhibits good ozone resistance. For example, after undergoing various ozone testing methods, the product shows virtually no cracking, splitting, and / or other defects. In another respect, the product does not crack after dynamic ozone testing, wherein the dynamic ozone test is performed in accordance with at least one of the methods detailed in ASTM Method D1149 or DIN Method 53509. In yet another respect, the product does not crack after static ozone testing, wherein the static ozone test is performed in accordance with at least one of the methods detailed in ASTM D1149 or DIN Method 53509.

[0075] While reluctant to be bound by theory, wax migration to the surface of rubber products (such as tire sidewalls or tire bead wraps) is believed to protect the products from ozone damage during static storage. However, wax migration can also lead to visible wax bloom on the surface of the product, which can be considered negative for users and sellers. Compared to similar products without rosin, the products of this disclosure maintain good ozone resistance while reducing visible wax bloom.

[0076] E. Aspect The exemplary aspects listed below support and are supported by the disclosures provided herein.

[0077] Aspect 1. A composition formed from residues selected from isobutylene and isoprene monomers.

[0078] Aspect 2. The composition according to aspect 1, wherein the elastomer comprises about 40 phr to about 60 phr of natural rubber and about 40 phr to about 60 phr of synthetic elastomer.

[0079] Aspect 3. The composition according to aspect 1 or aspect 2, wherein the first accelerator is selected from dithiocarbamates, thiuram compounds, guanidine compounds, and combinations thereof.

[0080] Aspect 4. The composition according to any one of Aspects 1-3, wherein the first accelerator is selected from zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; zinc N-ethyl-N-phenyldithiocarbamate; zinc dibenzyldithiocarbamate; tetrabenzylthiuram disulfide; diphenylguanidine; 1,3-di-o-tolueneguanidine; triphenylguanidine; and combinations thereof.

[0081] Aspect 5. The composition according to any one of aspects 1-4, wherein the promoter comprises a first promoter of about 0.1 phr to about 3 phr.

[0082] Aspect 6. The composition according to any one of Aspects 1-5, wherein the second accelerator is selected from amines, imines, sulfenamides, guanidines, dithiocarbamates, thiadiazoles, thiazoles, thiourea, thiurams, dithiophosphates, xanthates, and combinations thereof.

[0083] Aspect 7. The composition according to any one of Aspects 1-6, wherein the second accelerator is selected from cyclohexylethylamine; hexamethylenetetramine; ethylidene aniline; butyraldehyde diphenylamine condensate; N-cyclohexyl-2-benzothiazole sulfenamide; N-tert-butyl-2-benzothiazole sulfenamide; N,N-dicyclohexyl-2-benzothiazole sulfenamide; 2-(2,4'-dinitrophenylmercapto)benzothiazole; 1,3-di-o-toluidine; triphenylguanidine; zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; N-ethyl-N-phenyl Zinc dithiocarbamate; zinc dibenzyl dithiocarbamate; N-cyclohexyl-S-(1,3,4-thiadiazol-2-yl)thiohydroxylamine; 2-mercaptobenzothiazole; 2,2'-dithiobenzothiazole; zinc 2-mercaptobenzothiazole; 2-(morpholinothio)benzothiazole; ethylidene thiourea; N-N'-diphenylthiourea; tetramethylthiuram disulfide; tetraethylthiuram disulfide; tetramethylthiuram monosulfide; dipentamethylthiuram tetrasulfide; zinc dithiophosphate; zinc butyl xanthate; sodium isopropyl xanthate; and combinations thereof.

[0084] Aspect 8. The composition according to any one of aspects 1-7, wherein the accelerator comprises a second accelerator of about 0.1 phr to about 1 phr.

[0085] Aspect 9. The composition according to any one of aspects 1-8, wherein the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 180 mg KOH / g.

[0086] Aspect 10. The composition according to any one of aspects 1-9, wherein the hydrogenated rosin has a softening point of about 70°C to about 100°C.

[0087] Aspect 11. The composition according to any one of aspects 1-10, wherein the hydrogenated rosin is present in an amount of about 0.1 phr to about 5 phr.

[0088] Aspect 12. The composition according to any one of aspects 1-11, wherein the hydrogenated rosin is present in an amount of about 0.1 phr to about 3 phr.

[0089] Aspect 13. The composition according to any one of aspects 1-12, further comprising at least one wax.

[0090] Aspect 14. The composition according to any one of aspects 1-13, wherein the composition further comprises filler, wax, anti-degradation agent, fatty acid, processing oil, zinc oxide, curing agent or a combination thereof.

[0091] Aspect 15. The composition according to any one of aspects 1-14, wherein the composition comprises a filler comprising carbon black.

[0092] Aspect 16. An article comprising the composition described in any one of aspects 1-15.

[0093] Aspect 17. The article of manufacture according to aspect 16, wherein the article of manufacture includes a tire or a tire assembly.

[0094] Aspect 18. The article of manufacture according to aspect 16 or aspect 17, wherein the tire assembly includes a sidewall or bead wrapping.

[0095] Aspect 19. The article according to any one of aspects 16-18, wherein, compared with an equivalent article not containing the hydrogenated rosin, the article exhibits a visually reduced wax bloom on the surface of the article.

[0096] Aspect 20. Articles according to any one of Aspects 16-19, wherein the article does not crack after a dynamic ozone test, wherein the dynamic ozone test is performed in accordance with a method detailed in at least one of ASTM D1149 or DIN 53509.

[0097] Article 21. Articles according to any one of Articles 16-20, wherein the article does not crack after a static ozone test, wherein the static ozone test is performed in accordance with the method detailed in ASTM D1149 or DIN 53509.

[0098] Aspect 22. A method for rubber compounding, comprising: combining an elastomer with hydrogenated rosin of about 0.1 phr to about 10 phr to form an initial mixture; mixing the initial mixture at a temperature of about 130°C to about 180°C to form a first stage mixture; mixing the first stage mixture with a first accelerator of about 0.1 phr to about 5 phr and a second accelerator of about 0.1 phr to about 5 phr to form an intermediate mixture; and mixing the intermediate mixture at a temperature of about 90°C to about 110°C to form a second stage mixture; wherein the elastomer comprises natural rubber of about 25 phr to about 75 phr and synthetic elastomer of about 25 phr to about 75 phr; and wherein the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 200 mg KOH / g and a softening point of about 70°C to about 125°C.

[0099] Aspect 23. The method according to aspect 22, wherein forming the initial mixture further comprises combining at least one of filler, wax, anti-degradation agent, fatty acid or processing oil.

[0100] Aspect 24. The method according to aspect 23, wherein the filler comprises carbon black.

[0101] Aspect 25. The method according to any one of aspects 22-24, wherein forming the intermediate mixture further comprises combining at least one of a retarder, a curing activator, or a curing agent to form the intermediate mixture.

[0102] As will be seen from the foregoing, the aspects described herein are well-suited to achieving all the purposes and objectives set forth above, as well as other advantages that are evident and inherent to the structure. Although the specific elements and steps are discussed in conjunction with each other, it should be understood that any element and / or step provided herein is contemplated as being in combination with any other element and / or step, whether or not such elements and / or steps are explicitly specified, while remaining within the scope provided herein.

[0103] It will be understood that certain features and sub-combinations are useful and can be used without reference to other features and sub-combinations. This is contemplated by the claims and is within the scope of the claims. Those skilled in the art will recognize many variations and modifications of the aspects described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0104] Having described aspects of this disclosure, the following embodiments illustrate some additional aspects of this disclosure. While various aspects of this disclosure have been described in conjunction with the following embodiments and corresponding text, it is not intended to limit the aspects of this disclosure to this specification. Rather, it is intended to cover all alternatives, modifications, and equivalents included within the spirit and scope of this disclosure.

[0105] F. Examples The following examples are provided to provide those skilled 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, and are intended only as examples of this disclosure and not to limit the scope of the disclosure as the inventors believe it to be. Efforts have been made to ensure accuracy regarding figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise stated, parts are parts by weight, temperatures are in °C or at ambient temperature, and pressures are atmospheric pressure or near atmospheric pressure.

[0106] Evaluation of rubber compositions Table 1 provides seven rubber compositions containing polybutadiene rubber and natural rubber-based matrices. Significant differences between these compositions include the presence of rosin and the type of accelerator used.

[0107] Table 1. Rubber compositions, wherein amounts are shown in phr. 1 TSR Rank 2 N550 3 N220 4 Phenolic 5 Mixed aryl p-phenylenediamine 6 2,2,4-Trimethyl-1,2-dihydroquinoline 7 N-Phenylacetyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine 8 Processed distillate aromatic extract oil with low polycyclic aromatic hydrocarbon content 9 Non-productive mixture 1 10 Tetrabenzylthiuram disulfide 11 N-Cyclohexylbenzothiazole-2-sulfenamide 12 Diphenylguanidine.

[0108] Dynamic and static ozone resistance tests were conducted on the sidewall rubber samples formed from the compositions listed in Table 1. Figure 1A-1G This image shows a photograph of a tire sidewall rubber specimen after undergoing a dynamic ozone resistance test according to test methods such as ASTM D1149 and DIN 53509. Figure 1A The sidewall rubber sample in the sample corresponds to the control group composition, while Figure 1B-1G The sidewall rubber sample in the sample corresponds to the experimental group composition, specifically experimental group A ( Figure 1B Experimental group B Figure 1C Experimental group C () Figure 1D Experimental group D Figure 1E ), Experimental group E ( Figure 1F ) and experimental group F ( Figure 1G ). Figure 2A-2G This shows photographs of tire sidewall rubber specimens after undergoing static ozone resistance testing according to test methods such as ASTM D1149 and DIN 53509. Figure 2A The sidewall rubber sample corresponds to the control group composition, while Figure 2B-2GThe sidewall rubber sample in the sample corresponds to the experimental group composition, specifically experimental group A ( Figure 2B Experimental group B Figure 2C Experimental group C () Figure 2D Experimental group D Figure 2E ), Experimental group E ( Figure 2F ) and experimental group F ( Figure 2G In both dynamic and static ozone tests, the rubber samples exhibited an ozone resistance rating of 0, meaning that no cracks, fissures, or other defects were observed on the rubber samples. This indicates that all rubber samples demonstrated good ozone resistance.

[0109] In summary, both dynamic and static ozone tests are performed according to ASTM D1149, DIN 53509, or a combination thereof. Rubber specimens are prepared from vulcanized rubber compositions. The tested rubber specimens are rectangular strips, with the rectangular strip dimensions for dynamic ozone testing being 65 mm × 10 mm × 2 mm, and the rectangular strip dimensions for static ozone testing being 254 mm × 150 mm × 2 mm. The specimens are exposed to a known, controlled concentration of ozone at 38°C for 12 hours (dynamic ozone test) or 24 hours (static ozone test). In this embodiment, the ozone concentration is 50 pphm. For dynamic ozone testing, the specimens are tested under conditions of 60% relative humidity and a dynamic maximum amplitude tensile strain of 0% to 25% elongation applied at a fixed frequency of 0.5 Hz. For static ozone testing, the specimens are tested under conditions of 40% relative humidity and a constant tensile strain of 20% elongation.

[0110] Figures 3A-3B Images of tire sidewall rubber samples that have undergone flex static ozone resistance testing are shown. Figure 3A The sample did not contain rosin or diphenylguanidine, while Figure 3B The sample contained both rosin and diphenylguanidine. Figure 3A The sidewall rubber sample corresponds to the control group composition. Figure 3B The sidewall rubber samples corresponded to composition A in experiment group. Neither rubber sample showed stress marks after the flexural static ozone test. However, the sample containing rosin and diphenylguanidine showed significantly less visible wax bloom than the other sample. Not wanting to be bound by theory, it is believed that wax migrating to the surface of the tire sidewall and / or bead wrap protects the tire from ozone damage during static storage. However, such wax migration, or excessive wax migration, can also lead to visible wax bloom on the tire surface, which can be considered negative for those selling and buying tires. These compositions maintain ozone resistance while reducing visible wax bloom.

[0111] In summary, for the flexural static ozone test, the rubber specimen was prepared from a vulcanized rubber composition. The tested rubber specimen was a rectangular strip with dimensions of 150 mm × 20 mm × 6 mm. The specimen was exposed to a known, controlled concentration of ozone (200 pphm) for 46 hours in a chamber at 25°C and 60% relative humidity. In this example, the ozone concentration was 50 pphm. The sample was tested under these conditions while a continuous tensile strain of 7% elongation was applied.

[0112] It will be apparent to those skilled in the art that various modifications and variations can be made to this disclosure without departing from its scope or spirit. Other aspects of this disclosure will become apparent to those skilled in the art upon consideration of this specification and the practice of the contents disclosed herein. The specification and embodiments are intended to be illustrative only, and the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A composition comprising: An elastomer comprising about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; An accelerator comprising about 0.1 phr to about 5 phr of a first accelerator and about 0.1 phr to about 5 phr of a second accelerator; and Hydrogenated rosin from approximately 0.1 phr to approximately 10 phr; The hydrogenated rosin described therein has an acid value of about 140 mg KOH / g to about 200 mg KOH / g and a softening point of about 70°C to about 125°C.

2. The composition of claim 1, wherein the synthetic elastomer comprises repeating units formed from residues of monomers selected from ethylene, propylene, isobutylene, butadiene, isoprene, styrene, acrylonitrile, and combinations thereof.

3. The composition according to claim 1, wherein the first accelerator is selected from dithiocarbamates, thiuram compounds, guanidine compounds, and combinations thereof.

4. The composition according to claim 1, wherein the first accelerator is selected from zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; zinc N-ethyl-N-phenyldithiocarbamate; zinc dibenzyldithiocarbamate; tetrabenzylthiuram disulfide; diphenylguanidine; 1,3-di-o-tolueneguanidine; triphenylguanidine; and combinations thereof.

5. The composition according to claim 1, wherein the second accelerator is selected from amines, imines, sulfenamides, guanidines, dithiocarbamates, thiadiazoles, thiazoles, thiourea, thiuram, dithiophosphates, xanthates, and combinations thereof.

6. The composition according to claim 1, wherein the second accelerator is selected from cyclohexylethylamine; hexamethylenetetramine; ethylidene aniline; butyraldehyde diphenylamine condensate; N-cyclohexyl-2-benzothiazole sulfenamide; N-tert-butyl-2-benzothiazole sulfenamide; N,N-dicyclohexyl-2-benzothiazole sulfenamide; 2-(2,4'-dinitrophenylmercapto)benzothiazole; 1,3-di-o-tolueneguanidine; triphenylguanidine; zinc diethyldithiocarbamate; zinc N-dibutyldithiocarbamate; N-ethyl-N-phenyl Zinc dithiocarbamate; zinc dibenzyl dithiocarbamate; N-cyclohexyl-S-(1,3,4-thiadiazol-2-yl)thiohydroxylamine; 2-mercaptobenzothiazole; 2,2'-dithiobenzothiazole; zinc 2-mercaptobenzothiazole; 2-(morpholinothio)benzothiazole; ethylidene thiourea; N-N'-diphenylthiourea; tetramethylthiuram disulfide; tetraethylthiuram disulfide; tetramethylthiuram monosulfide; dipentamethylthiuram tetrasulfide; zinc dithiophosphate; zinc butyl xanthate; sodium isopropyl xanthate; and combinations thereof.

7. The composition according to claim 1, wherein the hydrogenated rosin has an acid value of about 140 mg KOH / g to about 180 mg KOH / g.

8. The composition according to claim 1, wherein the hydrogenated rosin has a softening point of about 70°C to about 100°C.

9. An article comprising the composition of claim 1.

10. A method for mixing rubber, comprising: The elastomer is combined with hydrogenated rosin of about 0.1 phr to about 10 phr to form an initial mixture; The initial mixture is mixed at a temperature of about 130°C to about 180°C to form a first-stage mixture; The first-stage mixture is combined with a first accelerator of 0.1 phr to about 5 phr and a second accelerator of about 0.1 phr to about 5 phr to form an intermediate mixture; and The intermediate mixture is mixed at a temperature of about 90°C to about 110°C to form a second-stage mixture; The elastomer comprises about 25 phr to about 75 phr of natural rubber and about 25 phr to about 75 phr of synthetic elastomer; and The hydrogenated rosin described therein has an acid value of about 140 mg KOH / g to about 200 mg KOH / g and a softening point of about 70°C to about 125°C.

Images