Rubber composition and product thereof

Abstract

The invention relates to a rubber composition and a product thereof. The uncured composition comprises a partially saturated elastomer, characterized in that less than or equal to 15% of all repeating units of the partially saturated elastomer comprise double bonds, and 2, 2, 4-trimethyl-1, 2-dihydroquinoline (TMDQ), or oligomers thereof, partially or completely in place of traditional antiozonizers such as, for example, 6PPD.

Description

Technical Field

[0001] This invention relates to an uncured composition, and more particularly to a vulcanized rubber composition and articles thereof. Background Technology

[0002] Rubber products (such as vehicle tires) are degraded by atmospheric oxygen and ozone, leading to discoloration and structural defects (such as cracking) under strain conditions (e.g., road use). Ozone can also react with some polymers in tires by generating free radicals. Damage caused by ozone and free radicals can result in aesthetic deterioration, as well as performance and safety issues. Therefore, antioxidants and anti-ozone agents have been introduced into tire sidewalls to protect against the effects of atmospheric oxygen and ozone.

[0003] 6PPD is a compound with anti-ozone properties and is often incorporated into rubber products, including vehicle tires.

[0004]

[0005] This compound migrates to the surface of the vehicle tire over time, essentially forming a film that removes ozone before it can degrade the rubber. 6PPD is primarily self-replenished on the tire surface through continuous blooming. However, due to its high reactivity, 6PPD can be converted into byproducts. For example, 6PPD-quinone is an oxidation byproduct of 6PPD in tires.

[0006]

[0007] Therefore, there is a need for an alternative compound with comparable or better antioxidant, anti-ozone, and migration properties through rubber. Summary of the Invention

[0008] For the purposes of this disclosure, as specifically embodied and broadly described herein, in one embodiment, this disclosure relates to uncured compositions comprising a partially saturated elastomer, wherein less than or equal to 15% of all repeating units of said partially saturated elastomer comprises double bonds, and 2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) or oligomers thereof. TMDQ or oligomers thereof provide ozone-resistant properties, eliminating the need for the use of conventional ozone-resistant agents such as, for example, 6PPD. The use of TMDQ or oligomers thereof provides good crack resistance. Vulcanized rubber compositions comprising the vulcanized uncured composition are also disclosed, as well as articles comprising tires and / or tire assemblies made from or containing the vulcanized rubber composition.

[0009] Other systems, methods, features, and advantages of this disclosure will be apparent to those skilled in the art after studying the following figures and detailed 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 described embodiments can be used in all embodiments 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 described embodiments, are combinable and interchangeable with each other.

[0010] The present invention discloses the following solutions:

[0011] Option 1. An uncured composition comprising:

[0012] At least one partially saturated elastomer comprising repeating units, wherein less than or equal to 15% of all repeating units of the partially saturated elastomer comprise double bonds, and

[0013] 2,2,4-Trimethyl-1,2-dihydroquinoline or its oligomers.

[0014] Option 2. The composition according to Option 1, wherein the composition comprises about 2 phr to about 8 phr of 2,2,4-trimethyl-1,2-dihydroquinoline or an oligomer thereof.

[0015] Option 3. The composition according to Option 1, wherein the composition does not contain a p-phenylenediamine compound.

[0016] Option 4. The composition according to Option 1, wherein the p-phenylenediamine compound is 6PPD, DTPD, or any combination thereof.

[0017] Option 5. The composition according to Option 1, wherein the partially saturated elastomer comprises repeating units formed from residues of one or more monomers selected from ethylene, propylene, butadiene, isoprene, styrene, and any combination thereof.

[0018] Option 6. The composition according to Option 1, wherein the partially saturated elastomer is partially hydrogenated styrene-butadiene rubber.

[0019] Option 7. The composition according to Option 1, wherein the partially saturated elastomer has a glass transition temperature of about -20°C to about -65°C.

[0020] Option 8. The composition according to Option 1, wherein the partially saturated elastomer has a weight-average molecular weight of 200,000 g / mol to 500,000 g / mol.

[0021] Option 9. The composition according to Option 1, wherein about 4% to about 11% of all repeating units have double bonds.

[0022] Option 10. The composition according to Option 1, comprising...

[0023] Partially saturated elastomers ranging from 75 phr to 100 phr, and

[0024] One or more of polybutadiene rubber, polyisoprene, hydrogenated styrene-butadiene rubber, and natural rubber, ranging from 0 phr to 25 phr.

[0025] Option 11. The composition according to Option 1, wherein the partially saturated elastomer comprises solution-polymerized styrene-butadiene rubber, said styrene-butadiene rubber having one or more of the following:

[0026] i) Less than 5% of the total number of non-hydrogenated vinyl groups based on the total number of vinyl groups in hydrogenated styrene-butadiene rubber;

[0027] ii) Based on the total number of cis-1,4- and trans-1,4-butadiene repeating units, less than 20% of the non-hydrogenated double bonds in the cis-1,4- and trans-1,4-butadiene repeating units;

[0028] iii) 80% to 99% of hydrogenated double bonds; and

[0029] iv) 5% to 40% by weight of bound styrene and 50% to 95% by weight of butadiene.

[0030] Option 12. The composition according to Option 1, wherein the composition further comprises silicon dioxide in an amount of 10 phr to 100 phr.

[0031] Option 13. The composition according to Option 1, further comprising 3 phr to 20 phr of polyoctenamer.

[0032] Option 14. The composition according to Option 1, wherein the composition further comprises a vulcanizing agent in an amount of 0.4 phr to 15.0 phr.

[0033] Option 15. The composition according to Option 1, wherein the composition further comprises a vulcanization accelerator in an amount of 0.3 phr to 4.0 phr.

[0034] Scheme 16. A vulcanized rubber composition comprising the uncured composition of Scheme 1 that has been vulcanized.

[0035] Option 17. The composition according to Option 16, wherein the composition has a PG flex crack length of about 3.0 mm to about 3.5 mm at 180 minutes as determined by ASTM D813, or has a PG flex crack length of about 4.0 mm to about 5.5 mm at 240 minutes as determined by ASTM D813.

[0036] Scheme 18. An article comprising the vulcanized rubber composition described in Scheme 16.

[0037] Option 19. The article of claim 18, wherein the article of claim 18 comprises a tire or a tire assembly.

[0038] Option 20. The article of claim 19, wherein the components of the tire include a tread, a base, a gusset, a bead wrap, a wirecoat, an inner liner, or any combination thereof. Attached Figure Description

[0039] Other embodiments of this disclosure will be readily understood when the various embodiments described below are read in conjunction with the accompanying drawings.

[0040] Figure 1 The prior art demonstrates the use of 6PPD and DTPD as anti-ozone agents, and the resulting rubber compositions are determined by ozone testing methods to be substantially free of cracks. The rubber compositions consist of partially saturated elastomers containing repeating units, wherein more than 15% of all repeating units of the partially saturated elastomers contain double bonds.

[0041] Figure 2 The use of TMDQ as an anti-ozone agent is demonstrated by the fact that the resulting rubber composition is determined to be substantially free of cracks by an ozone testing method. The rubber composition consists of a partially saturated elastomer containing repeating units, wherein less than or equal to 15% of all repeating units of the partially saturated elastomer contain double bonds.

[0042] Figures 3A and 3B show the use of TMDQ as an anti-ozone agent (3 phr and 5 phr, respectively), the resulting rubber compositions which, as determined by an ozone test method, have a number of small cracks, wherein the rubber compositions consist of a partially saturated elastomer containing repeating units, wherein more than 15% of all repeating units of the partially saturated elastomer contain double bonds. Detailed Implementation

[0043] Many modifications and other embodiments of the disclosed compositions and methods will arise to those skilled in the art from the teachings presented in the foregoing description and related drawings. Therefore, it should be understood that this disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Those skilled in the art will recognize many variations and modifications of the embodiments described herein. These variations and modifications are intended to be included in the teachings of this disclosure and are covered by the claims herein.

[0044] Although specific terms are used in this article, they are used only in a general and descriptive sense, and not for restrictive purposes.

[0045] As will be apparent to those skilled in the art upon reading this disclosure, each individual embodiment described and illustrated herein has discrete components and features that can be readily separated from or combined with features of any of the other plurality of embodiments without departing from the scope or spirit of this disclosure.

[0046] 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 embodiment 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 way of inferring the order. This applies to any possible non-explicit basis of interpretation, including the logical content of the arrangement of steps or procedures, the plain meaning derived from grammatical organization or punctuation, or the number or type of embodiments described in the specification.

[0047] It should also be understood that the terminology used herein is for the purpose of describing particular embodiments 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 pertain. It will be further understood that terms as defined in commonly used dictionaries should be interpreted as having the same meaning as they have in the context of the specification and the relevant field, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0048] Before describing the various embodiments of this disclosure, the following definitions are provided and should be used unless otherwise specified. Additional terms may be defined elsewhere in this disclosure.

[0049] definition

[0050] 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 embodiments covered by the terms “basically composed of” and “composed of.” Similarly, the term “basically composed of” is intended to include instances covered by the term “composed of.”

[0051] 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” or “vulcanizing agent” include, but are not limited to, mixtures or combinations of two or more such elastomers or vulcanizing agents.

[0052] 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 this document discloses quantities of many values, 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 forms another embodiment. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0053] When indicating a range, another embodiment 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 a range from "x" to "y" as well as ranges greater than "x" and less than "y". A range can also be expressed as an upper limit, such as "about x, y, z or less", and should be interpreted as including specific ranges of "about x", "about y", and "about z" as well as ranges of "less than x", "less than y", and "less than z". Similarly, the phrase "about x, y, z or greater" should be interpreted as including specific ranges of "about x", "about y", and "about z" as well as ranges of "greater than x", "greater than y", and "greater than z". Furthermore, the phrase "about "x" to "y" (where "x" and "y" are numerical values) includes "about "x" to about "y".

[0054] 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 explicitly listed values ​​that form the boundaries of the range, but also all individual values ​​or subranges covered within that range, just 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 listed 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 range shown (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).

[0055] 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.

[0056] 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.

[0057] 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.

[0058] Unless otherwise specified, the terms “rubber” and “elastomer” are used interchangeably in this document.

[0059] As used herein, “glass transition temperature” or “Tg” refers to the glass transition temperature of an elastomer or rubber in its uncured state, or, in some embodiments, in the case of an elastomer composition, Tg can be measured in the cured state. Tg can be appropriately determined as the midpoint of its peak value using differential scanning calorimetry (DSC) according to ASTM D3418 or an equivalent standard.

[0060] 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 additional 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 some embodiments, the uncured rubber composition is a masterbatch.

[0061] As used herein, the term "vulcanized rubber composition" refers to a rubber composition obtained by obtaining an uncured composition as described herein and curing or vulcanizing it, typically using sulfur compounds and / or other curing additives and performed 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 another embodiment, the rubber composition may be cured in a mold to form finished articles, including but not limited to tires.

[0062] As used herein, the term "repeating unit" in the context of partially saturated elastomers is derived from the monomers used to prepare partially saturated elastomers. For example, polybutadiene has repeating units provided below, wherein the repeating units may have cis or trans stereochemical formulas.

[0063]

[0064] In some embodiments, when the partially saturated elastomer is a polymer of two different monomers (e.g., A and B), the repeating unit can be represented by -AB-.

[0065] 2,2,4-Trimethyl-1,2-dihydroquinoline, also referred to herein as TMDQ, has the following structure:

[0066]

[0067] The above structure describes TMDQ as a monomer; however, oligomers (e.g., dimers, trimers, etc.) consisting of two or more repeating units of TMDQ can also be used. In one embodiment, a mixture of oligomers of TMDQ plus residual monomers of TMDQ can be used as an anti-ozone agent as described herein. Examples of TMDQDs used herein include, but are not limited to, RUBATAN 184 manufactured by General Quimica (Spain), VULKANOX HS / LG manufactured by Lanxess (Germany), and polymeric trimethyldihydroquinoline manufactured by SHANDONG SUNSINE CHEMICALS (China).

[0068] p-Phenylenediamine compounds have the following general formula structure

[0069]

[0070] Where R and R' are independently hydrogen, alkyl, cycloalkyl, or aryl. Examples of p-phenylenediamine compounds include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD).

[0071]

[0072] Another example of a p-phenylenediamine antiozone agent is DTPD, which is the product of the reaction of aniline and o-toluidine with hydroquinone. DTPD is a mixture of N,N'-o-tolyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, and N,N'-di-o-tolyl-p-phenylenediamine.

[0073] Unless otherwise stated, the pressures mentioned in this article are based on atmospheric pressure (i.e., one atmosphere).

[0074] rubber composition

[0075] It has been found that the combined use of TMDQ or its oligomers with partially saturated elastomers eliminates the need for conventional antiozone agents such as p-phenylenediamine compounds like 6PPD and DTPD. Therefore, the rubber compositions described herein do not include p-phenylenediamine compounds. In one embodiment, TMDQ or its oligomers are the only antiozone agent present in the rubber composition.

[0076] It was also found that using low amounts of TMDQ or its oligomers in the absence of other anti-ozone agents results in the formation of a rubber composition with favorable physical properties. In one embodiment, the rubber composition described herein comprises about 2 phr to about 8 phr of TMDQ or its oligomers. In one embodiment, the rubber composition described herein comprises about 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr, or 8 phr of TMDQ or its oligomers, wherein any value can be a lower and upper endpoint of the range (e.g., 3 phr to 6 phr).

[0077] When used in combination with TMDQ or its oligomers, the saturation of the partially saturated elastomer affects the physical properties of the rubber composition.

[0078] In one embodiment, the partially saturated elastomer comprises repeating units, wherein less than or equal to 15% of all repeating units contain double bonds. In other embodiments, the amount of repeating units containing double bonds can be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or less than or equal to 15%, where any value can be the lower or upper limit of the range (e.g., 5% to 10%). When counting double bonds, double bonds in aromatic structures or groups, such as those present in styrene repeating units, are not included in the count. However, styrene units are still counted as repeating units when determining the total number of repeating units in the elastomer.

[0079] In one embodiment, the partially saturated elastomer may comprise repeating units formed from residues of one or more monomers selected from ethylene, propylene, butadiene, isoprene, styrene, and any combination thereof. In other embodiments, the partially saturated elastomer is hydrogenated styrene-butadiene rubber, and in some embodiments, hydrogenated solution-polymerized styrene-butadiene rubber (SSBR). The styrene content of the hydrogenated styrene-butadiene rubber may be from about 5 wt% to about 40 wt%, or about 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt%, where any value may be the lower or upper limit of the range (e.g., 20 wt% to 40 wt%), and the butadiene content may be from about 60 wt% to about 95 wt%, or about 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%, where any value may be the lower or upper limit of the range (e.g., 75 wt% to 90 wt%). In some implementations, when less than or equal to 15% of all repeating units of the SSBR contain double bonds, the SSBR may be referred to as a partially hydrogenated SSBR (HSBR).

[0080] In other embodiments, the HSBR may be characterized by containing double bonds in about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or less than or equal to 15% of all repeating units, where any value may be the lower and upper limits of the range (e.g., 4% to 11%). HSBRs may also be characterized by a weight-average molecular weight (Mg) of approximately 100 kg / mol to approximately 4,000 kg / mol, or 100 kg / mol, 200 kg / mol, 300 kg / mol, 400 kg / mol, 500 kg / mol, 600 kg / mol, 700 kg / mol, 800 kg / mol, 900 kg / mol, 1,000 kg / mol, 1,100 kg / mol, 1,200 kg / mol, 1,300 kg / mol, 1,400 kg / mol, 1,500 kg / mol, 2,000 kg / mol, 3,000 kg / mol, or 4,000 kg / mol. w ), where any value can be the lower or upper limit of a range (e.g., 600 kg / mol to 900 kg / mol). In another embodiment, the HSBR may be characterized by having a polydispersity index (Mi) of about 1.05 to about 2.0 or 1.2, 1.4, 1.6, 1.8 or 2.0. w / M n M nThe molecular weight is a number-average molecular weight, where any value can be the lower or upper limit of the range (e.g., 1.4 to 1.8). The molecular weight parameter can be determined by gel permeation chromatography using a polystyrene calibration standard or equivalent according to ASTM 5296-11. In other embodiments, the HSBR can have a glass transition temperature of about -70°C to about -20°C, or about -70°C, -60°C, -50°C, -40°C, -30°C, or -20°C, where any value can be the lower or upper limit of the range (e.g., -60°C to -40°C).

[0081] In some embodiments, partially saturated elastomer HSBRs can be obtained by hydrogenating the elastomer. The method for hydrogenating the elastomer can be any method known in the art. In one embodiment, hydrogenation is carried out by blowing aqueous hydrogen into the elastomer or polymer solution in the presence of a catalyst, such as a heterogeneous catalyst, a homogeneous catalyst, or a metallocene catalyst (e.g., titanocene), or any combination thereof. Examples of heterogeneous catalysts include catalysts containing noble metals supported on porous inorganic materials. Examples of homogeneous catalysts include catalysts obtained by reacting dissolved salts of nickel, cobalt, etc., with organoaluminum, etc. The degree of hydrogenation in the resulting elastomer can be controlled by changing factors such as the amount of hydrogen added, hydrogen pressure, reaction time, reaction temperature, amount of catalyst added, polymer solution viscosity, or any combination thereof. In some embodiments, the hydrogenation reaction is carried out at a temperature of about 60°C to 105°C, or about 60°C, 70°C, 80°C, 90°C, 100°C, or 105°C, where any value can be the lower or upper limit of the range (e.g., 70°C to 100°C). In some embodiments, the hydrogenation reaction is carried out as a batch process, a continuous process, or a combination thereof. Additional details regarding the preparation of the partially saturated elastomer are described in U.S. Patent Application Publication US2023 / 0138073 A1 and European Patent Application Publication EP 4261234A1, and are incorporated herein by reference.

[0082] In one embodiment, the rubber composition comprises

[0083] Partially saturated elastomers ranging from 75 phr to 100 phr, and

[0084] One or more of polybutadiene rubber, polyisoprene, hydrogenated styrene-butadiene rubber, and natural rubber, ranging from 0 phr to 25 phr.

[0085] In another embodiment, the partially saturated elastomer comprises solution-polymerized styrene-butadiene rubber having one or more of the following characteristics:

[0086] i) The total amount of non-hydrogenated vinyls based on hydrogenated styrene-butadiene rubber is less than 5%;

[0087] ii) Based on the total number of cis-1,4- and trans-1,4-butadiene repeating units, less than 20% of the non-hydrogenated double bonds in the cis-1,4- and trans-1,4-butadiene repeating units;

[0088] iii) 80% to 99% of hydrogenated double bonds; and

[0089] iv) 5% to 40% by weight of bound styrene and 50% to 95% by weight of butadiene.

[0090] The uncured rubber composition described herein may include additional components commonly used in the preparation of rubber compositions. In one embodiment, the rubber composition may include silica of about 5 phr to about 100 phr. Various commercially available silicas may be used, such as, for example but not limited to, silica commercially available under the trademark Hi-Sil from PPGindustries, named 210, 243, etc.; silica available from Solvay, for example named Z1165MP, Z165GR and Zeosil Premium 200MP; and silica gel available from Degussa AG, for example named VN2 and VN3, etc. In other embodiments, blends of two or more silicas may also be used, for example, blends of silicas with relatively high surface area and silicas with relatively low surface area.

[0091] In one embodiment, the uncured rubber composition may further comprise a vulcanizing agent in amounts of about 0.4 phr to about 15.0 phr, or about 0.4 phr, 3.0 phr, 6.0 phr, 9.0 phr, 12.0 phr, or 15.0 phr, wherein any value may be the lower or upper limit of the range (e.g., 9.0 phr to 12.0 phr). In some embodiments, the vulcanizing agent comprises elemental sulfur, sulfur-containing silanes, or combinations thereof. Furthermore, the uncured rubber composition may further comprise a vulcanization accelerator. The vulcanization accelerator may be preferred, but not necessarily, used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized composition. The amount of vulcanization accelerator in the composition may be about 0.3 phr to about 4.0 phr, or 0.3 phr, 1.0 phr, 2.0 phr, 3.0 phr, or 4.0 phr, wherein any value may be the lower or upper limit of the range (e.g., 1.0 phr to 2.0 phr).

[0092] In some embodiments, the vulcanization accelerator includes dithiocarbamate accelerators, thiuram accelerators, diphenylguanidine accelerators, benzothiazole sulfenamide accelerators, or combinations thereof. Potential vulcanization accelerator compounds may include derivatives; for example, benzothiazole sulfenamide accelerators include benzothiazole sulfenamides, and may also include derivatives of benzothiazole sulfenamides. In other embodiments, the vulcanization accelerator includes amines, disulfides, guanidines, thioureas, thiazoles, thiuram, sulfenamides, dithiocarbamates, and xanthates. In yet another embodiment, the vulcanization accelerator includes a combination of primary and secondary accelerators, wherein the secondary accelerator is used in a small amount, such as 0.05 phr to 3.00 phr. In some embodiments, the secondary accelerator is selected from guanidine, dithiocarbamates, or thiuram. Furthermore, delayed-action accelerators can be used, which are unaffected by normal processing temperatures but produce satisfactory curing at ordinary vulcanization temperatures.

[0093] In one embodiment, the uncured rubber composition may contain additional components, such as oil. In some embodiments, the oil is a processing oil. Processing oil may be included in the composition as an extender oil typically used for extending elastomers. Processing oil may also be included in the elastomer composition by adding the oil directly during rubber compounding. The processing oil used may include extender oils present in the elastomer and 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-PCA oils such as MES, TDAE, SRAE, and heavy naphthenic oils. Suitable low-PCA oils may include those with a polycyclic aromatic hydrocarbon content of less than 3% by weight as determined by the IP346 method. The procedure for the IP346 method can be found in: Standard Test Methods for Analysis and Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, UK. Suitable TDAE oils are available as Tudalen SX500 from Klaus Dahleke KG, VivaTec 400 and VivaTec 500 from H&R Group, Enerthene 1849 from BP, and Extensoil 1996 from Repsol. The oils can be obtained as standalone oils or as additive elastomers. 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.

[0094] In one embodiment, the rubber composition comprises 3 phr to 20 phr of polyoctenamer. In another embodiment, the amount of polyoctenamer in the composition can be about 3 phr, 5 phr, 7 phr, 9 phr, 11 phr, 13 phr, 15 phr, 17 phr, or 20 phr, where any value can be the lower or upper limit of the range (e.g., 7 phr to 17 phr).

[0095] In one embodiment, polyoctene has one or more of the following: a glass transition temperature in the range of -50°C to -80°C, as described below, determined according to ASTM D3418; and a weight-average molecular weight M determined by gel permeation chromatography (GPC) using a polystyrene calibration standard according to ASTM 5296-11 or equivalent standards. W The melting point is in the range of 80,000 g / mol to 100,000 g / mol; and the melting point, measured by DSC upon second heating according to ASTM D3418 or equivalent standards, is in the range of 45°C to 55°C. In another embodiment, polyoctene has 65% to 85% trans double bonds, meaning that 65% to 85% of all double bonds in polyoctene are trans double bonds.

[0096] This document describes vulcanized rubber compositions, wherein any uncured rubber compositions described herein are vulcanized. In one aspect, when using TMDQ or its oligomers, the vulcanized rubber composition exhibits the same or improved reduction in crack propagation compared to the same cured composition containing the same amount of a p-phenylenediamine compound (e.g., 6PPD or DTPD). In one embodiment, when using TMDQ or its oligomers, the vulcanized rubber composition exhibits a 5% to 20% reduction in crack propagation compared to the same cured composition containing the same amount of a p-phenylenediamine compound using the same test method. In another embodiment, when using TMDQ or its oligomers, the vulcanized rubber composition exhibits a 5%, 10%, 15%, or 20% reduction in crack propagation compared to the same cured composition containing the same amount of a p-phenylenediamine compound using the same test method, where any value can be the lower or upper limit of the range (e.g., 10% to 20%). In one embodiment, ASTM D813 (perforation groove test or PG flexure) can be used to determine crack propagation.

[0097] In another embodiment, when compared to the same cured composition using the same test method and containing a partially saturated elastomer (of which more than 15% of all repeating units of the partially saturated elastomer have double bonds), the vulcanized rubber composition exhibits the same or improved reduction in crack propagation when using a partially saturated elastomer (of which less than or equal to 15% of all repeating units of the partially saturated elastomer have double bonds). In one embodiment, when compared to the same cured composition using the same test method and containing a partially saturated elastomer (of which more than 15% of all repeating units of the partially saturated elastomer have double bonds), the vulcanized rubber composition exhibits a 50% to 90% improvement in crack propagation reduction when using a partially saturated elastomer (of which less than or equal to 15% of all repeating units of the partially saturated elastomer have double bonds). In another embodiment, when using a partially saturated elastomer (where less than or equal to 15% of all repeating units of the partially saturated elastomer have double bonds), the vulcanized rubber composition exhibits 50%, 60%, 70%, 80%, or 90% improved crack propagation reduction compared to the same cured composition using the same test method and containing a partially saturated elastomer (where less than or equal to 15% of all repeating units of the partially saturated elastomer have double bonds).

[0098] In addition to reducing crack propagation, the use of TMDQ also reduces or prevents crack formation. As shown in the examples, rubber compositions prepared with TMDQ and partially saturated elastomers (where less than or equal to 15% of all repeating units of the partially saturated elastomer have double bonds) are substantially crack-free. Similarly, the same rubber compositions prepared with 6PPD and DTPD as ozone inhibitors are also substantially crack-free. Rubber compositions prepared with TMDQ exhibit comparable ozone resistance when compared to those using conventional ozone inhibitors such as 6PPD and DTPD. In one embodiment, ozone testing methods, such as, for example, DIN 53509 and DIN ISO 4131-1, can be used to assess crack formation.

[0099] Preparation and application of rubber compositions

[0100] The compositions disclosed herein can be compounded by methods commonly known in the field of rubber compounding, such as mixing partially saturated elastomers and TMDQ or oligomers thereof with various vulcanizable rubbers and various commonly used additive materials such as sulfur donors; curing aids, such as activators and scorch inhibitors; processing additives, such as oils, resins (including tackifying resins) and plasticizers; fillers; pigments; fatty acids; zinc oxide; waxes; antioxidants; anti-ozone agents; and solvents. The amount of zinc oxide that may be included is from about 1 phr to about 5 phr. The above additives are selected according to the intended use of the vulcanizable and vulcanizable material (rubber) and are generally used in conventional amounts. In some embodiments, the amount of tackifying resin included is from about 0.5 phr to 10 phr or from about 1 phr to 5 phr. In some embodiments, the amount of processing additive included is from about 1 phr to 50 phr. In some embodiments, the amount of antioxidant included is from about 1 phr to 5 phr. Representative antioxidants include, but are not limited to, diphenyl-p-phenylenediamine and other antioxidants, such as those disclosed in The Vanderbilt Rubber Handbook edited by Robert O. Babbit (Norwalk, Connecticut, RTVanderbilt Company, Inc., 1978), pages 344-346. In some embodiments, the amount of the anti-ozone agent included is from about 1 phr to 5 phr. Representative anti-ozone agents include, but are not limited to, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD) and N,N'-o-tolyl-p-phenylenediamine (DTPD). In some embodiments, the amount of the fatty acid included is from about 0.5 phr to 3 phr. Examples of fatty acids used include stearic acid. In some embodiments, the amount of the wax included is from about 1 phr to 5 phr. Microcrystalline waxes can be used. In some embodiments, the amount of the colloidal solvent included is from about 0.1 phr to 1 phr. Typical adhesive solvents include, for example, pentachlorothiophenol and dibenzoylaminodiphenyl disulfide.

[0101] The compositions disclosed herein can be mixed using methods known in the field of rubber compounding. For example, the components can typically be mixed in at least two stages: at least one non-productive stage followed by a productive mixing stage. In some embodiments, the mixing of the uncured composition comprises only a single non-productive stage. The final curing agent, including the vulcanizing agent, can typically be mixed in a final stage, often referred to as the “productive” mixing stage, where mixing is typically carried out at a temperature lower than the mixing temperature of the preceding non-productive mixing stages or at the final temperature. In one embodiment, the elastomeric composition can undergo a thermomechanical mixing step. A thermomechanical mixing step typically involves mechanical processing in a mixer or extruder for a period of time, for example, a time suitable for generating a rubber temperature in the range of about 140°C to 190°C. The appropriate duration of thermomechanical processing varies with operating conditions and variations in the volume and properties of the components. For example, thermomechanical processing can be from about 1 to 20 minutes.

[0102] This disclosure also provides articles incorporating any vulcanized rubber composition disclosed herein. In some embodiments, the articles comprise tires, such as pneumatic tires, or components of tires. Tires can be racing tires, passenger car tires, aircraft tires, agricultural tires, bulldozer tires, off-road tires, truck tires, etc. In one embodiment, the tire is a passenger car or truck tire. The tire can also be a radial tire or a bias-ply tire. Tire components can be tread, base, gusset, bead wrap, wirecoat, innerliner, or any combination thereof. In another embodiment, the components of a tire containing the composition are tread, base, sidewall, or any combination thereof. Vulcanization of the disclosed tires is typically carried out at conventional temperatures of about 100°C to about 200°C or about 110°C to about 180°C. Such tires can be constructed, shaped, molded, and cured by a variety of known methods that will readily be apparent to those skilled in the art.

[0103] Having described embodiments of this disclosure, the following examples illustrate some additional embodiments of this disclosure. While embodiments of this disclosure have been described in conjunction with the following examples and corresponding text and drawings, it is not intended to limit the embodiments 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.

[0104] Implementation Plan

[0105] This disclosure can be described according to embodiments numbered below, which should not be confused with the claims.

[0106] Implementation Scheme 1. An uncured composition comprising:

[0107] At least one partially saturated elastomer comprising repeating units, wherein less than or equal to 15% of all repeating units of the partially saturated elastomer comprise double bonds, and

[0108] 2,2,4-Trimethyl-1,2-dihydroquinoline or its oligomers.

[0109] Implementation Scheme 2. The composition according to Implementation Scheme 1, wherein the composition comprises about 2 phr to about 8 phr of 2,2,4-trimethyl-1,2-dihydroquinoline or an oligomer thereof.

[0110] Implementation Scheme 3. The composition according to Implementation Scheme 1 or 2, wherein the composition does not contain a p-phenylenediamine compound.

[0111] Implementation Scheme 4. The composition according to Implementation Scheme 1 or 2, wherein the p-phenylenediamine compound is 6PPD, DTPD, or any combination thereof.

[0112] Implementation Scheme 5. The composition according to any one of Implementation Schemes 1-4, wherein the partially saturated elastomer comprises repeating units formed from residues of one or more monomers selected from ethylene, propylene, butadiene, isoprene, styrene, and any combination thereof.

[0113] Implementation Scheme 6. The composition according to any one of Implementation Schemes 1-4, wherein the partially saturated elastomer is partially hydrogenated styrene-butadiene rubber.

[0114] Implementation Scheme 7. The composition according to any one of Implementation Schemes 1-6, wherein the partially saturated elastomer has a glass transition temperature of about -20°C to about -65°C.

[0115] Implementation Scheme 8. The composition according to any one of Implementation Schemes 1-7, wherein the partially saturated elastomer has a weight-average molecular weight of 200,000 g / mol to 500,000 g / mol.

[0116] Implementation Scheme 9. The composition according to any one of Implementation Schemes 1-8, wherein about 4% to about 11% of all repeating units have double bonds.

[0117] Implementation Scheme 10. The composition according to any one of Implementation Schemes 1-9, comprising

[0118] Partially saturated elastomers ranging from 75 phr to 100 phr, and

[0119] One or more of polybutadiene rubber, polyisoprene, hydrogenated styrene-butadiene rubber, and natural rubber, ranging from 0 phr to 25 phr.

[0120] Implementation Scheme 11. The composition according to any one of Implementation Schemes 1-10, wherein the partially saturated elastomer comprises solution-polymerized styrene-butadiene rubber having one or more of the following:

[0121] i) The total amount of non-hydrogenated vinyls based on hydrogenated styrene-butadiene rubber is less than 5%;

[0122] ii) Based on the total number of cis-1,4- and trans-1,4-butadiene repeating units, less than 20% of the non-hydrogenated double bonds in the cis-1,4- and trans-1,4-butadiene repeating units;

[0123] iii) 80% to 99% of hydrogenated double bonds; and

[0124] iv) 5% to 40% by weight of bound styrene and 50% to 95% by weight of butadiene.

[0125] Implementation Scheme 12. The composition according to any one of Implementation Schemes 1-11, wherein the composition further comprises an amount of silicon dioxide from 10 phr to 100 phr.

[0126] Implementation Scheme 13. The composition according to any one of Implementation Schemes 1-12, further comprising 3 phr to 20 phr of polyoctene.

[0127] Implementation Scheme 14. The composition according to any one of Implementation Schemes 1-13, wherein the composition further comprises a vulcanizing agent in an amount of 0.4 phr to 15.0 phr.

[0128] Implementation Scheme 15. The composition according to any one of Implementation Schemes 1-14, wherein the composition further comprises a vulcanization accelerator in an amount of 0.3 phr to 4.0 phr.

[0129] Implementation Scheme 16. A vulcanized rubber composition comprising an uncured composition of any one of Implementation Schemes 1-15 that has been vulcanized.

[0130] Implementation Scheme 17. The composition according to Implementation Scheme 16, wherein the composition has a PG flexural crack length of about 3.0 mm to about 3.5 mm at 180 minutes as determined by ASTM D813.

[0131] Implementation Scheme 18. The composition according to Implementation Scheme 16, wherein the composition has a PG flexural crack length of about 4.0 mm to about 5.5 mm at 240 minutes as determined by ASTM D813.

[0132] Implementation Scheme 19. An article comprising the vulcanized rubber composition described in any one of Implementation Schemes 16-18.

[0133] Implementation Scheme 20. The article of manufacture according to Implementation Scheme 19, wherein the article of manufacture comprises a tire or a tire assembly.

[0134] Implementation Scheme 21. The article of manufacture according to Implementation Scheme 20, wherein the components of the tire include a tread, a base, a gusset, a bead wrap, a steel wire wrap, an inner liner, or any combination thereof.

[0135] Example

[0136] 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. These examples are intended merely as examples of this disclosure and are not intended 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 taken into account. Unless otherwise stated, parts are parts by weight, temperatures are in °C or at ambient temperature, and pressures are at or near atmospheric pressure.

[0137] Example 1: Comparison of different anti-ozone agents

[0138] Table 1 provides four elastomer compositions comprising a solution-polymerized styrene-butadiene rubber (SSBR) matrix. The most significant difference is that SSBR 2 contains TMDQ as an anti-ozone agent, while SSBR 1 contains 6PPD and DTPD as anti-ozone agents.

[0139] In the case of SSBR 3 and SSBR 4, these compositions contain more than 15% of the partially saturated elastomer having double bonds in all repeating units of their partially saturated elastomer, while SSBR 2 contains less than 15% of the partially saturated elastomer having double bonds in all repeating units of its partially saturated elastomer.

[0140] Table 1

[0141]

[0142]

[0143] 1 Tg is the Tg of hydrogenated solution polymerized styrene-butadiene rubber at -30℃, such as NT120 from Eneos.

[0144] 2 Styrene-butadiene rubber (SBR) polymerized from hydrogenated solution at a Tg of -63℃.

[0145] 3 For Vestenamer from Evonik TM 8012

[0146] 4 Zeosil from Solvay TM Premium 200MP precipitated silica

[0147] 5 For Santoflex from Flexsys TM 6PPD

[0148] 6 Polystay for Goodyear Chemical TM 100

[0149] 7 For Vulkanox from Lanxess TM HS / LG

[0150] 8 SI266 from Evonik TM bis(triethoxysilylpropyl) disulfide

[0151] 9 Contains glyceryl monostearate and zinc fatty acid soap

[0152] 10 Diphenylguanidine (accelerator)

[0153] 11 N-Cyclohexyl-2-benzothiazole sulfenamide (accelerator)

[0154] 12 2-Mercaptobenzothiazole (accelerator), we can add

[0155] Table 2 provides the crack resistance results for each rubber composition. As shown in Table 2, the use of TMDQ in SSBR 2 provided approximately the same or improved reduction in crack propagation compared to the use of 6PPD and DTPD in SSBR 1. Furthermore, SSBR 2 provided a significantly improved reduction in crack propagation compared to SSBR 3 and SSBR 4. In fact, under the PG flexure test (ASTM D813), SSBR 3 and SSBR 4 completely cracked after 240 minutes.

[0156] In addition to reducing crack propagation, the use of TMDQ can also reduce or prevent crack formation. Rubber compositions SSBR 2 prepared with TMDQ and partially saturated elastomers containing repeating units (where less than or equal to 15% of all repeating units of the partially saturated elastomer contain double bonds) (i.e., the compositions of the present invention) are substantially crack-free. Figure 2 Similarly, according to measurements in DIN 53509 and DIN ISO 4131-1, the same rubber composition (SSBR 1; comparative example) prepared using 6PPD and DTPD as anti-ozone agents also showed essentially no cracking. Figure 1 These results indicate that rubber compositions prepared with TMDQ exhibit comparable ozone resistance compared to those using conventional anti-ozone agents such as 6PPD and DTPD.

[0157] In another experiment, rubber compositions SSBR 3 and SSBR 4 were prepared using 3 phr and 5 phr of TMDQ and partially saturated elastomers containing repeating units (wherein more than 15% of all repeating units of the partially saturated elastomer contain double bonds), respectively. SSBR 3 and SSBR 4 are comparative examples. According to measurements in DIN 53509 and DIN ISO 4131-1, SSBR 3 and SSBR 4 exhibit numerous small cracks (Figures 3A and 3B, respectively).

[0158] Finally, replacing traditional anti-ozone agents such as 6PPD and DTPD with TMDQ does not alter the physical properties (dynamic and static properties) of unaged and aged (4 days at 90°C in air) rubber compositions.

[0159] Table 2

[0160] PG flexion SSBR 1 SSBR 2 SSBR 3 SSBR 4 Crack length at 180 minutes 3.33 3.30 14.70 11.80 Crack length at 240 minutes 4.60 4.17 Complete crack Complete crack

[0161] It should be emphasized that the above embodiments of this disclosure are merely possible examples of implementation methods described for the purpose of clearly understanding the principles of this disclosure. Many changes and modifications can be made to the above embodiments without substantially departing from the spirit and principles of this disclosure. All such modifications and changes are intended to be included within the scope of this disclosure and protected by the appended claims.

Claims

1. An uncured composition comprising: At least one partially saturated elastomer comprising repeating units, wherein less than or equal to 15% of all repeating units of the partially saturated elastomer comprise double bonds, and 2,2,4-Trimethyl-1,2-dihydroquinoline or its oligomers.

2. The composition according to claim 1, wherein the composition comprises about 2 phr to about 8 phr of 2,2,4-trimethyl-1,2-dihydroquinoline or an oligomer thereof.

3. The composition according to claim 1, wherein the composition does not contain a p-phenylenediamine compound.

4. The composition according to claim 1, wherein the p-phenylenediamine compound is 6PPD, DTPD, or any combination thereof.

5. The composition of claim 1, wherein the partially saturated elastomer comprises repeating units formed from residues of one or more monomers selected from ethylene, propylene, butadiene, isoprene, styrene, and any combination thereof.

6. The composition according to claim 1, wherein the partially saturated elastomer is partially hydrogenated styrene-butadiene rubber.

7. The composition according to claim 1, wherein the partially saturated elastomer has a glass transition temperature of about -20°C to about -65°C.

8. The composition according to claim 1, wherein the partially saturated elastomer has a weight-average molecular weight of 200,000 g / mol to 500,000 g / mol.

9. A vulcanized rubber composition comprising the uncured composition of claim 1 that has been vulcanized.

10. An article comprising the vulcanized rubber composition of claim 9.

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