Chemically Surface-Modified Carbon Black and Method for Producing the Same

Abstract

Surface-modified and functionalized carbon black for use in rubber compounds suitable for tire tread compounds can be described as surface-modified low hysteresis carbon black. The modified carbon black contains at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds. Surface-modified low hysteresis carbon black in a typical rubber tire tread compound is superior to compounds containing N234 carbon black or silica because it has improved rolling resistance, improved wet traction, and improved or maintained abrasion resistance. Improving tire rolling resistance by using a compound containing surface-modified low hysteresis carbon black is highly desirable for reducing CO2 emissions, reducing pollution, sustainability, and environmental protection.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Provisional Application No. 63 / 357,991, filed on July 1, 2022, entitled “Thermochemically Surface Modified Carbon Black to Improve Tire Rolling Resistance, Wet Traction, and Wear Resistance Comparable to the Silica and Methods of Making Same” and U.S. Provisional Application No. 63 / 460,242, filed on April 18, 2023, entitled “Carbon Black for Truck Tire Tread Compound”, each of which is hereby incorporated by reference in its entirety for all purposes.

[0002] The present disclosure generally relates to rubber - carbon black compositions, which are generally referred to as compounds by those skilled in the art. In particular, the present disclosure relates to treated carbon black materials and methods of manufacturing the same.

Background Art

[0003] Disclosed herein are unpurified surface - modified low - hysteresis carbon black (SMLHCB) or purified surface - modified low - hysteresis carbon black (SMLHCB - R) products, which include low - hysteresis carbon black having a surface modified such that a surface modifier or a fragment of the surface modifier adheres thereto, the surface modifier including at least one amine group and at least one thiol group, its di - and / or polysulfide bonds, the surface modifier adhering to a portion of the surface of the low - hysteresis carbon black, and the surface modifier being present in discrete spaced - apart regions on the surface of the low - hysteresis carbon black.

[0004] Also, this specification discloses a method for manufacturing SMLHCB. The method involves treating the surface of low hysteresis carbon black with a surface modifier at about 0.1% (w / v) to about 50% (w / v) in a suitable solvent (such as water), followed by heat treatment. Here, the surface modifier contains at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds.

[0005] Also, this specification discloses a rubber compound containing SMLHCB or an SMLHCB-R product. Here, SMLHCB or SMLHCB-R has a surface modified such that a surface modifier or a fragment of the surface modifier adheres thereto. The surface modifier contains at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds. The surface modifier in SMLHCB or SMLHCB-R adheres to a part of the surface of the low hysteresis carbon black, and the surface modifier exists in discrete and spaced-apart regions on the surface of the low hysteresis carbon black.

Summary of the Invention

[0006] Embodiments of an unrefined surface-modified low hysteresis carbon black (SMLHCB) or a refined surface-modified low hysteresis carbon black (SMLHCB-R) compound include a low hysteresis carbon black having a surface modified to have a surface modifier attached thereto, the surface modifier including at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, the surface modifier being attached to a fraction of the surface of the low hysteresis carbon black in discrete spaced-apart regions of the surface of the low hysteresis carbon black. In some embodiments, the surface modifier includes an amino acid compound or a derivative of an amino acid compound. In some embodiments, the surface modifier includes at least one of a naturally occurring amino acid, a modified natural amino acid, a synthetic amino acid, its dimer, its polymer, its salt, and its derivative. In certain embodiments, the surface modifier includes at least one of cysteine, cystine, homocysteine, homocystine, methionine, cysteamine, cystamine, and cystine dimethyl ester. In certain embodiments, the surface modifier includes an amino acid compound or a derivative of the amino acid compound having at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds, and / or an organic or inorganic compound including at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds. In some embodiments, the amine group of the surface modifier is configured to bind to the surface of the low hysteresis carbon black. In some embodiments, the amine group of the surface modifier is a primary amine, secondary amine, or tertiary amine having a catalyst for binding to the surface of the low hysteresis carbon black. In certain embodiments, the surface modifier is attached to the surface via a single bond or multiple bonds. In certain embodiments, the surface modifier is attached to the surface of the low hysteresis carbon black by amide or other bond formation, chemisorption, and / or physisorption.In some embodiments, the surface modifier is bound to the surface of the low hysteresis carbon black by at least one of van der Waals interactions, ionic interactions, and / or covalent or other non-covalent interactions with the active surface moieties of the surface. In some embodiments, the active surface moieties include oxygen, nitrogen, and / or sulfur on the surface. In certain embodiments, the surface modifier comprises from about 0.1 weight percent (wt.%) to about 50 wt.% of the SMLHCB or SMLHCB-R compound. In certain embodiments, the SMLHCB or SMLHCB-R compound has a higher proportion of larger aggregates and a broader aggregate size distribution than a standard American Society for Testing and Materials (ASTM) grade carbon black that does not exhibit low hysteresis when compounded. In some embodiments, the aggregate size of the low hysteresis carbon black ranges from about 0.005 micrometers (μm) to about 1.0 μm. In some embodiments, the SMLHCB or SMLHCB-R compound has a surface area in the range of about 10 square meters / gram (m 2 / g) to about 250 m 2 / g. In certain embodiments, the surface of the low hysteresis carbon black is oxidized. In certain embodiments, the surface of the low hysteresis carbon black is oxidized by at least one of ozone treatment, heat treatment, plasma treatment, nitrogen oxide treatment, hydrogen peroxide gas or hydrogen peroxide solution treatment, and liquid nitric acid treatment.

[0007] Embodiments of a method for manufacturing an SMLHCB or SMLHCB-R compound include treating the surface of low hysteresis carbon black with a surface modifier in a solvent at about 0.1 weight percent (w / v) to about 50 weight percent (w / v), and after treating the surface with the surface modifier, heat treating the surface of the low hysteresis carbon black to form an SMLHCB compound. The surface modifier includes at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds. In some embodiments, the surface modifier is bonded to the carbon black surface via thermochemical coupling. In some embodiments, the thermochemical coupling includes heat treatment. In certain embodiments, the heat treatment is performed by any suitable heating source. In certain embodiments, the low hysteresis carbon black is treated with the surface modifier over a period of 72 hours or less at a temperature in the range of about 60 °C to about 450 °C. In some embodiments, the method includes purifying the SMLHCB compound by contacting the SMLHCB compound with a fluid to form an SMLHCB-R compound. In some embodiments, the aggregate size of the low hysteresis carbon black is in the range of about 0.005 micrometers (μm) to about 1.0 micrometer (μm), about 0.01 to about 0.8 μm, or about 0.02 μm to about 0.6 μm. In certain embodiments, the SMLHCB compound has a surface area in the range of about 10 square meters / gram (m 2 / g) to about 250 m 2 / g, or about 20 m 2 / g to about 200 m 2 / g, or about 30 to about 150 m 2 / g.

[0008] Embodiments of the rubber compound include a polymer and an SMLHCB or SMLHCB-R compound, where the SMLHCB or SMLHCB-R compound includes a surface modified to have a surface modifier attached thereto, and the surface modifier includes at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, and the surface modifier is attached to a portion of the surface in discrete spaced regions of the surface. In certain embodiments, the polymer is a natural polymer, a synthetic polymer, or a polymer blend. In some embodiments, the polymer includes at least one of natural rubber, solution styrene butadiene rubber (SBR), emulsion SBR, functional solution SBR, polyisoprene, polybutadiene, EPDM, nitrile, butyl, halogenated butyl, silicone rubber. In some embodiments, the polymer includes a solution styrene butadiene rubber (SBR)-polybutadiene rubber (BR) blend. In certain embodiments, the polymer has a weight ratio of solution styrene butadiene rubber to polybutadiene rubber (SSBR:BR) in the range of about 100.0, or 100:0 to about 0:100. In certain embodiments, the polymer includes at least one of 100 parts per hundred (PHR) of natural rubber, technical specification rubber (TSR) 5 of natural rubber grade, TSR10 of natural rubber grade, TSR20 of natural rubber grade, ribbed smoked sheet rubber-1 (RSS1), RSS2, RSS3, RSS4, and RSS5. In some embodiments, the rubber compound is manufactured using a standard American Society for Testing and Materials (ASTM) grade carbon black that is not of low hysteresis and includes a decrease in network formation between fillers, an increase in the interaction between the polymer and the filler, or both a decrease in network formation between fillers and an increase in the interaction between the polymer and the filler as compared to the same rubber compound in other respects. In some embodiments, a rubber compound containing a solution styrene butadiene rubber (SBR)-polybutadiene rubber (BR) blend and SMLHCB or SMLHCB-R is configured for use in a passenger tire tread compound formulation.In certain embodiments, the rubber compound comprises natural rubber and an SMLHCB or SMLHCB-R compound and is configured for commercial truck tire applications. In certain embodiments, a rubber compound containing SMLHCB-R has improved rolling resistance compared to industry standard ASTM grade carbon black, and thus improved tire and vehicle fuel efficiency. In some embodiments, a rubber compound containing SMLHCB-R has improved tire traction performance compared to industry standard ASTM grade carbon black. In some embodiments, a rubber compound containing SMLHCB-R has improved tire tread wear performance compared to industry standard ASTM grade carbon black. In certain embodiments, a rubber compound containing SMLHCB-R simultaneously improves rolling resistance performance, tire traction performance, and tire wear performance compared to industry standard ASTM grade carbon black. In certain embodiments, a rubber compound containing SMLHCB-R has improved rolling resistance compared to industry standard silica tread-based compounds, and thus improved tire and vehicle fuel efficiency. In some embodiments, a rubber compound containing SMLHCB-R has improved tire tread wear performance compared to industry standard silica tread-based compounds. In the rubber compound according to claims 26-30, a rubber compound containing SMLHCB-R is comparable to industry standard silica tread-based compounds and simultaneously improves rolling resistance, tire traction performance, and tire wear performance. In some embodiments, a rubber compound containing SMLHCB has improved rolling resistance compared to industry standard silica tread-based compounds, and thus improved tire and vehicle fuel efficiency. In certain embodiments, a rubber compound containing SMLHCB has improved tire traction performance compared to industry standard silica tread-based compounds. In certain embodiments, a rubber compound containing SMLHCB or SMLHCB-R reduces the compound pay effect compared to industry standard ASTM grade carbon black.In some embodiments, a rubber compound containing SMLHCB or SMLHCB-R is suitable for a passenger tire tread compound formulation. In some embodiments, a rubber compound containing SMLHCB or SMLHCB-R can replace N234 carbon black at an equivalent level or in part without impairing the compound properties measured in the laboratory. In certain embodiments, it is desirable that a rubber compound containing SMLHCB or SMLHCB-R reduces the compound Payne effect without accompanying changes in other basic properties. In certain embodiments, a rubber compound containing SMLHCB or SMLHCB-R has a significantly increased rebound at 60 °C and 70 °C. As a result, the fuel efficiency of the tire and the vehicle is significantly improved. In some embodiments, a rubber compound containing SMLHCB or SMLHCB-R shows a reduction in the compound tangent delta at 30 °C and 60 °C, indicating an improved (lowered) rolling resistance. In some embodiments, the shift of the tangent delta of a rubber compound containing SMLHCB or SMLHCB-R is mainly due to a decrease in the loss modulus G". In certain embodiments, a rubber compound containing SMLHCB-R improves the hysteresis while maintaining the abrasion resistance and tear strength, and as a result, reduces the tire rolling resistance, and as a result, improves the fuel efficiency of the tire and the vehicle. In certain embodiments, a rubber compound containing SMLHCB or SMLHCB-R is suitable for use in commercial truck tires at all wheel positions.

Brief Description of the Drawings

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Mode for Carrying Out the Invention

[0010] Table I provides a list of abbreviations used in the present disclosure.

Table 1

[0011] Tires play an important role in the safety of motor vehicles as the sole link between the vehicle and the road surface, and also directly affect fuel consumption and many other vehicle-tire system characteristics. A tire is a highly engineered rubber product composed of various parts, such as a tread area and a carcass or casing. There are three important characteristics for passenger tire manufacturers, which are rolling resistance (RR), wet traction (WT), and wear resistance (WR), forming the "magic triangle". Tire rolling resistance is related to vehicle fuel consumption, wet traction is related to traction on wet pavements, and wear resistance is related to tire life. In laboratory tests, the rolling resistance and traction characteristics correlate with the compound hysteresis plot of the tangent delta value against temperature, and the DIN wear described in test procedures DIN 53516 and ASTM D5963 can provide an estimate of tread wear. The tangent delta at a temperature of 30°C to 70°C, preferably 60°C to 70°C, is used as a predictor of rolling resistance, and the tangent delta at 0°C is used as a predictor of wet traction. In this example, at 50°C to 70°C, preferably 70°C, reducing the tangent delta is desirable to reduce rolling resistance, and increasing the tangent delta at 0°C is desirable to improve wet traction. In the case of ASTM grade carbon black, the plot of the tangent delta against temperature shifts up and down depending on the grade, so either wet traction or rolling resistance can be improved. Since the 1990s, tire manufacturers have used silica as a reinforcing filler in tire tread compounds to significantly optimize both rolling resistance and wet traction without sacrificing tread wear resistance.

[0012] However, compounding with silica has its own drawbacks. The drawbacks are that due to the abrasiveness of silica, processing is more difficult and the maintenance cost of the machine increases. When silica is used as a filler, problems also occur during mixing. Due to its polar surface, silica is difficult to mix with hydrocarbon rubbers, and it is necessary to use a coupling agent in the compound formulation to crosslink between the silica filler and the polymer. Another drawback of silica is that an electrostatic charge accumulates on the tread compound due to the non-conductivity of silica, and the static electricity generated within the tire cannot be dissipated. Therefore, silica is often used in combination with carbon black to dissipate such electrostatic discharges. Other drawbacks of silica in the tire industry are that it emits ethanol and the manufacturing cost is high because the plant throughput speed is slow. More recently, silica has introduced significant challenges to the sustainability initiative where carbon black and polymers are recovered from recycled tires. Furthermore, although using silica can improve the rolling resistance and wet traction in certain rubber compounds, these advantages do not exist in all rubber compounds, especially natural rubber used in truck tire treads. Since the late 1980s, scientists have been researching ways to overcome these challenges by using various approaches, developing new special carbon blacks, and / or modifying ASTM grade carbon blacks to develop compounds with properties similar to silica compounds. These strategies mainly focus on increasing the interaction between the filler and the polymer and reducing the interaction between the fillers by modifying the compound components (e.g., carbon black, polymer) and the mixing procedure.

[0013] To reduce the interaction between fillers, carbon black manufacturers have introduced low hysteresis carbon black (LH) that has a higher proportion of larger aggregates and a wider aggregate size distribution (ASD) compared to standard ASTM carbon black. Low hysteresis carbon black reduces the network strength between fillers by increasing the average inter-aggregate spacing while maintaining the same average strength of the interaction between the polymer and the filler, and as a result, improves rolling resistance (see, for example, U.S. Patent No. 7,238,741). In particular, low hysteresis carbon black is not suitable for increasing the interaction between the polymer and the filler to improve compound properties other than rolling resistance.

[0014] To increase the interaction between the filler and the polymer, researchers have attempted to chemically modify carbon black. Extensive research on the surface treatment of carbon black has been conducted with this approach (see, for example, U.S. Patent No. 9,005,359). Although improvements in rolling resistance or other properties have been achieved, it has not been successful in simultaneously improving all three properties (rolling resistance, wet traction, and abrasion resistance). The interaction between the filler and the polymer has been improved, but the network formation between the fillers still predominates.

[0015] In the present disclosure, by chemically modifying low hysteresis carbon black, the above two main strategies are combined, such that in low hysteresis carbon black, while the network strength between fillers advantageously decreases, the interaction between the filler and the polymer increases, and as a result, rolling resistance, tire traction, and tire resistance are simultaneously improved.

[0016] Truck tire Fuel cost is one of the major costs faced by the trucking industry. In recent years, many improvements have been made to increase the energy efficiency of commercial trucks and tractor-trailer combinations. For example, better fuel efficiency has been achieved by implementing more aerodynamic designs on both tractors and trailers, which together provide a lower coefficient of drag. The breakdown of energy losses for a truck or tractor-trailer combination traveling at 88 km / h (55 mph) is as follows. 42% of the required horsepower is needed to overcome aerodynamic drag, 15% for driveline losses, 9% for accessories, and 34% for tire rolling resistance. Since the ratio of losses varies with vehicle speed and load, tires contribute significantly to energy consumption in highway trucks. Further reference to the technology for testing truck fuel economy can be obtained in the text Tire Engineering by B. Rodgers, published by CRC Press. Reducing tire rolling resistance can have a direct impact on truck fuel consumption. In the case of long-haul trucks, reducing tire rolling resistance from 2.5% to 3.5% can result in a 1% fuel savings. In passenger car tires, the improvement is not as significant at ratios close to 7:1. Therefore, reducing the rolling resistance of truck tires has greater benefits for commercial vehicle operators both in terms of cost and the environment. However, one challenge in achieving these objectives is the conflicting characteristics that low energy losses are advantageous for good rolling resistance and high energy losses are advantageous for good traction characteristics.

[0017] By designing tires with low rolling resistance, fuel efficiency can be improved. To reduce the rolling resistance of tires, a rubber compound having a high resilience measured by a simple rebound test can be used in the production of tire treads. Tires made of such rubber have less energy loss during rolling. However, a conventional problem associated with this approach is that the tread compound of a tire suitable for use in commercially available large truck tires must also exhibit high tensile strength and excellent tear strength, so the choice of polymer is limited to natural rubber only. Therefore, the available variables that can be used to improve natural rubber-based truck tire tread compounds are limited to filler systems such as carbon black and silica.

[0018] A passenger tire tread compound containing a high level of highly dispersible silica (abbreviated as HDS) and containing a silane coupling agent and solution SBR has been proven to be very effective in improving tire vehicle fuel efficiency and wet traction, as described in U.S. Patent No. 5,227,425. However, in commercially available truck tires, the loss of tread wear performance due to the use of silica has nullified the improvement in reducing the overall rolling resistance of the tire. In the present disclosure, a new technology carbon black has been developed, thereby achieving the necessary compound hysteresis merit required to reduce low truck tire rolling resistance and improve fuel efficiency, but without the loss of wear resistance found when the silica content in the tread compound formulation is high.

[0019] In addition to the present disclosure, low hysteresis compounding additives typically reduce the compound tear resistance, which affects the durability of the tire, an important performance parameter for commercial truck tires operating in long-haul service, short-haul and stop-and-go conditions, and on- and off-road service.

[0020] Natural rubber is a preferred rubber for truck tire tread compounds, but retread truck tires for general use most often use oil extended emulsion SBR (ESBR) in the tread compound. Such treads are prepared by one of two methods. i) In mold curing, the tire casing is prepared, a new tread compound is extruded onto the prepared casing, and then the tire is vulcanized in a mold at a defined time and temperature. A more common method, called pre-curing, is by extrusion of the tread and then partial curing in a mold to form the tread pattern. This product is later applied to the prepared tire casing and then the newly retreaded tire is placed in an autoclave to complete the vulcanization process. Emulsion SBR is preferred for such applications because of its excellent compound mixing efficiency, compound resistance to backset, and abrasion resistance. However, equally important for new tires is the rolling resistance of retread tires. The use of SMLHCB in emulsion SBR retread compounds promotes the rolling resistance performance required by truck drivers and thus the achievement of vehicle fuel economy, which cannot be achieved by other means without sacrificing manufacturing efficiency or other tire characteristics. SMLHCB in ESBR and oil extended ESBR mixes with equal efficiency to conventional carbon black grades while reducing compound hysteresis, improving truck fuel efficiency without sacrificing wear performance or traction.

[0021] As described in the present disclosure, when carbon black is treated with a chemical substance such as an amino acid compound or a derivative thereof, the chemical reactivity of the carbon black surface is improved, enabling the reinforcement of polymer fillers, and as a result, the compound hysteresis represented by the reduction of the Payne effect can be lowered. The treatment level is further expected to improve as the surface area of the carbon black particles increases. Therefore, the principle demonstrated in this example using ASTM carbon black grade N234 is equally applicable to all furnace grades of carbon black. Further, reference can be made to ASTM D1765, which describes the properties of such carbon black, including the major groups and then each specific grade. Further specifying the grades to which the present disclosure is applicable, but not limited to, tread grade carbon blacks such as N110, N121, and N134, N220, N234, etc., and then casing grade carbon black grades, examples of casing grade carbon black grades include N330 typically used for tire sidewalls, N326, N339, N347, and N351 that can be used for tire or industrial rubber product fabric or wire coat or skim compound, N660 typically used for inner liners, and N550 that can be used for parts such as shoulder wedges and bead fillers. Since all furnace grades can be surface-treated with amino acid compounds such as cystine and derivatives thereof such as disodium salts, this list is exemplary and not limited to the grades specified.

[0022] This specification discloses a surface-treated low hysteresis carbon black material. In one or more embodiments, the carbon black is characterized as low hysteresis carbon black. As used herein, the term "low hysteresis" refers to carbon black that exhibits low energy dissipation during normal operation of a tire in a rubber tire compound. In one or more embodiments, the low hysteresis carbon black material of the present disclosure is functionalized by introducing chemical moieties to the surface of the material. In one or more other embodiments, the surface density of the chemical moieties introduced to the low hysteresis carbon black is increased by functionalizing the surface using the methods disclosed herein. The low hysteresis carbon black of the present disclosure may be utilized in any suitable application. Further, the basic principles can be applied to all types of carbon black such as furnace type, thermal type, and acetylene type, which are known to anyone skilled in rubber compounding. Further, the basic principles can be applied to all types of carbon black as shown in Table II.

[0023] Further, the basic principles described in the present disclosure can be applied to all specific grades of furnace type carbon black used in tire and industrial rubber product compounding, defined by ASTM D1765 and listed in Table III, which are known to anyone skilled in rubber compounding. Further, the basic principles can be applied to any type of non-ASTM carbon black. [Table 2]

[0024] The present disclosure further contemplates rubber compositions comprising natural polymers, synthetic polymers or blends thereof and functionalized low hysteresis carbon black of the type disclosed herein. The surface-functionalized, treated, or modified low hysteresis carbon black material prepared as disclosed herein is referred to as SMLHCB. [Table 3]

[0025] SMLHCB for Passenger Tires Disclosed herein are thermochemically functionalized low hysteresis carbon black, SMLHCB, and methods for making the same. In one or more embodiments, SMLHCB is a component of a rubber composition used in the manufacture of products such as tires, and more specifically, is a filler in the rubber composition. Treads of tires containing SMLHCB may be characterized by (i) improved rolling resistance, (ii) improved wet traction, (iii) improved abrasion resistance, (iv) a combination of (i), (ii), and (iii), or any combination of (i), (ii), or (iii). Treads of tires containing SMLHCB have silica as a filler and may exhibit properties (e.g., mechanical properties) comparable to those obtained with similarly composed materials in other respects.

[0026] Without wishing to be bound by theory, using SMLHCB of the type disclosed herein advantageously reduces the network formation strength between fillers, while increasing the interaction between the polymer and the filler. These effects simultaneously improve the desired rubber tread compound properties and thus address the above-mentioned drawbacks of conventional methods. In one or more embodiments, the method of the present disclosure includes treating low hysteresis carbon black under conditions suitable for thermally bonding at least a portion of the low hysteresis carbon black surface to functional groups derived from a surface modifier.

[0027] SMLHCB for Truck Tires Disclosed herein are embodiments of compounds of surface modified low hysteresis carbon black (SMLHCB) in natural rubber truck tire tread compounds, which improve rolling resistance while maintaining tear strength and abrasion resistance, and thus address the drawbacks of conventional compounds and methods.

[0028] Also disclosed herein is a tread rubber compound formulation suitable for application to truck bus radial (TBR) tires. As used herein, TBR refers to a tire for use on vehicles that transport goods or passengers, such as buses, tractors, line-haul trucks, travel trailers, and multi-stop trucks. It is contemplated that the TBRs of the present disclosure may find utility in other situations where improvement of the rolling resistance of vehicle (including, by way of non-limiting example, off-road vehicles such as all-terrain vehicles) tires is desired.

[0029] Referring to FIGS. 1 and 2, for a better understanding of the subject matter of the present disclosure, FIG. 1 shows a schematic view of a notch of a truck tire tread 1 having five continuous ribs 2, four continuous grooves 3, and a four-rib configuration. Further, FIG. 2 shows a tread region 12 of an embodiment of a tire 10 that is the subject matter of the present disclosure. In particular, FIG. 2 shows a tire 10 including a sidewall 13, a belt 14, a ply 15, and an undertread or base 16.

[0030] Referring to FIG. 3, the key elements of the performance of a commercially available truck tire tread compound can be defined by its impact on the rolling resistance, wet traction, abrasion resistance, and cut resistance of the tire (FIG. 3). In one or more aspects, compositions suitable for use in the preparation of TBR treads include (i) natural rubber, (ii) surface-modified low hysteresis carbon black, and (iii) antioxidants. In one or more aspects, the TBR tread composition may be further characterized by a low sulfur curing agent content and the exclusion of silica and silane coupling agents. The method of the present disclosure may be further characterized by the use of minimally processed rubber.

[0031] Referring to FIGS. 4A - 4D, schematic views of rib tread patterns 20, 22, 24, and 26 are shown respectively. In particular, the rib tread pattern 20 of FIG. 4A is a rib tire tread design including five straight ribs, four grooves, and a slip within the traction rib. The rib tread pattern 22 of FIG. 4B is a rib lug design including an outer lug for traction and an inner rib for improving tread wear. The rib tread pattern 24 of FIG. 4C is another rib lug design including an outer rib for improving fuel efficiency, an inner lug for improving traction, and a tie bar connecting the lugs in the circumferential direction for improving lug stability. Finally, the rib tread pattern 26 of FIG. 4D is a trailer tire rib tread design including a plurality of straight ribs, shallow grooves, a high net - to - gross footprint for improving lateral stability, and a central groove for water dispersion.

[0032] Commercially available truck tires are designed for wheel positions, namely, rear axle tires, drive axle tires, and trailer axle tires. Further, the design can vary according to tire mission profile, for example, short - distance pickup and delivery, buses and coaches, and off - road. Rear axle tires, all - position tires, and trailer axle tires tend to have a rib tread pattern (e.g., rib tread patterns 20 and 26). Such designs facilitate natural rubber tread compounds. The tendency in the tire tread design for highway drive axle trucks is to have a solid shoulder (e.g., rib tread pattern 24) rather than an outer lug (e.g., rib tread pattern 22). Despite the outer lug showing greater traction characteristics, such tread designs require compounds consisting of both natural rubber and synthetic rubbers such as polybutadiene and solution SBR, and as a result, a high level of carbon black is required to achieve the required tensile strength and, more importantly, fatigue resistance. Such compounds tend to have a high hysteresis (the tangent δ is large), and as a result, the rolling resistance is high and the vehicle's fuel consumption increases. In the case of a tread pattern with closed shoulders (i.e., rib tread pattern 24), all natural rubber compounds can be used with much lower hysteresis, and as a result, the tire rolling resistance is improved (becomes lower). Then, the traction is changed by adjusting the dimensions of the central row of lugs and the net foot print contact area. As a result, the same all - natural rubber tread compound formulation can be used in all three tire designs, namely, the tread compounds of the steer tire, drive tire, and trailer tire.

[0033] Accordingly, the present disclosure also contemplates sulfur-vulcanized tread compounds based on the natural rubbers and modified carbon blacks described herein. Further, the present disclosure contemplates a plurality of commercially available truck tire types for vehicles described by the Society of Automobile Engineers (SAE) and the Federal Highway Administration as classes 5 (16,001 pounds or 7,258 kg gross vehicle weight rating) through 8 (80,000 pounds or 36,287 kg gross vehicle weight rating), which can include tires for commercially available truck rear axles, drive axles, trailer axles, long-haul operations, short-haul, pickup and delivery, buses, and coaches. The range of such tires for such vehicles is also suitable for light transport vehicles such as those described by the Society of Automobile Engineers as classes 1 through 4, with a total vehicle weight up to 16,000 pounds, and such tires have a fabric ply construction.

[0034] In the present disclosure, in order to help advantageously achieve and improve such characteristics, carbon black described as surface-modified low hysteresis carbon black is combined with other compounding materials described herein. Aspects of the combination of elastomers, carbon black, antioxidants, processing aids, and vulcanization systems for cured truck tire treads are considered important herein for achieving tire tread performance (e.g., maintaining traction, rolling resistance, and abrasion resistance). In addition to the above performance characteristics of the ground tread rubber composition of the cured tire, important aspects of the present disclosure are: (i) the use of natural rubber, (ii) designed to promote optimal crosslinking and high chain extension of the tread rubber composition, a relatively low level (content) of sulfur curing agent called a semi-efficient vulcanization system (semi-EV), (iii) the elimination of silica and silane coupling agents for silica and the resulting manufacturing efficiency benefits, (iv) the elimination of ethanol emissions and the associated environmental benefits, (v) the improvement of tire uniformity, (vi) potential cost reduction compared to such compositions using conventional silica, highly dispersible silica, and silane coupling agents, (vii) surface-modified low hysteresis carbon black, which is a tire tread grade of carbon black, (viii) the content of antioxidants, usually in the range disclosed for the combination of antioxidants and antiozonants, to achieve appropriate long-term durability and fatigue resistance, (ix) a relatively low level of rubber processing oil to promote relatively high tensile strength and optimized processing of the composition for tire tread rubber. Accordingly, the present disclosure also contemplates sulfur-vulcanized tread compounds.

[0035] SMLHCB composition Referring to FIG. 5, in an embodiment, the surface modifier includes an amino acid compound or a derivative thereof, and any stereocenter present in the compound can be in the R and / or S configuration. For example, in an embodiment, the amino acid compound includes a naturally occurring amino acid, a modified natural amino acid, a synthetic amino acid, a dimer thereof, a polymer thereof, a salt thereof, a derivative thereof, or a combination thereof. Non-limiting examples of surface modifiers suitable for use in the present disclosure include cysteine, cystine, homocysteine, homocystine, methionine, cysteamine, cystamine, and cystine dimethyl ester, and combinations thereof. Some examples of surface modifiers suitable for use in the present disclosure are shown in FIG. 5.

[0036] In an embodiment, the surface modifier includes an amino acid compound or a derivative thereof having at least one amine group and one thiol group, and / or a di- and / or polysulfide bond, and / or an organic or inorganic compound including at least one amine group and at least one thiol group, and / or a di- and / or polysulfide bond. In an embodiment, the amine group described herein is not limited to a primary amine group and can be any type of amine suitable for binding to the carbon black surface (e.g., a secondary or tertiary amine in the presence of a suitable catalyst). The surface modifier may include multiple amines or other functional groups. The surface modifier may be chemically bonded to the surface of the carbon black (e.g., the surface of the low hysteresis carbon black) via a single bond or a multiple bond. In an embodiment, the surface modifier functions to form at least one bond (e.g., an amide bond) to the surface of the low hysteresis carbon black.

[0037] In one aspect of the method of the present disclosure, the low hysteresis carbon black is treated with a surface modifier using any suitable methodology, with or without pretreatment. In one aspect, the SMLHCB is prepared by treating the surface of the low hysteresis carbon black with a surface modifier in a suitable solvent (e.g., water) at about 0.1% (w / v) to about 50% (w / v), about 0.1% (w / v) to 30% (w / v), preferably about 1% (w / v) to about 20% (w / v), followed by heat treatment. In one aspect, the mixing of the carbon black and the surface modifier-containing solution can be carried out by techniques such as pouring, spraying, injecting, dispersing, or diffusing. The heat treatment of the surface modifier-mixed carbon black can be achieved at a temperature in the range of about 600°C to about 450°C, or about 900°C to about 350°C, or about 1200°C to about 300°C, for a period of about 0 to about 72 hours, or about 0 to about 24 hours, or about 0 to about 8 hours, or preferably about 0 to about 0.5 hours. In one aspect, the heat treatment step for thermochemical coupling may be carried out using a suitable heat source. After the reaction, the resulting material is SMLHCB. The SMLHCB is then preferably dried to remove the excess reaction solution and may be used without further purification.

[0038] In another aspect, the SMLHCB is purified using a suitable solvent (e.g., water) to remove the weakly bound surface modifier. The purification of the SMLHCB as a slurry may be carried out without stirring in any suitable container, but it is preferably carried out with stirring. In some aspects, after the SMLHCB is purified with a solvent, the solid carbon material and the fluid are separated, and the solid carbon material may be used with or without further purification.

[0039] In some embodiments, the purification of SMLHCB is carried out multiple times in a cycle that includes contacting the SMLHCB with a first amount of solvent, removing the fluid, and purifying the SMLHCB with a second amount of solvent. This may be done over any number of cycles to meet the objectives, desired properties, and end-product performance. In another embodiment, the purification cycle may be carried out just once, or alternatively, the number of purification cycles may range from about 1 to about 10 times, or from about 1 to about 6 times, or from about 1 to about 4 times. The resulting material is referred to as purified SMLHCB and is called SMLHCB-R.

[0040] In an embodiment, the obtained SMLHCB or SMLHCB-R contains functional groups derived from a surface modifier bound to the surface of the low hysteresis carbon black. In embodiments where the SMLHCB is unpurified, the material further contains a favorable associated surface modifier or a fragment thereof that is electrostatically (ionically) bonded, covalently bonded, van der Waals force bonded, hydrogen bonded, or otherwise non-covalently bonded to, or not bonded to, the active surface portion of the surface of the low hysteresis carbon black, and thus at least a portion of it can be easily removed by purifying the material. Thus, non-limiting examples of the types of bonds that can occur between the functional groups present in the surface modifier and the low hysteresis carbon black include van der Waals interactions with the active surface portion of the surface, covalent bond interactions (including donor bonds), and / or ionic interactions or other non-covalent bond interactions. In one or more embodiments, the active surface portion of the surface of the SMLHCB and / or SMLHCB-R contains oxygen, nitrogen, and / or sulfur, and other elements found in materials used in carbon black production and rubber compounding. As a further example, a surface modifier containing an amine group may bind to the carbon black surface by reacting with strongly acidic groups present on the surface (see, for example, Chemical Bonding of tetraethylene pentaamine to Nitric Acid-Oxidized Carbon Fibers: An XPS / ISS Investigation, Steven D. Gardner, Chakravarthy S. K. Singamsetty, Guoren He, and Charles U. Pittman, 51(5), 636, 1997).

[0041] In one or more embodiments, the low hysteresis carbon black suitable for use in the preparation of SMLHCB can be pretreated by oxidation prior to treatment with a surface modifier. Such an oxidation process can be carried out, for example, to increase the number of acidic groups on the surface of the carbon black available to react with the amine groups of the surface modifier. In an embodiment, the pretreatment by oxidation of the carbon black can be carried out by methods such as ozone treatment, heat treatment, plasma treatment, nitrogen oxide treatment, hydrogen peroxide gas or hydrogen peroxide solution treatment, liquid nitric acid treatment, or combinations thereof, but is not limited thereto.

[0042] Another pretreatment may include increasing the number of acidic groups on the surface of the low hysteresis carbon black before or during the treatment with the surface modifier. Thus, in an embodiment, the method can further include directly using the low hysteresis carbon black without acid treatment, without activating the surface, and / or without treating the surface with an acid to facilitate the treatment of the surface with the surface modifier.

[0043] A further pretreatment may include converting carboxylic acid groups on the low hysteresis carbon black to acyl chlorides or acid anhydrides prior to treatment with the surface modifier. Acyl chlorides and acid anhydrides react more readily with amines compared to carboxylic acids.

[0044] In one embodiment, the surface modifier comprises from about 0.1 wt% to about 50 wt%, from about 0.1 wt% to about 30 wt%, from about 1 wt% to about 16 wt%, or from about 3 wt% to about 20 wt% of SMLHCB.

[0045] In one or more embodiments, the SMLHCB of the present disclosure is characterized by a carbon black material having a higher proportion of larger aggregates and a wider aggregate size distribution than a standard ASTM grade carbon black that does not exhibit low hysteresis when compounded. In an embodiment, the aggregate size of the low hysteresis carbon black can range from about 0.005 to about 1.0 micrometers (μm), from about 0.01 to about 0.8 μm, or from about 0.02 to about 0.6 μm. In one or more embodiments, the SMLHCB is about 10m 2 / g to about 250m 2 / g, or about 20m 2 / g to about 200m 2 / g, or about 30 to about 150m 2 / g (e.g., BET surface area).

[0046] In an embodiment, the thiol groups present in the surface modifier may form chemical bonds with the unsaturated bonds present in the polymer. The di / polysulfide bonds in the surface modifier can be broken during vulcanization and form chemical bonds with the unsaturated polymer. In a further embodiment, the surface modifier can further react with elemental sulfur to form additional di / polysulfide bonds between the filler and the polymer.

[0047] The SMLHCB or SMLHCB-R prepared as disclosed herein may be characterized by a surface with an increased number of functional groups present on the surface of the particles as compared to other similar compositions prepared in the absence of thermal coupling. By increasing the number of functional groups per particle area, the number of interactions between the polymer and the filler (e.g., SMLHCB or SMLHCB-R) increases, and as a result, the tread compound is characterized by (i) improved rolling resistance, (ii) improved wet traction, (iii) improved abrasion resistance, (iv) a combination of (i), (ii), and (iii), or any combination of (i), (ii), or (iii).

[0048] Compared with the coating and acid-base mixing procedure (see, for example, U.S. Patent Application No. 2022 / 0243068), the thermochemical coupling procedure of the present disclosure provides several advantages such as an improvement in the reaction rate of coupling at high temperatures, avoidance of reformation of insoluble surface-modified compounds, reduction in the inhomogeneity of the reaction and coating products, direct exposure of carbon black surface groups to the surface-modified compound, acceleration of the coupling reaction due to rapid water loss in the amide bond formation reaction at high temperatures, and shortening of the drying time of the surface-treated carbon black.

[0049] Polymer composition Also disclosed herein is a rubber composition comprising (i) SMLHCB and / or SMLHCB-R as defined in Table I and (ii) a polymer. In one or more embodiments, the polymer compositions of the type disclosed herein may be useful in the formation of tire treads and are referred to as T-COMPS. The rubber of T-COMPS may include natural rubber and its various unprocessed, recycled, or modified forms, various synthetic rubber polymers, and any combination thereof, depending on the desired end use.

[0050] Representative synthetic rubber polymers are homopolymerization products of butadiene and its homologs and derivatives, such as methylbutadiene, dimethylbutadiene, and pentadiene, and copolymers formed from butadiene or its homologs or derivatives and other unsaturated monomers. Among the latter are acetylene, such as vinylacetylene; olefins, such as isobutylene which copolymerizes with isoprene to form butyl rubber; vinyl compounds, such as acrylic acid, acrylonitrile (which polymerizes with butadiene to form NBR), methacrylic acid, and styrene, and the latter compounds polymerize with butadiene to form SSBR (solution SBR) or ESBR (emulsion SBR), and further, vinyl esters and various unsaturated aldehydes, ketones, and ethers, such as acrolein, methyl isopropenyl - ketone, and vinyl - ethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis - 1,4 - polybutadiene), polyisoprene (including cis - 1,4 - polyisoprene), butyl rubber, halobutyl rubber such as chlorobutyl rubber or bromobutyl rubber, styrene / isoprene / butadiene rubber, copolymers of 1,3 - butadiene or isoprene with monomers such as styrene, acrylonitrile (NBR), methyl methacrylate, and ethylene / propylene / diene monomer (EPDM), also known as ethylene / propylene terpolymer, including ethylene / propylene / dicyclopentadiene terpolymer.

[0051] In one aspect, the rubber is selected from the group consisting of styrene - butadiene rubber (SBR), polybutadiene rubber, natural rubber, halogenated butyl rubber, butyl rubber, polyisoprene rubber, and styrene / isoprene / butadiene terpolymer rubber.

[0052] Examples of styrene-butadiene rubbers suitable for use in the present disclosure include copolymers containing any amount of styrene. When the composition contains a styrene-butadiene copolymer, the styrene-butadiene rubber may contain 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, and 95% by weight (including any and all ranges and sub-ranges therein) of styrene. Examples of polybutadiene rubbers suitable for use in the present disclosure include, but are not limited to, those having a 1,4 configuration or a 1,2 configuration.

[0053] In one aspect, the rubber includes a styrene-butadiene copolymer (SBR), and the double bonds of the rubber polymer or copolymer may be at least partially hydrogenated. The styrene-butadiene copolymer may contain, for example, double bonds in which more than 50% or less than 50% of the butadiene portion of the copolymer is hydrogenated. Alternatively, the rubber may be 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100% (including any and all ranges and sub-ranges therein) hydrogenated. An equivalent high level of hydrogenation is also carried out using hydrogenated nitrile rubber within the scope of the present disclosure as well.

[0054] SSBR In another aspect, the rubber compound of the present disclosure includes a solution SBR (SSBR)-polybutadiene (BR) blend. For example, the rubber compound can have a weight ratio of SSBR:BR in the range of about 100:0, 99.9:0.1, 75:25, 0.1:99.9, or 0:100, or in the range of about 100:0 to about 0:100, about 99.9:0.1 to about 0.1:99.9, about 90:10 to about 10:90, or about 80:20 to about 20:80, and in many cases, preferably in the range of 75:25 to about 65:35.

[0055] natural rubber In one or more embodiments, the rubber compound of the present disclosure includes natural rubber. Natural rubber is a composition of 94% cis-polyisoprene and 6% other compounds such as carbohydrates, lipids, and proteins. Natural rubber is a truly renewable resource and is thus important with respect to sustainability and conservation. There are six general grades of technical classification of natural rubber, and these grades are shown in Table 1 along with their properties.

Table 4

[0056] Non-limiting examples of natural rubber suitable for use in the present disclosure are 100 PHR natural rubber, where the term PHR defines the amount of polymer. In one or more embodiments, the TBR tread composition includes natural rubber grade TSR5, natural rubber grade TSR10, natural rubber grade TSR20, or a combination thereof. In alternative embodiments, the TBR tread composition includes natural rubber grade TSR5 derivative, natural rubber grade TSR10 derivative, or natural rubber grade TSR20 derivative. Derivatives of these grades of natural rubber may have their physical properties modified to meet one or more user and / or process goals. In one embodiment, the TBR tread includes natural rubber grade TSR5 derivative, natural rubber grade TSR10 derivative, natural rubber grade TSR20 derivative, or a combination thereof, and the material is derivatized to provide a constant viscosity version.

[0057] Natural rubber suitable for use in the present disclosure may be characterized as visually inspected, and further defined grades of natural rubber may be produced by smoking and air drying. Smoke sheet rubber suitable for use in the present disclosure includes those described as ribbed smoke sheet (RSS) grades 1-5. In one embodiment, the natural rubber includes RSS1, RSS2, RSS3, RSS4, or a combination thereof, or the natural rubber includes RSS2, or the natural rubber includes RSS3, or the natural rubber includes a combination of RSS2 and RSS3.

[0058] Emulsion SBR In another aspect, the application of SMLHCB is not limited to natural rubber and solution SBR, and can also be added to emulsion SBR (ESBR) formulated to contain 100.0 PHR ESBR, or can also be added together with ESBR blended with special elastomers including but not limited to polybutadiene, natural rubber, or ethylene propylene copolymer or terpolymer diene (EP and EPDM), nitrile rubber (NBR), or polychloroprene (CR). Such compositions provide advantages in energy efficiency due to their low rolling resistance, and applications include, for example, conveyor belt cover compounds. SMLHCB in the emulsion SBR compound is used in conveyor belts and conveyor belt systems with multiple flights, which consume a significant amount of energy to operate, so it becomes more efficient. Other applications include hose cover compounds, power transmission belts, and dynamic mounts, etc., where low compound hysteresis is desired but not currently possible with existing polymers. Other applications include tire tread compounds, tire sidewall compounds, and inner tire components containing emulsion SBR ESBR in compounds containing 100.0 PHR or blends of inner tire components with other elastomers.

[0059] Other components A rubber tire tread formulation suitable for use in the present disclosure may contain, alone or in combination, a vulcanizing agent, an accelerator, an antioxidant, an anti-degradant, an extender oil, a peptizer, an organosilane coupling agent, a tackifier, and all other additives that may be included in T-COMPS with rubber, in an amount effective to meet the needs of one or more users and / or processes.

Examples

[0060] Although aspects have been generally described, the following examples are given as specific aspects of the present disclosure and are given to demonstrate its practice and advantages. It is understood that the examples are given by way of illustration and are not intended to limit the scope of the claims in any way.

[0061] <Example 1> Preparation I of Purified and Unpurified Surface-Modified Carbon Blacks (SMLHCB and SMLHCB-R) The thermochemical processes described herein use cystine disodium salt (Figure 1) as a non-limiting example. Cystine disodium salt (1% - 50% (w / v)) is dissolved in water, or cystine (1% - 50% (w / v)) is dissolved in a caustic solution (e.g., sodium hydroxide), with or without heat assistance, and the solution is added to a pre-weighed carbon black. The mixture is held in an oven at 140 °C for 8 hours. The dried surface-modified carbon black was then used in rubber tests. Further, some of the surface-modified carbon blacks were further purified 1 - 4 times with water to remove weakly bound cystine disodium salt. The wet carbon / cystine salt slurry was air-dried and subsequently oven-dried at 140 °C overnight to form SMLHCB-R as defined in Table I.

[0062] The surface-modified carbon black was characterized using X-ray fluorescence (XRF) in accordance with ASTM D1619-16, Method B. Samples N234 and LH11 are reference carbon blacks, and the sample STC# of the surface-modified carbon black is the SMLHCB of the present disclosure treated with different amounts of surface modifier. Specifically, the term # is either 2 or 5 or 8, and this number indicates the concentration of the coupling agent in weight / volume percent (% w / v) in the treated solution. A sample with the name W of STC#W indicates that the sample was purified after treatment with the surface modifier to form SMLHCB-R. The coverage rate reacted with cystine disodium salt was calculated from the difference in sulfur content before and after surface modification of the carbon black. The results are shown in Table IV. Table V further shows the effect of surface modification on carbon black properties including iodine number, surface area (NSA and STSA), coloring, and structure (OAN and COAN). It is clear that the iodine number decreased due to surface modification, which is desirable for compound hysteresis and reduction of rolling resistance. Some structures of the surface-modified carbon black are not affected, which may be desirable for wear resistance. [Table 5] [Table 6]

[0063] <Example 2> Preparation II of Purified and Unpurified Surface-Modified Carbon Blacks (SMLHCB and SMLHCB-R) The carbon black was treated with different surface modifiers as follows (Table VI).

[0064] Carbon black was weighed and added to a filter (or batch pelletizer), and then an aqueous solution of the surface modifier was poured onto the carbon black. The mixture was immersed as such for 30 seconds, and then a vacuum was applied (or the pelletizer was rotated) to remove the excess solution. The wet carbon black was transferred to a rotary dryer for heat treatment to form SMLHCB. The dryer was rotated at a relatively low rpm, and the temperature of the dryer was set at 180 °C. Then, the rotary drying was continued to remove the excess solution according to the normal industrial process.

[0065] Furthermore, some of the surface-modified carbon black was further purified with water 1 to 4 times to remove the weakly bound surface modifier. The wet carbon black slurry was air-dried and then oven-dried at 140 °C overnight to form SMLHCB-R. The sulfur content of SMLHCB and SMLHCB-R was determined by XRF according to ASTM D1619-16, Method B to calculate the coating level (Table VI). The coating rate of SMLHCB and SMLHCB-R was calculated from the difference in sulfur content before and after the surface modification of the carbon black. The sulfur content of the low hysteresis carbon black before surface modification was 0.82%.

Table 7

[0066] <Example 3> Preparation III of Purified and Unpurified Surface-Modified Carbon Black (SMLHCB and SMLHCB-R) Carbon black was weighed and added to a filter, and then a 20% aqueous solution of cystine disodium salt was poured onto the carbon black. The mixture was immersed as is for 30 seconds, and then a vacuum was applied to remove the excess solution. The wet carbon black was heat-treated by holding it in an oven at 240 °C to prepare SMLHCB. The SMLHCB was further purified with water to remove the weakly bound cystine disodium salt. The wet carbon / cystine salt slurry was air-dried and then dried in an oven at 140 °C overnight to form SMLHCB-R. Table VII further shows the effect of surface modification on carbon black properties including surface area (NSA and STSA) and structure (COAN). It is clear that the surface area (NSA and STSA) decreased due to surface modification, which is desirable for compound hysteresis and reduction of rolling resistance. The structure (COAN) was not significantly affected, which may be desirable for wear resistance.

Table 8

[0067] <Example 4> Effect of Pretreatment of Carbon Black by Oxidation Before Surface Modification Low hysteresis carbon black was pretreated with 30% (v / v) aqueous hydrogen peroxide solution and 10% (v / v) nitric acid solution to increase the number of acidic groups on the carbon black surface. The oxidation was confirmed by pH measurement of the pretreated carbon black (Table VIII). The dried oxidized virgin carbon black was weighed and added to a filter, and then a 10% aqueous solution of cystamine was poured onto the carbon black. The mixture was immersed as is for 30 seconds, and then a vacuum was applied to remove the excess solution. The wet carbon black was held in an oven at 180 °C for 4 hours to form SMLHCB. The coating percentage of SMLHCB was calculated by the difference in sulfur content before and after surface modification of the carbon black (Table VIII). Comparing with virgin carbon black, it shows that it is possible to increase the coating level of the surface modifier because the oxidized carbon black has a higher coating level and an increase in acidic groups on the carbon black surface.

Table 9

[0068] <Example 5> Rubber Compound I (SSBR Compound) As described above, the three main characteristics of passenger tire performance are rolling resistance, wet traction, and abrasion resistance. In laboratory tests, these characteristics generally correspond to the tanδ values at 60°C to 70°C, 0°C, and DIN abrasion measured according to ASTM 5963, respectively. It is desirable to have a high tanδ at 0°C, a low tanδ at 60°C to 70°C, and a low DIN abrasion.

[0069] Two rubber compound formulations were prepared as exemplary embodiments (Table IX). The silica tread compound formulation can be regarded as the standard silica tread compound presented in U.S. Patent No. 5,227,425, where further reference is recommended. The carbon black compound developed under the present disclosure shows improvements over other carbon black types.

Table 10

[0070] <Example 6> SSBR formulation: Formulation with unpurified surface-modified low hysteresis carbon black (SMLHCB) Nine tread compounds containing three SMLHCBs and three SMLHCB-Rs were prepared. In this example, the compounds having SMLHCB are discussed. Table IX lists the materials used in carbon black and silica tire tread compounds.

[0071] According to the formulation in Table IX, a silica compound (Compound 1), a control compound using N234 carbon black (Compound 2), and a control compound using LH11, a low hysteresis N234 type carbon black manufactured by Continental Carbon Company in Houston, Texas (Compound 3) were prepared. Further, three compounds (Compounds 4, 5, 6) were prepared using the surface-modified carbon black described in Example 1 as STC2, STC5, and STC8. Table X summarizes the rubber compound data of these compounds.

[0072] It is clear that SMLHCB can be used as a tread grade carbon black, and if further optimization of additional compound properties is required, it can be easily achieved by adjusting the rubber compound components such as the process oil content.

[0073] The predicted tire performance data is shown in Table XI. When compared with the carbon black and reference compound 2, the improvement in the DIN index was only seen in Compound 4 (STC3). The improvement in wet traction by the STC5 compound was comparable to that of the silica compound, and in the case of the STC8 compound, it was significantly better than the silica compound.

[0074] In the case of rolling resistance, all three compounds having carbon black treated as a filler showed improvement compared to the N234 compound, and the improvement by the STC5 and STC8 carbon blacks was significantly higher than that of silica. This result clearly shows that using this SMLHCB can significantly improve the fuel consumption of the tire and the vehicle, which is highly desirable.

[0075] Referring to FIG. 6, in FIG. 6, it is clear that by surface-treating the carbon black, the tread compound has almost no trade-off in wet traction or tread wear performance and can have a lower rolling resistance.

Table 11

Table 12

[0076] <Example 7> Pain effect of SMLHCB (compounded with SSBR) The Payne effect is an important parameter in rubber compounding. The Payne effect is defined as a decrease in the storage modulus (denoted as G') in a filled rubber compound as the strain applied to the material increases. When the critical strain value is exceeded, the storage modulus rapidly decreases with an increase in strain and begins to level off at large deformations. This appears as the dependence of the storage modulus and loss modulus on the amplitude of the applied strain. When a certain critical strain amplitude is exceeded, the storage modulus rapidly decreases with an increase in amplitude and saturates at fairly large deformations, while the loss modulus shows a maximum in the region where the storage modulus decreases. The Payne effect depends on the filler content of the material and disappears for unfilled elastomers. This non-linear effect strongly depends on filler dispersion and aggregation and, as a result, strongly depends on filler surface treatment, which will ultimately control the final filler structure at different observation scales. In fact, the well-known practice in the rubber industry and in compounding with carbon black (or fumed silica) is to obtain optimal dispersion of the filler without completely suppressing their aggregation into large structures. Therefore, a low Payne effect is desirable as it indicates improved dispersion and the interaction between the polymer and the filler.

[0077] Referring to Figure 7, this figure shows that the surface modification of carbon black by the SMLHCB process described herein results in a significant reduction in the Payne effect that cannot be achieved by other means.

[0078] <Example 8> SSBR compounding: compounding with purified surface-modified low hysteresis carbon black (SMLHCB-R) I The compounds prepared for this example were the same as those of Example 5, except that the materials were further purified with water after treatment, and the compounding results are shown in Table XII (grades STC2W, STC5W, and STCSW were purified versions of STC2, STC5, and STC8). In this case, it was found from the compound data that all three performance indices were improved compared to the N234 reference compound. From the data, it was found that the DIN index decreased with the coating level and finally, for Compound 9 (STCSW), it became comparable to the N234 compound.

[0079] The wet traction of the treated carbon black compounds was improved, but all of these were smaller than the improvement of the silica compounds. The wet traction index of the STC2W compound was approximately equal to that of the N234 compound, and the most improved was the STC5W compound. The improvement in wet traction by the STCSW compound was half of the potential of the silica compound.

Table 13

[0080] The results of the predicted performance of the compounds are listed in Table XIII. In the case of the rolling resistance index, all three compounds prepared using the treated carbon black were improved compared to the N234 compound, but these improvements were smaller than the improvements of the silica compounds. The best index was achieved by the STC8W compound, which was equivalent to the index of the SCT5W compound.

[0081] Regarding the DIN index, the performance of the compounds prepared using the purified treated carbon black was good compared to the compounds prepared using the unpurified carbon black, but the DIN index decreased slightly by increasing the treatment level.

Table 14

[0082] Effect of SMLHCB-R on the predicted tire performance of Example 8 Referring to FIG. 8, with respect to wet traction and rolling resistance index, the performance of the compound prepared using the purified carbon black was lower compared to the compound prepared using the unpurified carbon black, but still better than the model tread N234 compound. The general trend of wet traction and rolling resistance index was that the higher the coating level, the better the index. However, one exception to this trend was that, as shown in FIG. 8, in terms of the wet traction index, the STC5W compound had a better index than the STC8W compound.

[0083] <Example 9> Pay effect of SMLHCB-R (SSBR compounding) Referring to FIG. 9, the pay effect as described in Example 6 is well known to those skilled in the rubber compounding science and technology. In addition to the description of Example 6, the pay effect was measured for the compound containing the purified SMLHCB whose characteristics are also listed in Table XII. Here too, it is shown that the pay effect has significantly decreased, which indicates to those proficient in rubber compounding that there is an improvement in dispersion and wear improvement due to the interaction between the filler and the polymer instead of the interaction between the fillers. Furthermore, the improved pay effect approaches the effect of the silica compound, suggesting that the rolling resistance characteristics are excellent, as shown in FIG. 9.

[0084] <Example 10> SSBR compounding: compounding with purified surface-modified low hysteresis carbon black (SMLHCB-R) II Four tread compounds were prepared. Table IX lists the materials used in carbon black and silica tire tread compounds. Table IX lists the materials used in carbon black and silica tire tread compounds. According to the formulations in Table IX, a silica compound (Compound a), a control compound using N234 carbon black (Compound b), and a control compound using LH11 (Compound c) were prepared (the full formulations disclosed in Table IX). Also, one compound using the surface-modified carbon black described in Example 3 was prepared (Compound d). Table XIV summarizes the compound data of these compounds.

Table 15

[0085] The results of the predicted performance of the compounds are listed in Table XV. All three indices of rolling resistance, wet traction, and DIN for SMLHCB-R showed improvement compared to the N234 compound. The improvement in both wet traction and DIN indices for both SMLHCB-R and silica was the same. The SMLHCB-R compound showed a 6% improvement in rolling resistance compared to the silica compound.

Table 16

[0086] Referring to FIG. 10, based on Examples 6, 8 and 10, as a result of changing the surface treatment conditions, the coating levels of the surface modifier on the carbon black became different. Therefore, the tire performance characteristics can be adjusted based on the coating level on the carbon black. Thus, compared with the silica compound (shown in FIG. 6), the rolling resistance and wet traction are improved; compared with the silica compound (shown in FIG. 8), the abrasion resistance is improved; compared with the silica compound (FIG. 10), the wet traction and abrasion resistance are equivalent, but the rolling resistance is improved; or compared with the N234-containing compound (shown in FIGS. 8 and 10), the rolling resistance, wet traction and abrasion resistance can be adjusted to be improved.

[0087] <Example 11> Rubber Compound II (NR Compound) The natural rubber tread compound formulation of the type disclosed herein (i.e., the TBR tread composition) is shown in Table XVI. This formulation is considered suitable for use as a tread compound for commercially available rear axle tires used in long-haul trucks, short-haul trucks, buses and coaches, as well as pickup and delivery vehicles. The formulation is also suitable for new truck tire drive axle and trailer axle positions.

Table 17

[0088] NR Compound: Blends with SMLHCB and SMLHCB-R Four compounds were prepared using the formulation of Table XVI of Example 11. Compound 1 contained 50 PHR of ASTM carbon black grade N234 available from Continental Carbon Company (Houston, Texas). Compound 2 contained 50 PHR of low hysteresis carbon black grade LH11, also available from Continental Carbon Company (Houston, Texas), and had properties similar to N234. Compounds 3 and 4 were prepared using the SMLHCB-R and SMLHCB prepared in Example 3. Compound 3 had 50 PHR of purified SMLHCB, and Compound 4 similarly contained an equal amount of unpurified low hysteresis carbon black. Table XVII provides the rheological and mechanical properties of the indicated compounds.

Table 18

[0089] Referring to Figure 11, it was observed that treating carbon black with cystine disodium salt shifted the vulcanization rate, which could be adjusted by changing the accelerator and sulfur content in the formulation. The tensile strength and modulus of elasticity were not affected by treating and purifying the carbon black (Compound 3). Similarly, the complex hardness and tear strength were not affected. Therefore, it is clear that replacing N234 carbon black with SMLHCB (purified) at the same PHR does not require reformulation, i.e., it is a drop-in. The rheometer vulcanization profiles of the four compounds are shown in Figure 11.

[0090] <Example 13> Payne effect of SMLHCB and SMLHCB-R (NR formulation) Referring to Figure 12, stress softening of the filled rubber sample is known as the Payne effect, which is the difference in modulus of elasticity ΔG measured at low and high strain *It is defined as such. The reduction in stress softening is due to the reduction in the interaction between fillers and the improvement in the interaction between the filler and the polymer, and as a result, an improvement in wear resistance and tread wear performance is implied. Figure 12 shows the strain sweep for each of the four compounds from Example 12. As we proceed from Compound 1 containing 50 PHR of N234 carbon black to Compound 2 having 50 PHR of LH11 carbon black, the Payne effect (about 20%) is significantly reduced, which is desirable. Further proceeding to the purified SMLHCB, there is an even greater reduction (about 60%), and thus an improvement in compound dispersion and compound wear resistance is implied. Here too, the Payne effect undergoes a further reduction (about 85%) using the unpurified SMLHCB (Compound 4).

[0091] <Example 14> Compound Dynamic Characteristics of SMLHCB and SMLHCB-R (NR Compounding) For the samples from Example 12, dynamic mechanical test analysis (DMTA) was carried out and the results are shown in Table XVIII. Two sets of data are provided, the data of the dynamic tests carried out in the rebound and compression modes of the compound. The rebound was measured at 0 °C, 21 °C, 60 °C, and 70 °C. The rebound samples swell, thus providing a more representative view of the elasticity of the test compound. Those skilled in the art of rubber compounding know that the rebound at high temperatures, i.e., above 60 °C, is representative of the tire rolling resistance, and the higher the rebound, the lower the rolling resistance, which is more preferable. Conversely, as a predictive tool, the rebound at low temperatures indicates the traction characteristics, and the lower the rebound at 0 °C, the better the traction.

[0092] Regarding DMTA and the test method, the compression mode was investigated. It has been proposed that the truck tire has a rib tread pattern rather than individual tread elements such as blocks found in automotive tires. Automotive tread blocks are subject to lateral and forward shear and distortion when the tire tread enters its footprint. In the case of a commercially available large truck tire with a rib tread pattern, there is much less lateral or radial shear, but the vertical load (pressure) on the ribs is greater. This hysteresis generated in the compression mode may be more indicative of the deformation that occurs in the liner circumferential tread ribs when the truck tire enters and then leaves its footprint while rotating.

[0093] Looking at Table XVIII, when carbon black is treated with cystine salt (e.g., SMLHCB), the rebound at 60 °C and 70 °C increases significantly. This shift in rebound is sufficient to indicate that the rolling resistance of the entire tire has been significantly improved. At 0 °C, this shift is too small to have a significant effect on traction.

[0094] Similarly, regarding the DMTA data at 30 °C and 60 °C, the treatment of carbon black results in a decrease in tangent delta, suggesting an improvement in rolling resistance. It should be noted that over the past 30 years, as the rolling resistance of tires has continued to decrease, the tire operating temperature has also decreased accordingly. Therefore, in addition to measurements at 60 °C, it is appropriate to measure the compound hysteresis at lower temperatures such as 30 °C. Similar to the case of higher temperatures, the tangent delta at 30 °C shows a significant decrease, suggesting that the contribution of the tread compound to rolling resistance is lower, which is highly desirable. Tangent delta is a function of both the storage modulus G' and the loss modulus G". Both parameters change with the treatment of carbon black, but the magnitude of the shift in tangential delta is largely due to the loss modulus, which indicates lower hysteresis and energy loss, rather than a loss of rigidity that would be harmful to wear resistance. [Table 19]

[0095] <Example 15> Wear resistance of SMLHCB and SMLHCB-R (NR compound) Tread wear of truck tires is a complex phenomenon involving tensile fracture and tearing, as well as the occurrence of thermo-oxidation mechanisms. Furthermore, as the hysteresis or heat generation of the tread compound of truck tires decreases along with the reduction of rolling resistance, it is generally the case that the wear resistance decreases as a trade-off. So far, in carbon black tread compounds, this problem has remained unsolved.

[0096] As an index of wear resistance, a DIN wear test was conducted on four compounds (Table XVII). The reference compounds described in DIN 53516, ISO4649, and ASTM D5963 may show a wear volume loss range of + / - 5%, and the results within this range are considered equivalent. In this example, the test results for the surface-treated low hysteresis carbon black in Compounds 3 and 4 show that they are equivalent to the reference Compound 1 containing carbon black N234. Therefore, it is clear that by replacing carbon black N234 with SMLHCB, a significant improvement in compound hysteresis and tire rolling resistance can be achieved without impairing the tread compound wear resistance, tensile strength, or tear strength.

Table 20

[0097] <Discussion of the examples> Although various aspects have been shown and described, those skilled in the art can make modifications thereto without departing from the spirit and teachings of the present disclosure, as previously mentioned. The aspects described herein are merely illustrative and are not intended to be limiting. Many variations and modifications of the aspects disclosed herein are possible and are within the scope of the present disclosure. When a numerical range or limitation is clearly stated, such a clear range or limitation is to be understood to include similar-sized iterative ranges or limitations that fall within the clearly stated range or limitation (e.g., by way of example, about 1 to about 10 includes 2, 3, 4, etc., and greater than 0.10 includes 0.11, 0.12, 0.13). The use of the term "optionally" with respect to any element of a claim is intended to mean that the element of the subject matter may or may not be required. Both alternative forms are intended to be within the scope of the claims. The use of broader terms such as "comprises," "including," "having," etc. is to be understood to support narrower terms such as "consisting of," "consisting essentially of," and "comprised of."

[0098] Accordingly, the scope of protection is not limited by the above description but only by the following claims, and that scope includes all equivalents of the subject matter of the claims. Each claim is incorporated herein as an aspect of the present disclosure. Accordingly, the claims are a further description and an addition to the aspects disclosed herein. Consideration of the references herein, particularly any references that may have a publication date after the priority date of the present disclosure, is not an admission that they are prior art to the present disclosure.

[0099] Additional Disclosure The following are non-limiting specific aspects in accordance with the present disclosure.

[0100] The first aspect is an unpurified surface-modified low hysteresis carbon black (SMLHCB) or a purified surface-modified low hysteresis carbon black (SMLHCB-R) product, comprising low hysteresis carbon black having a surface modified such that a surface modifier or a fragment of the surface modifier adheres thereto, the surface modifier comprising at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, the surface modifier adhering to a portion of the surface of the low hysteresis carbon black, and the surface modifier being present in discrete, spaced-apart regions of the surface of the low hysteresis carbon black.

[0101] The second aspect is the SMLHCB or SMLHCB-R of the first aspect, wherein the surface modifier comprises an amino acid compound or a derivative thereof.

[0102] The third aspect is the SMLHCB or SMLHCB-R of the second aspect, wherein the amino acid compound comprises a naturally occurring amino acid, a modified natural amino acid, a synthetic amino acid, its dimer, its polymer, its salt, its derivative, or a combination thereof.

[0103] The fourth aspect is the SMLHCB or SMLHCB-R of the second and third aspects, wherein the amino acid compound or its derivative comprises cysteine, cystine, homocysteine, homocystine, methionine, cysteamine, cystamine, and cystine dimethyl ester, and combinations thereof.

[0104] The fifth aspect is the SMLHCB or SMLHCB-R of the first to fourth aspects, wherein the surface modifier comprises an amino acid compound or its derivative having at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds, and / or an organic or inorganic compound comprising at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds.

[0105] The sixth aspect is any of the SMLHCB or SMLHCB-R products of the first to fifth aspects, wherein the amine group contained in the surface modifier is any type of amine suitable for binding to the carbon black surface.

[0106] The seventh aspect is any of the SMLHCB or SMLHCB-R products of the first to sixth aspects, wherein the amine group contained in the surface modifier is a primary amine, secondary amine, or tertiary amine having a catalyst suitable for binding to the carbon black surface.

[0107] The eighth aspect is any of the SMLHCB or SMLHCB-R products of the first to seventh aspects, wherein the surface modifier is bound to the surface via a single bond or multiple bonds.

[0108] The ninth aspect is any of the SMLHCB or SMLHCB-R products of the first to eighth aspects, wherein the surface modifier is bound to the carbon black surface by amide or other bond formation, chemisorption, and / or physisorption.

[0109] The tenth aspect is any of the SMLHCB or SMLHCB-R products of the first to ninth aspects, wherein the surface modifier is bound to the surface of the low hysteresis carbon black by at least one of van der Waals interaction, ionic interaction, and / or covalent interaction or other non-covalent interaction with the active surface portion of the surface.

[0110] The eleventh aspect is any of the SMLHCB or SMLHCB-R products of the first to tenth aspects, wherein the active surface portion contains oxygen, nitrogen, and / or sulfur on the surface.

[0111] The twelfth aspect is any of the SMLHCB or SMLHCB-R products of the first to eleventh aspects, wherein the surface modifier contains from about 0.1 wt% to about 50 wt%, from about 0.1 wt% to about 30 wt%, from about 1 wt% to about 16 wt%, or from about 3 wt% to about 20 wt% of surface-modified carbon black (e.g., SMLHCB).

[0112] The thirteenth aspect is an SMLHCB or SMLHCB-R product according to any one of the first to twelfth aspects, wherein the SMLHCB or SMLHCB-R product has a higher proportion of aggregates and a wider aggregate size distribution than a standard ASTM grade carbon black that does not exhibit low hysteresis when compounded.

[0113] The fourteenth aspect is an SMLHCB or SMLHCB-R product according to any one of the first to thirteenth aspects, wherein the aggregate size of the low hysteresis carbon black can be in the range of about 0.005 to about 1.0 micrometers (μm), about 0.01 to about 0.8 μm, or about 0.02 to about 0.6 μm.

[0114] The fifteenth aspect is an SMLHCB or SMLHCB-R product according to any one of the first to fourteenth aspects, wherein the SMLHCB or SMLHCB-R has a surface area in the range of about 10 m 2 / g to about 250 m 2 / g, or about 20 m 2 / g to about 200 m 2 / g, or about 30 to about 150 m 2 / g.

[0115] The sixteenth aspect is an SMLHCB or SMLHCB-R product according to any one of the first to fifteenth aspects, wherein the surface was oxidized prior to the surface modification of the low hysteresis carbon black filler in order to produce the SMLHCB or SMLHCB-R.

[0116] The seventeenth aspect is an SMLHCB or SMLHCB-R product according to any one of the first to sixteenth aspects, wherein the surface was oxidized by ozonation, heat treatment, plasma treatment, nitrogen oxide treatment, hydrogen peroxide gas or hydrogen peroxide solution treatment, liquid nitric acid treatment, or a combination thereof.

[0117] In an eighteenth aspect, there is provided a method for manufacturing SMLHCB, the method comprising treating the surface of a low hysteresis carbon black in a suitable solvent (such as water) with a surface modifier in an amount of from about 0.1% (w / v) to about 50% (w / v), from about 0.1% (w / v) to 30% (w / v), preferably from about 1% (w / v) to about 20% (w / v), and subsequently performing a heat treatment, wherein the surface modifier contains at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds.

[0118] A nineteenth aspect is the method of the eighteenth aspect, wherein the surface modifier is bonded to the carbon black surface via thermochemical coupling.

[0119] A twentieth aspect is the method of the eighteenth and nineteenth aspects, wherein the thermochemical coupling includes a heat treatment.

[0120] A twenty - first aspect is the method of the eighteenth to twentieth aspects, wherein the heat treatment is carried out by any suitable heating source.

[0121] A twenty - second aspect is the method of the eighteenth to twenty - first aspects, wherein the heat treatment of the surface modifier - mixed carbon black is carried out at a temperature in the range of from about 600 °C to about 450 °C, from about 90 °C to about 350 °C, or preferably from about 120 °C to about 300 °C, for a period of from about 0 to about 72 hours, from about 0 to about 24 hours, from about 0 to about 8 hours, or preferably from about 0 to about 0.5 hours.

[0122] A twenty - third aspect is the method of the eighteenth to twenty - second aspects, wherein the SMLHCB is further purified at least once by contacting the SMLHCB with a fluid (such as water) to form a purified surface - modified low hysteresis carbon black (SMLHCB - R).

[0123] The twenty-fourth aspect is the method of the eighteenth to twenty-third aspects, wherein the aggregate size of the low hysteresis carbon black can be in the range of about 0.005 to about 1.0 micrometer (μm), about 0.01 to about 0.8 μm, or about 0.02 to about 0.6 μm.

[0124] The twenty-fifth aspect is the method of the eighteenth to twenty-third aspects, wherein the SMLHCB or SMLHSB-R is about 10 m 2 / g to about 250 m 2 / g, or about 20 m 2 / g to about 200 m 2 / g, or about 30 to about 150 m 2 / g.

[0125] The twenty-sixth aspect is a rubber compound containing an SMLHCB or SMLHCB-R product, wherein the SMLHCB or SMLHCB-R has a surface modified such that a surface modifier or a fragment of the surface modifier adheres thereto, the surface modifier contains at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, the surface modifier in the SMLHCB or SMLHCB-R adheres to a part of the surface of the low hysteresis carbon black, and the surface modifier is present in discrete spaced regions on the surface of the low hysteresis carbon black.

[0126] The twenty-seventh aspect is the rubber compound of the twenty-sixth aspect, wherein the polymer contained in the rubber compound is natural or synthetic or a polymer blend.

[0127] The twenty-eighth aspect is the rubber compound of the twenty-seventh aspect, wherein the polymer contained in the rubber compound includes natural rubber, solution SBR, emulsion SBR, functional solution SBR, polyisoprene, polybutadiene, EPDM, nitrile, butyl, halogenated butyl, silicone rubber, and any combination thereof.

[0128] The twenty-ninth aspect is the rubber compound of the twenty-seventh and twenty-eighth aspects, wherein the polymer contained in the rubber compound includes a solution styrene butadiene rubber (SBR) - polybutadiene rubber (BR) blend.

[0129] The thirtieth aspect is the rubber compound of the twenty-eighth aspect, wherein the polymer contained in the rubber compound has a weight ratio of SSBR:BR in the range of about 100.0, or 100:0 to about 0:100.

[0130] The thirty-first aspect is the rubber compound of the twenty-seventh and twenty-eighth aspects, wherein the polymer contained in the rubber compound includes 100 PHR natural rubber, natural rubber grade TSR5, natural rubber grade TSR10, natural rubber grade TSR20, RSS1, RSS2, RSS3, RSS4, RSS5, derivatives thereof or combinations thereof.

[0131] The thirty-second aspect is the rubber compound of the twenty-sixth to thirty-first aspects, wherein the rubber compound is manufactured using a standard American Society for Testing and Materials (ASTM) grade carbon black that is not of low hysteresis, and includes a decrease in network formation between fillers, an increase in the interaction between the polymer and the filler, or both a decrease in network formation between fillers and an increase in the interaction between the polymer and the filler, as compared to other rubber compounds that are the same in other respects.

[0132] The thirty-third aspect is the rubber compound of the twenty-sixth to thirtieth aspects, wherein the rubber compound containing SMLHCB-R has improved rolling resistance compared to an industry standard ASTM grade carbon black, and thus the fuel efficiency of the tire and the vehicle is improved.

[0133] The thirty-fourth aspect is the rubber compound of the twenty-sixth to thirtieth aspects, wherein the rubber compound containing SMLHCB-R has improved tire traction performance compared to an industry standard ASTM grade carbon black.

[0134] The thirty-fifth aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB-R has improved tire tread wear performance compared to the carbon black of industry standard ASTM grade.

[0135] The thirty-sixth aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB-R simultaneously improves the rolling resistance performance, tire traction performance, and tire wear performance compared to the carbon black of industry standard ASTM grade.

[0136] The thirty-seventh aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB-R improves the rolling resistance compared to the industry standard silica tread-based compound, and thus improves the fuel efficiency of the tire and the vehicle.

[0137] The thirty-eighth aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB-R has improved tire tread wear performance compared to the industry standard silica tread-based compound.

[0138] The thirty-ninth aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB-R is comparable to the industry standard silica tread-based compound, and simultaneously improves the rolling resistance, tire traction performance, and tire wear performance.

[0139] The fortieth aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB improves the rolling resistance performance compared to the industry standard silica tread-based compound, and thus improves the fuel efficiency of the tire and the vehicle.

[0140] The forty-first aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB has improved tire traction performance compared to the industry standard silica tread-based compound.

[0141] The forty-second aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB or SMLHCB-R reduces the compound pain effect compared to the industry standard ASTM grade carbon black.

[0142] The forty-third aspect is the rubber compound of the twenty-sixth to thirtieth aspects. The rubber compound containing SMLHCB or SMLHCB-R is suitable for passenger tire tread compound formulation.

[0143] The forty-fourth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The rubber compound containing SMLHCB or SMLHCB-R can replace N234 carbon black at an equivalent level or in part without impairing the compound properties measured in the laboratory.

[0144] The forty-fifth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The rubber compound containing SMLHCB or SMLHCB-R reduces the compound pain effect without accompanying changes in other basic properties, which is desirable.

[0145] The forty-sixth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The rubber compound containing SMLHCB or SMLHCB-R has a significantly increased rebound at 60 °C and 70 °C. As a result, the fuel efficiency of the tire and the vehicle is significantly improved.

[0146] The forty-seventh aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects, and the rubber compound containing SMLHCB or SMLHCB-R shows a reduction in the compound tangent delta at 30 °C and 60 °C, indicating an improvement in rolling resistance.

[0147] The forty-eighth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The shift of the tangent delta of the rubber compound containing SMLHCB or SMLHCB-R is mainly due to a decrease in the loss modulus G".

[0148] The forty-ninth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The rubber compound containing SMLHCB-R improves hysteresis while maintaining abrasion resistance and tear strength. As a result, the tire rolling resistance is reduced, and as a result, the fuel efficiency of the tire and the vehicle is improved.

[0149] The fiftieth aspect is the rubber compound of the twenty-sixth to twenty-eighth and thirty-first aspects. The rubber compound containing SMLHCB or SMLHCB-R is suitable for use in commercially available truck tires at all wheel positions.

[0150] Although the embodiments have been illustrated and described, those skilled in the art can make modifications without departing from the spirit and teachings of the present disclosure. The embodiments described in this specification are merely examples and are not intended to be limiting. Many variations and modifications of the embodiments disclosed in this specification are possible and are within the scope of the present disclosure. When a numerical range or limitation is clearly stated, such a clear range or limitation is understood to include a similar magnitude of repetitive ranges or limitations that fall within the clearly stated range or limitation (e.g., about 1 to about 10 includes 2, 3, 4, etc., and greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, when a numerical range with a lower limit Rl and an upper limit Ru is disclosed, any number within that range is always specifically disclosed. In particular, the following numbers within this range are specifically disclosed. R = Rl + k* (Ru - Rl), wherein k is a variable in the range of 1% to 100% with 1% increments, i.e., k is 1%, 2%, 3%, 4%, 5%, …, 50%, 51%, 52%, …, 95%, 96%, 97%, 98%, 99%, or 100%. Further, any numerical range defined by the number of two Rs as defined above is also specifically disclosed. The use of the term "optionally" with respect to any element of a claim is intended to mean that the element of the subject matter may or may not be required. Both alternative forms are intended to be within the scope of the claims. The use of broader terms such as "comprises", "including", "having", etc. should be understood to support narrower terms such as "consisting of", "consisting essentially of", "comprised substantially of", etc.

[0151] Accordingly, the scope of protection is not limited by the above description, but only by the following claims, which scope includes all equivalents of the subject matter of the claims. All claims are incorporated herein as embodiments of the present disclosure. Accordingly, the claims are a further description and an addition to the embodiments of the present disclosure. Consideration of references herein, particularly any references that may have a publication date after the priority date of the present application, does not admit that it is prior art. The disclosures of all patents, patent applications, and publications cited herein are incorporated herein by reference to the extent that they provide exemplary procedures, or other details supplementing those described herein.

Claims

Claim 1 An unrefined surface-modified low hysteresis carbon black (SMLHCB) or a refined surface-modified low hysteresis carbon black (SMLHCB-R) compound, which is a low hysteresis carbon black having a surface modified to adhere a surface modifier, wherein the surface modifier contains at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, and the surface modifier adheres to a part of the surface of the low hysteresis carbon black in discrete spaced regions of the surface of the low hysteresis carbon black, and the SMLHCB or SMLHCB-R compound has a higher proportion of aggregates and a wider aggregate size distribution than a standard American Society for Testing and Materials (ASTM) grade carbon black that does not show low hysteresis when compounded, the low hysteresis carbon black comprising an SMLHCB or SMLHCB-R compound. Claim 2 The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier contains an amino acid compound or a derivative of the amino acid compound. Claim 3 The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier contains at least one of a naturally occurring amino acid, a modified natural amino acid, a synthetic amino acid, its dimer, its polymer, its salt, and its derivative. Claim 4 The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier contains at least one of cysteine, cystine, homocysteine, homocystine, methionine, cysteamine, cystamine, and cystine dimethyl ester. Claim 5 The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier contains an amino acid compound or a derivative of the amino acid compound having at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds, and / or an organic or inorganic compound containing at least one amine group and at least one thiol group, and / or di- and / or polysulfide bonds. Claim 6 The SMLHCB or SMLHCB-R compound according to claim 1, wherein the amine group of the surface modifier is configured to bind to the surface of the low hysteresis carbon black.

7. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the amine group of the surface modifier is a primary amine, secondary amine, or tertiary amine having a catalyst for binding to the surface of the low hysteresis carbon black.

8. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier is bound to the surface via a single bond or a multiple bond.

9. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier is bound to the surface of the low hysteresis carbon black by amide or other bond formation, chemisorption, and / or physisorption.

10. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier is bound to the surface of the low hysteresis carbon black by at least one of van der Waals interaction, ionic interaction, and / or covalent bond interaction or other non-covalent bond interaction with the active surface portion of the surface.

11. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the active surface portion contains oxygen, nitrogen, and / or sulfur on the surface.

12. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface modifier contains from about 0.1 weight percent (wt.%) to about 50 wt.% of the SMLHCB or SMLHCB-R compound.

13. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the aggregate size of the low hysteresis carbon black ranges from about 0.005 micrometers (μm) to about 1.0 μm.

14. The SMLHCB or SMLHCB-R compound has a surface area in the range of about 10 square meters / gram (m ２ / g) to about 250 m ２ / g, and is the SMLHCB or SMLHCB-R compound according to claim 1.

15. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface of the low hysteresis carbon black is oxidized.

16. The SMLHCB or SMLHCB-R compound according to claim 1, wherein the surface of the low hysteresis carbon black is oxidized by at least one of ozone treatment, heat treatment, plasma treatment, nitrogen oxide treatment, hydrogen peroxide gas or hydrogen peroxide water treatment, and liquid nitric acid treatment.

17. A method for producing a surface-modified low hysteresis carbon black (SMLHCB) or a purified surface-modified low hysteresis carbon black (SMLHCB-R) compound, comprising: treating the surface of the low hysteresis carbon black with a surface modifier in a solvent at about 0.1 wt% (w / v) to about 50 wt% (w / v); after treating the surface with the surface modifier, heat-treating the surface of the low hysteresis carbon black to form an SMLHCB compound, wherein the surface modifier comprises at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, and the aggregate size of the low hysteresis carbon black is in the range of about 0.005 micrometers (μm) to about 1.0 micrometers (μm), about 0.01 to about 0.8 μm, or about 0.02 μm to about 0.6 μm; A method comprising the above steps.

18. The method according to claim 17, wherein the surface modifier is bonded to the carbon black surface via thermochemical coupling.

19. The method according to claim 17, wherein the thermochemical coupling comprises heat treatment.

20. The method according to claim 17, wherein the heat treatment is performed by any suitable heating source.

21. The method according to claim 17, wherein the low hysteresis carbon black is treated with the surface modifier at a temperature in the range of about 60 °C to about 450 °C for a period of 72 hours or less.

22. The method according to claim 17, further comprising purifying the SMLHCB compound by contacting the SMLHCB compound with a fluid to form an SMLHCB-R compound.

23. The SMLHCB compound has a surface area in the range of about 10 square meters / gram (m ２ / g) to about 250 m ２ / g, or about 20 m ２ / g to about 200 m ２ / g, or about 30 to about 150 m ２ / g, according to the method of claim 17.

24. A rubber compound comprising: a polymer; a surface-modified low hysteresis carbon black (SMLHCB) or a purified surface-modified low hysteresis carbon black (SMLHCB-R) compound, wherein the SMLHCB or SMLHCB-R comprises a surface modified such that a surface modifier adheres thereto; and comprising the above components. The surface modifier contains at least one amine group and at least one thiol group, and / or its di- and / or polysulfide bonds, the surface modifier is attached to a part of the surface in discrete spaced regions of the surface, and the polymer contains at least one of 100 parts per hundred (phr) of natural rubber, technical specification rubber (TSR) 5 of natural rubber grade, TSR10 of natural rubber grade, TSR20 of natural rubber grade, ribbed smoked sheet rubber - 1 (RSS1), RSS2, RSS3, RSS4, and RSS5. The rubber compound is manufactured using a standard American Society for Testing and Materials (ASTM) grade of carbon black that is not low hysteresis, and includes a decrease in network formation between fillers, an increase in the interaction between the polymer and the filler, or both a decrease in network formation between fillers and an increase in the interaction between the polymer and the filler, compared to the same rubber compound in other respects. Claim 25 The rubber compound according to claim 24, wherein the polymer is a natural polymer, a synthetic polymer, or a polymer blend. Claim 26 The rubber compound according to claim 24, wherein the polymer includes at least one of natural rubber, solution styrene-butadiene rubber (SBR), emulsion SBR, functional solution SBR, polyisoprene, polybutadiene, EPDM, nitrile, butyl, halogenated butyl, and silicone rubber. Claim 27 The rubber compound according to claim 24, wherein the polymer includes a solution styrene-butadiene rubber (SBR) (SSBR)-polybutadiene rubber (BR) blend. Claim 28 The rubber compound according to claim 24, wherein the weight ratio of the solution styrene-butadiene rubber to the polybutadiene rubber (SSBR:BR) is in the range of about 100.0, or 100:0 to about 0:

100. Claim 29 The rubber compound according to claim 24, wherein the polymer includes at least one of 100 parts per hundred (phr) of natural rubber, technical specification rubber (TSR) 5 of natural rubber grade, TSR10 of natural rubber grade, TSR20 of natural rubber grade, ribbed smoked sheet rubber - 1 (RSS1), RSS2, RSS3, RSS4, and RSS5. Claim 30 The rubber compound containing solution styrene butadiene rubber (SBR) (SSBR) - polybutadiene rubber (BR) blend and SMLHCB or SMLHCB-R is the rubber compound according to claim 24, which is configured for a passenger tire tread compound formulation.

31. The rubber compound contains natural rubber and the SMLHCB or SMLHCB-R compound, and is the rubber compound according to claim 24, which is configured for commercial truck tire applications.

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