Tire composition and method for manufacturing the same

Abstract

The present invention relates to a composition for a tire comprising a blend of a rubber component and 50-200 parts by weight (phr) of a filler, 0-25 phr of a plasticizer, and 5-90 phr of a dimeric decarboxylated rosin (DDCR) based on 100 phr of the rubber component. The DDCR resin comprises 50-10 wt% of polycyclic hydrocarbon compounds having one or more aliphatic unsaturated groups or aromatic groups and 34-80 carbon atoms, a molecular weight M n of 250-900 Da, a polydispersity index of 1.0-1.35, and an oxygen to carbon ratio of <5%.

Description

Technical Field

[0001] This invention relates to compositions for tire applications and methods of manufacturing the same. Background Technology

[0002] Ideally, a rubber tire should have a tread that offers excellent wet grip (wet traction) and rolling resistance, such as resistance to kinetic forces as the tire rolls over the surface. While many rubber compositions generally maintain good dry grip, they typically fail to achieve satisfactory wet grip. Rubber compositions with good wet grip improve resistance to slippage but increase rolling resistance, which leads to reduced fuel economy.

[0003] The properties of lower rolling resistance and higher wet grip are influenced by often conflicting characteristics. When optimizing tread rolling resistance, wet grip is usually compromised; conversely, when optimizing wet grip, rolling resistance is often negatively affected. For example, it is known that using resins (additives) can improve wet grip but may be detrimental to rolling resistance.

[0004] Therefore, improved resins are still needed to improve the wet grip and rolling resistance of rubber compositions. Invention Overview

[0005] On one hand, a rubber composition is disclosed. The composition comprises (essentially composed of or consisting of) a rubber component and, based on 100 parts by weight (phr), 50-200 phr of filler, 0-25 phr of plasticizer, and 5-90 phr of dimerized decarboxylated rosin (DDCR) resin. The DDCR resin comprises (essentially composed of or consisting of) 50-100% by weight of a polycyclic hydrocarbon compound having one or more aliphatic unsaturated groups or aromatic groups and 34-80 carbon atoms. The DDCR resin is characterized by a molecular weight (Mn) of 250-900 Da, a polydispersity index of 1.0-1.35, and an oxygen-to-carbon ratio of <5%. The DDCR resin is formed by decarboxylating dimerized rosin acid or dimerizing decarboxylated rosin.

[0006] In another aspect, a method for preparing a rubber composition is disclosed. The method comprises (essentially consisting of or consisting of the following steps): providing 0-100 parts by weight (phr) of a rubber component, providing 5-90 phr of a dimerized decarboxylated rosin (DDCR) resin, providing 50-200 phr of filler and optionally up to 75 phr of plasticizer, mixing the rubber component, DDCR resin, filler and optionally plasticizer to form a mixture, kneading the mixture, and adding a crosslinking system to the kneaded mixture to form a tire rubber composition. The DDCR resin comprises (essentially consisting of or consisting of) 50-100% by weight of a polycyclic hydrocarbon compound having one or more aliphatic unsaturated groups or aromatic groups and 34-80 carbon atoms. The DDCR resin is characterized by a molecular weight M. n The Da value is 250-900, measured using gel permeation chromatography and polystyrene calibration standards, with a polydispersity index of 1.0-1.35 and an oxygen-to-carbon ratio of <5%. DDCR resin is formed by decarboxylating dimerized rosin acid or dimerizing decarboxylated rosin. Invention Details

[0007] Unless otherwise stated, the following terms have the following meanings.

[0008] "At least one of [groups A, B, and C]" or "any one of [groups A, B, and C]" or "selected from [groups A, B, and C]" means a single member of a group, multiple members of a group, or a combination of members of a group. For example, at least one of A, B, and C includes, for example, only A, only B, or only C, as well as A and B, A and C, B and C; or A, B, and C, or any other combination of A, B, and C. In another example, at least one of A and B means only A, only B, and A and B. A series of embodiments represented as "A, B, or C" should be interpreted as including the following embodiments: only A, only B, only C, "A or B", "A or C", "B or C", or "A, B, or C".

[0009] “phr” refers to the number of parts per hundred parts diene elastomer (rubber).

[0010] The term “elastomer” is used interchangeably with the term “rubber” and refers to any polymer or combination of polymers that conforms to the definition in ASTM D1566.

[0011] "Polymer" and "interpolymer" are used interchangeably, both indicating number-average molecular weight (M). n Advanced oligomers with a value of 100 or greater are prepared by polymerization or oligomerization of at least two different monomers, including copolymers, trimers, tetramers, etc.

[0012] M w The formula for calculating the average molecular weight distribution is as follows:

[0013] In the formula, N i Molecular weight M i The number of molecules. M w GPC-SEC measurements can be performed according to ASTM D5296 (2005).

[0014] M n The number-average molecular weight is calculated using the following formula:

[0015]

[0016] In the formula, N i Molecular weight M i The number of molecules. M n GPC-SEC measurements can be performed according to ASTM D5296 (2005).

[0017] M z It is the higher-order average molecular weight, or the cubic molecular weight, and its calculation formula is:

[0018]

[0019] In the formula, N i M is the mass of substance i. i M is the molecular weight of substance i. z GPC-SEC measurements can be performed according to ASTM D5296 (2005).

[0020] The formula for calculating the Polydispersity Index (PDI) is: PDI = M w / M n .

[0021] Tg (glass transition) can be measured according to ASTM D 6604 (2013).

[0022] T sp The softening point can be measured by ASTM E28, or by ring and ball, or ring and cup softening point test.

[0023] Acid value can be measured using ASTM D1240-14(2018).

[0024] Properties such as tensile strength, elongation, and modulus can be measured according to the procedures described in ASTM D412 or ISO 37.

[0025] Hardness refers to the Shore A hardness according to DIN 53506.

[0026] Density can be measured using ASTM D792-13.

[0027] GPC molecular weight can be measured using a triple detector array and a hybrid column array based on polystyrene calibration standards.

[0028] Mooney viscosity at 100°C, MS or ML(1+4), can be measured according to DIN 53523.

[0029] DIN abrasion resistance can be measured according to ISO 4649.

[0030] One method for characterizing viscoelastic polymer materials is to measure their complex modulus, defined as: G* = G' + iG"; where G' and G" are the storage modulus and loss modulus, respectively, and "i" is the imaginary unit. The storage modulus G' and loss modulus G" can be measured through dynamic mechanical analysis (DMA). G' relates to energy storage and release during periodic deformation, while G" relates to energy dissipation and its conversion into heat. G' and G" allow for comparison of a material's ability to recover energy and its ability to lose energy. The complex modulus |G*| is also defined as [(G')]... 2 +(G) 2 ] 1 / 2 , which represents the ratio of maximum stress to maximum strain (σ° / ε°).

[0031] Dynamic mechanical properties such as storage modulus (G'), loss modulus (G"), and phase angle (δ), as well as damping, can be measured according to ASTM D7605 via dynamic mechanical analysis (DMA) between -100°C and +100°C, as a function of strain amplitude, providing indications of durability, traction, and handling. The magnitude of the storage modulus (G') at -20°C and -30°C is used as an indicator of ice grip.

[0032] Tanδ is the ratio of energy lost due to heat (loss modulus) to energy stored and released (storage modulus), or G" / G', where δ is the phase angle between the applied force and the material's response to that force. A larger Tanδ indicates a larger loss modulus and therefore a lower resilience. Wear parameters are given by the amount of volume loss (relative to the initial volume) that occurs after a material is subjected to wear. Tanδ can be measured using DMA, which employs a dynamic viscoelasticity tester and a temperature scan in dual shear mode from -60°C to +100°C, with a heating rate of 1°C / min, 10 Hz, 0.1% dynamic strain (-60°C to -5°C), and 3% dynamic strain (-5°C to 100°C). tanδ at 100°C indicates tire grip and other enhanced performance characteristics under extreme operating conditions. A commonly used indicator of wet grip is tanδ at 0°C, and a commonly used indicator of rolling resistance is tanδ at 60°C. The magnitude of tanδ at -20°C can be used as an indicator of snow grip.

[0033] This invention discloses a rubber composition suitable for various applications, including tires. The rubber composition comprises rubber, resin, optional plasticizer, and filler. The resin is dimerized decarboxylated rosin (DDCR).

[0034] Resin Component - DDCR: The resin component is dimerized decarboxylated rosin (DDCR) comprising 50-100 wt% of one or more polycyclic compounds containing one or more aliphatic unsaturated groups or aromatic groups having 34-80, 34-60, 34-40, or 36-38 carbon atoms. Examples of polycyclic compounds include, but are not limited to, dimers, trimers, and more advanced oligomers / polymers. In some embodiments, the DDCR resin comprises a polycyclic compound having exemplary structures as shown in (I) and (II):

[0035]

[0036] DDCR resin mainly comprises dimer and trimer substances, wherein the total amount of dimer and trimer substances is ≥75 wt%, or ≥80 wt%, or ≥85 wt%, or ≥90 wt%, or ≥95 wt%, or ≥99 wt%, or 75-99.9 wt%, or 75-98 wt%, or 80-97 wt%. In some embodiments, DDCR resin is mainly a dimer substance, in an amount of ≥50 wt%, or ≥60 wt%, or ≥70 wt%, or ≥80 wt%, or ≥90 wt%, or ≥95 wt%, or ≥99 wt%, or 50-99.9 wt%, or 60-99.9 wt%, or 70-95 wt%, or 70-90 wt%. In some embodiments, the DDCR resin is primarily a trimer in an amount of ≥50 wt%, or ≥60 wt%, or ≥70 wt%, or ≥80 wt%, or ≥90 wt%, or ≥95 wt%, or ≥99 wt%, or 50-99.9 wt%, or 60-99.9 wt%, or 70-95 wt%, or 70-90 wt%. The remainder of the DDCR resin may be monomeric material and / or larger polymeric groups.

[0037] In some embodiments, DDCR resin is prepared by decarboxylating dimerized rosin acid (DRA) and separating and purifying DDCR from it. In a second embodiment, DRA is first prepared in situ from rosin acid starting material. The in-situ formed DRA is then decarboxylated to produce crude DDCR for subsequent separation / purification to generate DDCR resin. In a third embodiment, rosin acid is first decarboxylated, and the resulting decarboxylated rosin dimerizes to produce crude DDCR. The crude DDCR is then separated / purified in one or more steps, for example by boiling point difference separation, such as by fractionation, evaporation (e.g., scraped film evaporation), or a combination thereof.

[0038] In some implementations, DDCR is unhydrogenated, partially hydrogenated, or hydrogenated.

[0039] In some embodiments, the DDCR resin can be monofunctionalized or difunctionalized with a hydrogenated silanizing agent, such as a compound (cyclic or acyclic) having Si-H bonds that catalyze a reaction with the main chain of the DDCR resin. The DDCR resin component can be used as a extender in the rubber composition.

[0040] In some embodiments, DDCR resin is used in combination with other known resins, such as those derived from substituted or unsubstituted units: cyclopentadiene homopolymer or copolymer resins (CPD), dicyclopentadiene homopolymer or copolymer resins (DCPD), terpene homopolymer or copolymer resins, rosin-derived resins, rosin / rosin esters, pinene homopolymer or copolymer resins, C5 fraction homopolymer or copolymer resins, C9 fraction homopolymer or copolymer resins, α-methylstyrene homopolymer or copolymer resins, and combinations thereof.

[0041] In some implementations, the molar mass (M) of the DDCR resin is... n The values ​​are 250-900 Da, or 300-600 Da, or 350-450 Da, or 380-420 Da (relative to polystyrene calibration standards), measured using GPC with a triple detector array and hybrid column group.

[0042] In some embodiments, the polydispersity index (PDI) (GPC) of the DDCR resin is 1.0-1.35, or 1.0-1.34, or 1.0-1.33, or 1.0-1.32, or 1.0-1.31, or 1.0-1.30, or 1.0-1.2 or 1.05-1.15.

[0043] In some embodiments, the glass transition temperature (Tg) of the DDCR resin is >-20°C, or >-10°C, or >0°C, or >15°C, or -20°C to 110°C, or 0-90°C, or 15-75°C, or 25-70°C, or <110°C, or <100°C, or <90°C, or <80°C, or <70°C, measured by differential scanning calorimetry according to ASTM E1356.

[0044] In some embodiments, the Tg / Mn ratio (K / Da) of the DDCR resin is >0.6, or 0.6-1.0, or 0.65-0.9, or 0.7-0.85, or <0.85.

[0045] In some implementations, the DDCR resin has an acid value of <80 mg KOH / g, or <50 mg KOH / g, or <40 mg KOH / g, or <30 mg KOH / g, or <25 mg KOH / g, or <15 mg KOH / g, or <5 mg KOH / g, or 0-80 mg KOH / g, or 0-50 mg KOH / g, or 0-25 mg KOH / g, or 0-20 mg KOH / g, or 0-10 mg KOH / g, or 1-15 mg KOH / g, or 0-5 mg KOH / g, according to ASTM D-465.

[0046] DDCR resin is a solid with ring and ball softening points of >30℃, >35℃, >40℃, or >50℃, or >60℃, or >70℃, or >75℃, or 30-160℃, or 50-125℃, or 60-120℃, or 70-120℃, or 75-120℃, <160℃, or <125℃, or <120℃, as measured according to ASTM E28-18.

[0047] In some embodiments, the Gardner color (solid color) of the DDCR resin is >18, or >10, or >5, or >2, or 0-18, or 1-14, or 2-10, according to ASTM D6166. In embodiments of hydrogenated DDCR, the Gardner color of the DDCR resin is <18, <12, or <8, or <5, or 0-18, or 1-14, or 2-10.

[0048] In some embodiments, the Brookfield viscosity of the DDCR resin is >15 mPa·s, or >20 mPa·s, or >25 mPa·s, or 15-1000 mPa·s, or 20-750 mPa·s, or 25-500 mPa·s, or 35-250 mPa·s, <1000 mPa·s, or <750 mPa·s, or <500 mPa·s, or <250 mPa·s, as measured at 177°C according to ASTM D2196.

[0049] In some implementations, the flash point of the DDCR resin is >150°C or >175°C, according to ASTM D 92.

[0050] In some embodiments, the density of the DDCR resin is 1.00-1.05, or 1.00-1.04, or 1.01-1.03, or 1.015-1.025 g / cm³. 3 .

[0051] In some embodiments, the DDCR resin is characterized by an oxygen content of <5%, or <3%, or <2%, or 0-5%, or 0-4%, or 0-3%, or 0-2% or 0-1%. The oxygen content of DDCR (in %) is calculated as the oxygen-to-carbon ratio—or the sum of the oxygen atoms present divided by the sum of the carbon atoms present in the DDCR, the amounts of oxygen and carbon atoms being obtained from elemental analysis.

[0052] In some embodiments, the DDCR resin exhibits a low cloud point in the polyolefin, indicating high compatibility with nonpolar polymers. In some embodiments, the DDCR resin has a cloud point in the polyolefin of <70°C, or <60°C, or <50°C, or <40°C, or >-30°C, or >-15°C, or -30°C to 70°C, or -20°C to 65°C, or -10°C to 60°C, or 0-50°C, wherein the starting DRA material is immiscible in a temperature range of 0-200°C.

[0053] The DDCR resin component can be used alone or in combination with two or more of the resins, at a dosage of 1-90 phr, or 5-80 phr, or 10-50 phr. In some embodiments, the rubber composition comprises any one of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 85, or any range of the above numbers for the DDCR resin component.

[0054] Rubber Component: The terms "rubber" or "elastomer" include natural rubber and its various virgin and recycled forms, as well as various synthetic rubbers. In some embodiments, the rubber component comprises any unsaturated diene elastomer selected from polybutadiene, natural rubber, synthetic polyisoprene, butadiene copolymers, isoprene copolymers, and mixtures thereof.

[0055] In some embodiments, the rubber is selected from butyl rubber, halogenated butyl rubber, EPDM (ethylene propylene diene monomer rubber), and mixtures thereof. In another embodiment, the rubber component is selected from natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), synthetic polyisoprene rubber, epoxy natural rubber, polybutadiene rubber, hydrogenated butadiene butadiene rubber (HNBR), hydrogenated styrene-butadiene rubber, ethylene propylene diene monomer rubber, ethylene propylene rubber, maleic acid modified ethylene propylene rubber, butyl rubber, isobutylene-aromatic vinyl or diene monomer copolymer, brominated NR, chlorinated NR, brominated isobutylene-p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymer rubber. Epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubber, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubber, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubber, tetrafluoroethylene propylene rubber, fluorinated silicone rubber, fluorinated phosphagen rubber, styrene elastomers, thermoplastic olefin elastomers, polyester elastomers, polyurethane elastomers, and polyamide elastomers.

[0056] Examples of SBR rubbers include emulsion-polymerized styrene-butadiene rubber (unmodified E-SBR), solution-polymerized styrene-butadiene rubber (unmodified S-SBR), and modified SBRs obtained by modifying their ends (modified E-SBR and modified S-SBR). In some embodiments, the rubber component includes rubber components other than SBR and BR, such as natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber (ENR), butyl rubber, nitrile rubber (NBR), ethylene propylene diene monomer rubber (EPDM), chloroprene rubber (CR), styrene-isoprene-butadiene rubber (SIBR), and may be used alone or in combination as needed.

[0057] The rubber component can be coupled, star-branched, branched, and / or functionalized using coupling agents and / or star-branching agents or functionalizing agents. Branched rubber can be branched (star-branched) butyl rubber, halogenated star-branched butyl rubber, poly(isobutylene-co-p-methylstyrene), brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, and mixtures thereof.

[0058] In some embodiments, the rubber is end-functionalized to improve its affinity for fillers such as carbon black and / or silica. Examples of coupling / functional groups include C-Sn bonds or amination functional groups (e.g., benzophenone), silanol functional groups or polysiloxane functional groups with silanol ends, alkoxysilyl groups, and polyether groups.

[0059] Filler: The rubber composition further comprises 30-200 phr or 30-150 phr of filler. Examples include, but are not limited to, calcium carbonate, carbon nanotubes, clay, mica, silica, silicates, talc, titanium dioxide, alumina, zinc oxide, starch, wood flour, carbon black, or mixtures thereof. The filler can be of any size, for example, 0.0001-100 μm.

[0060] Other examples of fillers include ultra-high molecular weight polyethylene (UHMWPE), granular polymer gels, and plasticized starch composite fillers known in the art.

[0061] In some embodiments, the filler is surface-treated, for example by coating or mixing with the aforementioned resin, or by coating or reacting with an organosilane substance.

[0062] Coupling agent: In some embodiments, the rubber composition further comprises a coupling agent. A "coupling agent" is any agent capable of promoting stable chemical and / or physical interactions between two substances that would not otherwise interact, such as a filler like silica and an elastomer. The coupling agent enables silica to reinforce the rubber. In some embodiments, the coupling agent is a sulfur-based coupling agent, an organic peroxide-based coupling agent, an inorganic coupling agent, a polyamine coupling agent, a resin coupling agent, a sulfur compound-based coupling agent, an oxime-nitrosamine-based coupling agent, and sulfur.

[0063] In some embodiments, the coupling agent is bifunctional. Examples include organosilanes or polyorganosiloxanes. Other examples of suitable coupling agents include silane polysulfides. The coupling agent may also be a bifunctional polyorganosiloxane or a hydroxysilane polysulfide. The coupling agent may also include other silane sulfides, such as silanes having at least one thiol (-SH) functional group (referred to as mercaptosilanes) and / or at least one masked thiol functional group. The coupling agent may also include combinations of one or more coupling agents described herein. In some embodiments, the coupling agent is an alkoxysilane or a polysulfide alkoxysilane, such as a polysulfide alkoxysilane.

[0064] The coupling agent content is 1-20 phr, or 1-10 phr, or 3-15 phr.

[0065] Optional plasticizer components: Plasticizers (also known as processing oils) refer to petroleum-derived processing oils and synthetic plasticizers used to extend elastomers and improve the processing properties of compositions. Suitable plasticizers include, but are not limited to, aliphatic esters, hydrocarbon processing oils, tall oil asphalt and modified tall oil asphalt, and combinations thereof.

[0066] In some embodiments, the plasticizer is selected from modified tall oil bitumen selected from the following: bitumen esters, decarboxylated tall oil bitumen, tall oil bitumen soap, heat-treated tall oil bitumen, and heat- and catalytically treated tall oil bitumen.

[0067] In some embodiments, the plasticizer comprises augmenting oils present in the elastomer and processing oils added during compounding. Suitable processing oils include aromatic oils, paraffinic oils, naphthenic oils, and low-PCA oils, such as MES, TDAE, and heavy naphthenic oils, as well as vegetable oils, such as sunflower oil, soybean oil, and safflower oil. Examples of low-PCA oils include oils with a polycyclic aromatic hydrocarbon content of less than 3% by weight. Suitable vegetable oils include, for example, soybean oil, sunflower oil, and rapeseed oil, which are present in the form of esters containing a certain degree of unsaturation.

[0068] In some embodiments, the plasticizer content is 0-25 phr or 5-15 phr. In another embodiment, the plasticizer content is a resin-to-plasticizer weight ratio >1, >3, or >6.

[0069] Crosslinking agent: In some embodiments, the rubber component in the composition can be crosslinked by adding a curing agent (e.g., sulfur, metals, metal oxides such as zinc oxide, peroxides, organometallic compounds, free radical initiators, fatty acids, and other agents common in the art). Other known curing methods that can be used include peroxide curing systems, resin curing systems, and thermal or radiation-induced crosslinking of polymers. Accelerators, activators, and retarders may also be used in the vulcanization process.

[0070] The content of the crosslinking agent is 0.3-10 phr, or 0.5-5.0 phr, or >0.3 phr, or >0.5 phr, or <15 phr, or <10 phr, or <8 phr, or <5 phr.

[0071] Other additives: The composition may be compounded with other components known in the art in amounts of up to 10 phr, such as sulfur donors, curing aids (e.g., accelerators, activators and retarders), processing additives, pigments, fatty acids, zinc oxide, waxes, antioxidants, anti-ozone agents and adhesives.

[0072] Molding method of tire rubber composition: The tire composition can be molded by methods known in the field of rubber compounding. The formulation is mixed in a 379 ml Banbury internal mixer using a three-stage mixing scheme known in the art. For example, the components are typically mixed in two stages, for example, at least one mixing stage, followed by an accelerator stage. The final curing agent (e.g., a sulfur curing agent) is mixed in the final stage, which is generally referred to as the "accelerator" stage, wherein the mixing is typically carried out at a lower mixing temperature than the previous mixing stages.

[0073] A thermomechanical mixing step can be performed on the tire composition. This step typically involves mechanically processing the material in a mixer or extruder for a suitable time to achieve a rubber temperature of 140-190°C. The duration of thermomechanical processing varies depending on the operating conditions and the volume and properties of the components. For example, thermomechanical processing can be 1-20 minutes.

[0074] Performance: Tire compositions containing DDCR resin exhibit reduced rolling resistance and improved wet grip performance.

[0075] In some embodiments, tire tread compositions containing DDCR resin exhibit similar wet grip (tanδ at 0°C) and lower rolling resistance (expressed as tanδ at 60°C), with rolling resistance reduced by >5%, or >10%, or >15% compared to tire tread compositions containing similar amounts of α-methylstyrene resin (AMS).

[0076] In some embodiments, tire tread compositions containing DDCR resin exhibit similar wet grip (tanδ at 0°C) and lower rolling resistance (expressed by tanδ value) at 60°C, with rolling resistance reduced by >5%, or >10%, or >15%, or >20% compared to tire tread compositions containing similar amounts of dimer rosin acid.

[0077] In some embodiments, tire tread compositions containing DDCR resin exhibit improved wet grip (expressed as tanδ value at 0°C) by >5%, or >10%, or >15% compared to tire tread compositions containing a similar amount of treated distilled aromatic extract oil.

[0078] In some embodiments, the wet grip to rolling resistance ratio (tanδ at 0°C / tanδ at 60°C) of the tire tread composition containing DDCR resin is >5%, >10%, >15%, or >20% higher than that of the tire tread composition containing an equivalent amount of AMS.

[0079] In some embodiments, the wet grip to rolling resistance ratio (tanδ at 0°C / tanδ at 60°C) of the tire tread composition containing DDCR resin is >20%, >30%, >40%, or >50% higher than that of the tire tread composition containing an equivalent amount of dimer rosin acid.

[0080] In some embodiments, the wet grip to rolling resistance ratio (tanδ at 0°C / tanδ at 60°C) of the tire tread composition containing DDCR resin is >5%, >10%, >15%, >20%, or >25% higher than that of the tire tread composition containing a considerable amount of treated distilled aromatic extract oil.

[0081] In some embodiments, tire tread compositions containing DDCR resin exhibit a lower storage modulus G' at 60°C compared to tire tread compositions containing a similar amount of AMS, namely, lower than 3%, or lower than 5%, or lower than 10%, or lower than 15%, or lower than 20%.

[0082] In some embodiments, tire tread compositions containing DDCR resin exhibit a lower loss modulus G" at 60°C compared to tire tread compositions containing a similar amount of AMS, namely lower by >5%, or lower by >10%, or lower by >20%, or lower by >30%, or lower by >40%.

[0083] Applications: In addition to tire applications, the composition can also be extruded, compressed, injection molded or laminated into various molded articles, such as fibers, films, laminates, layers, industrial parts such as automotive parts, appliance housings, consumer products, packaging, etc.

[0084] In tire applications, the rubber composition can be used to produce various tires, such as truck tires, bus tires, automobile tires, motorcycle tires, off-road tires, and aircraft tires. The rubber composition can also be used to make tire components, such as treads, sidewalls, scuff strips, tire rubber layers, reinforcing cord coating materials, and padding layers. The rubber composition can also be used in other applications, such as in cured bladders, inner tubes, air jackets, hoses, belts, footwear components, rollers, vibration damping devices, adhesives, sealants, enamel compounds, protective coatings, air cushions, pneumatic springs, and air bellows.

[0085] The rubber composition can also be used to produce molded rubber parts, such as automotive suspension dampers, automotive exhaust pipe hangers, and body mounts. In other applications, the rubber composition can also be used in medical applications, such as pharmaceutical stoppers and sealants, and coatings for medical devices.

[0086] Example: The following exemplary embodiments are non-limiting.

[0087] In the embodiments, the resins described in Table 1 were added to the tire tread compositions shown in Table 2, and their performance was tested.

[0088] The formulation was mixed in a 379 ml Banbury mixer using a three-stage mixing method known in the art.

[0089] The performance characteristics of the tire tread composition are shown in Table 3 below.

[0090] Tanδ measurements were performed using a DMA with a Metravib+450N, employing a temperature scan in dual shear mode from -60°C to +100°C, a heating rate of 1°C / min, 10 Hz, and dynamic strain measurements of 0.1% (-60°C to -5°C) and 3% (-5°C to 100°C). Tensile strength, elongation, and modulus were measured according to the procedure described in ISO 37. DIN abrasion resistance was measured using a DIN abrasion tester according to ISO 4649.

[0091]

[0092]

[0093]

[0094]

[0095] As used herein, the term “comprising” means the element or step identified after the term, but any such element or step is not exhaustive, and the implementation may include other elements or steps.

Claims

1. A rubber composition comprising a blend of the following substances: Rubber components, 50-200 parts by weight of filler, 0-25 parts by weight of plasticizer, and 5-90 parts by weight of dimerized decarboxylated rosin resin, which contains 50-100% by weight of a polycyclic hydrocarbon compound having one or more aliphatic unsaturated groups or aromatic groups and 34-80 carbon atoms. The dimerized decarboxylated rosin resin has the following characteristics: a molecular weight (Mn) of 250-900 Da, measured using gel permeation chromatography and polystyrene calibration standards; a polydispersity index of 1.0-1.33; and an oxygen-to-carbon ratio of <5%. The dimerized decarboxylated rosin resin is formed by decarboxylating dimerized rosin acid or dimerizing decarboxylated rosin. The parts by weight are based on 100 parts by weight of the rubber component; The dimerized decarboxylated rosin resin contains ≥50 wt% dimer, with the remainder being monomers, trimers, and larger polymers.

2. The rubber composition according to claim 1, wherein the dimerized decarboxylated rosin resin is characterized by having one or more of the following properties: Acid value <80mg KOH / g, measured using ASTM D465. Flash point >150℃, according to ASTM D92, The softening point Tsp of rings and spheres is >30℃, according to ASTM E28-18. Brookfield viscosity of 15-1000 mPa·s, measured at 177°C according to ASTM D2196. The glass transition temperature Tg from -20℃ to 110℃, according to ASTM E1356. 1.00-1.05 g / cm 3 The density, according to ASTM D792-13, T in K / Da >0.6 g / M n than, and The cloud point in polyolefins is less than 70°C.

3. The rubber composition according to any one of claims 1-2, wherein the dimeric decarboxylated rosin resin has a polydispersity index of 1.05-1.2 as measured by GPC.

4. The rubber composition according to any one of claims 1-2, wherein the dimerized decarboxylated rosin resin has a T (K / Da) content. g / M n The ratio is 0.6-1.

0.

5. The rubber composition according to any one of claims 1-2, wherein the oxygen content of the dimerized decarboxylated rosin resin is <3%.

6. The rubber composition according to any one of claims 1-2, wherein the dimerized decarboxylated rosin resin is unhydrogenated, partially hydrogenated, or fully hydrogenated.

7. The rubber composition according to any one of claims 1-2, wherein the rubber composition is extruded, compressed, injection molded or laminated into a molded rubber part.

8. A method for preparing a tire rubber composition, comprising: a) Provide 100 parts by weight of the rubber component; b) Provides a dimerized decarboxylated rosin resin with a rubber component of 5-75 parts by weight per 100 parts by weight, comprising 50-100% by weight of a polycyclic hydrocarbon compound having one or more aliphatic unsaturated groups or aromatic groups and 34-80 carbon atoms, and having the following characteristics: a molecular weight Mn of 250-900 Da, a polydispersity index of 1.0-1.33, and an oxygen-to-carbon ratio of <5%, as measured by gel permeation chromatography and a polystyrene calibration standard; and said dimerized decarboxylated rosin resin is formed by decarboxylating dimerized rosin acid or dimerizing decarboxylated rosin; and said dimerized decarboxylated rosin resin comprises ≥50 wt% dimer, the remainder being monomers, trimers, and larger polymers; c) Provide 50-200 parts by weight of filler and optionally up to 75 parts by weight of plasticizer based on 100 parts by weight of rubber component; d) Mix the rubber component, dimerized decarboxylated rosin resin, filler, and optional plasticizer to form a mixture; e) Knead the mixture; and f) The crosslinking system is added to the kneaded mixture to form a tire rubber composition.

9. The method according to claim 8, wherein the dimerized decarboxylated rosin resin is characterized by having one or more of the following properties: Acid value <80mg KOH / g, measured using ASTM D465. Flash point >150℃, according to ASTM D92, The softening point Tsp of rings and spheres is >30℃, according to ASTM E28-18. Brookfield viscosity of 15-1000 mPa·s, measured at 177°C according to ASTM D2196. The glass transition temperature Tg from -20℃ to 110℃, according to ASTM E1356. 1.00-1.05 g / cm 3 The density, according to ASTM D792-13, T in K / Da >0.6 g / M n than, and The cloud point of polyolefins at <70℃.

10. The method according to any one of claims 8-9, wherein the dimerized decarboxylated rosin resin comprises ≥75 wt% of the sum of dimer and trimer substances.

11. The method according to any one of claims 8-9, wherein the polydispersity index of the dimerized decarboxylated rosin resin, as measured by GPC, is 1.05-1.

15.

12. The method according to any one of claims 8-9, wherein the T of the dimerized decarboxylated rosin resin in K / Da is... g / M n The ratio is 0.6-1.

0.

13. The method according to any one of claims 8-9, wherein the oxygen content of the dimerized decarboxylated rosin resin is <3%.

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