Method for preparing a composite containing resin

Abstract

A method for preparing the composite is provided. Disclosed herein is a method for preparing a composite comprising mixing a solid elastomer, a wet filler and a resin. A single stage mixing process or a multi-stage mixing process can be used. Further disclosed is a composite comprising a filler dispersed in an elastomer at a loading of at least 20 phr, the composite having a liquid content of 10% by weight or less, based on the total weight of the composite.

Description

[Technical Field]

[0001] Technical field of inventions Disclosed herein are methods for preparing composites by combining solid elastomers, wet fillers, and resins. Furthermore, corresponding vulcanized products derived from these composites are also disclosed. [Background technology]

[0002] background In the rubber industry, there is a constant demand for developing methods to disperse fillers in elastomers, and it is particularly desirable to develop methods that can be performed very efficiently in terms of quality, time, labor, and / or cost of filler dispersion.

[0003] Many commercially important products are formed from elastic compositions in which reinforcing fillers are dispersed in a variety of synthetic elastomers, natural rubber, or elastomer blends. For example, carbon black and silica are widely used to reinforce natural rubber and other elastomers. It is common to produce masterbatches, i.e., premixtures of various optional additives such as reinforcing fillers, elastomers, and extender oils. Such masterbatches are then compounded with processing additives and curing additives, and upon curing, many commercially important products are produced. Such products include, for example, pneumatic, non-pneumatic, or solid tires for vehicles, including tread sections with caps and bases, undertreads, inner liners, sidewalls, wire skims, and carcasses. Other products include, for example, engine mounts and bearing cylinders, conveyor belts, windshield wipers, rubber components for aerospace and marine equipment, vehicle track elements, seals, liners, gaskets, wheels, bumpers, and vibration damping systems. [Overview of the Initiative]

[0004] While there are many methods for incorporating fillers into solid elastomers, there is a constant need for novel methods to achieve acceptable or improved dispersion quality and functionality derived from elastomer composite masterbatches, which can be shaped to produce acceptable or improved properties in the corresponding vulcanized rubber compounds and rubber articles.

[0005] overview One aspect is, (a) Putting into the mixer at least a solid elastomer; a wet filler containing a filler (e.g., silica and / or carbon black and / or silicon-treated carbon black) and a liquid present in an amount of at least 15% by mass based on the total mass of the wet filler; and a resin; (b) in one or more mixing steps, mixing at least a solid elastomer, a wet filler, and a resin to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; and (c) Discharge from the mixer a composite containing a filler dispersed in an elastomer at a filling volume of at least 20 phr, wherein the composite has a liquid content of 10% by mass or less based on the total mass of the composite. This is a method for preparing a composite containing [the specified element].

[0006] Another aspect is, (a) Putting into a first mixer a wet filler comprising at least a solid elastomer; and a filler (e.g., silica and / or carbon black and / or silicon-treated carbon black) and a liquid present in an amount of at least 20% by mass based on the total mass of the wet filler; (b) in one or more mixing steps, mixing at least a solid elastomer and a wet filler to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; (c) Discharging from the first mixer a mixture comprising a filler dispersed in an elastomer at a loading of at least 20 phr, having a liquid content reduced to an amount less than the liquid content at the start of step (b), and having a material temperature in the range of 100 °C to 180 °C; (d) Mixing the mixture from (c) in a second mixer to obtain a composite; and (e) Discharging from the second mixer a composite having a liquid content of less than 3% by mass based on the total mass of the composite, A method for preparing a composite comprising: The resin is introduced into the first mixer, the second mixer, or both the first mixer and the second mixer.

[0007] For any aspect or method or embodiment disclosed in the present disclosure, where applicable, the method may further comprise any one or more of the following embodiments: The resin has a Tg in the range of at least 25 °C or 25 °C to 110 °C; The resin has a softening point of at least 50 °C, or in the range of 50 °C to 150 °C, determined according to ASTM E-28; The resin is selected from one or more of C5 resins, C5 / C9 resins, C9 resins, rosin resins, terpene resins, aromatic modified terpene resins, dicyclopentadiene resins, alkylphenol resins, and combinations thereof.

[0008] With respect to any aspect or method or embodiment disclosed in the present disclosure, where applicable, the method may further include any one or more than one of the following embodiments: Feeding may include feeding separate feeds of resin and wet filler into a mixer; Feeding may include multiple additions of solid elastomer, wet filler, and / or resin; Feeding may include introducing a dry filler into the mixer, where the dry filler is wetted by adding a liquid to form a wet filler in the mixer; The mixing is carried out in one mixing step; The mixing is carried out in two or more mixing steps; The mixing in (b) is a second mixing step, and the first mixing step includes mixing at least a portion of the solid elastomer and at least a portion of the wet filler, and then feeding resin into the mixer; Feeding in (a) may include feeding a mixture containing resin and wet filler into the mixer; Feeding in (a) may include feeding a co-pellet containing resin and wet filler into the mixer.

[0009] With respect to any aspect or method or embodiment disclosed in the present disclosure, where applicable, the method may further include any one or more than one of the following embodiments: In at least one of the mixing steps, the method includes carrying out the mixing, where the mixer has at least one temperature control means set to a temperature Tz of 65°C or higher; In at least one of the mixing steps, the method includes carrying out the mixing by one or more rotors of a mixer operating at a tip speed of at least 0.6 m / s for at least 50% of the mixing time.

[0010] With respect to any aspect, method or embodiment disclosed herein, where applicable, the method may further comprise one or more of the following embodiments: the wet filler is selected from at least one material selected from carbonaceous materials, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or other fillers disclosed herein, or combinations thereof, as well as coated materials thereof and treated materials thereof; the wet filler comprises silica; the wet filler comprises silica in an amount of at least 50% by mass relative to the total mass of the filler, and the wet filler further comprises carbon black and / or silicon-treated carbon black; the wet filler has a liquid present in an amount ranging from 20% to 80% by mass based on the total mass of the wet filler; and the wet filler is in the form of a powder, paste, pellet or cake.

[0011] With respect to any aspect, method, or embodiment disclosed in this disclosure, where applicable, the method may further include one or more of the following embodiments: the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomers, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers, and blends thereof; the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, and blends thereof.

[0012] With respect to any aspect, method, or embodiment disclosed in this disclosure, where applicable, the method may further include one or more of the following embodiments: one or more mixing steps are a continuous process; one or more mixing steps are a batch process; the resin is introduced into a first mixer, and step (b) includes mixing at least a solid elastomer, a wet filler, and the resin to form a mixture; the resin is introduced into a second mixer, and step (d) includes mixing the mixture from (c) and the resin in the second mixer to obtain a composite. The first and second mixers are the same; the first and second mixers are different; the second mixer operates under at least one of the following conditions: (i) ram pressure of 5 psi or less; (ii) ram raised to at least 75% of its highest level; (iii) ram operating in floating mode; (iv) ram positioned so as not to be substantially in contact with the mixture; (v) mixer without ram; and (vi) mixture filling rate in the range of 25% to 70%; the second mixer operates under at least one of the following conditions (i) to (vi) for at least 50% of the mixing time.

[0013] Another aspect provides a method for preparing a vulcanized product, comprising curing a composite prepared by any one of claims 1 to 32 in the presence of at least one curing agent to form a vulcanized product. Furthermore, vulcanized products prepared from the composites disclosed herein and articles containing such vulcanized products are disclosed. [Modes for carrying out the invention]

[0014] Detailed explanation Certain rubber compounds, such as those containing solution styrene-butadiene rubber (SBR) or a blend of solution SBR and butadiene rubber (BR) in combination with silica or a silica / carbon black blend, can be applied to passenger car and light truck (PC / LT) treads to reduce rolling resistance and enhance wet traction. There is a recent trend toward electric vehicles (EVs). Compositions containing natural rubber and silica in addition to SBR, or an SBR / BR blend, may be used in PC / LT tread compounds for tires used in EVs. This is because natural rubber is known for its high tear strength and high mechanical strength, and silica can provide reduced rolling resistance.

[0015] However, there is a need to reduce tire rolling resistance to extend the driving range of EVs. Compared to tires used in vehicles powered by internal combustion engines, tires used in EVs are subjected to heavier loads and higher torque. Such tires may experience more severe mechanical stress and, therefore, may wear out more rapidly. Thus, there is a need to develop new tread compositions for tires that provide reduced rolling resistance for EVs while maintaining or even improving tread wear performance.

[0016] Natural rubber / silica compositions can be a good option for PC / LT compounds and tires used in electric vehicles because natural rubber is known for its high tear strength and high mechanical strength. However, there are challenges in developing silica compositions based on natural rubber. Natural rubber / silica compounds prepared from conventional mixing processes may exhibit inferior strengthening properties and reduced tread wear performance compared to natural rubber / carbon black compounds (see, for example, U.S. Patent No. 9,758,645).

[0017] PCT Publication No. WO2020 / 247663 (the disclosure of which is incorporated herein by reference) describes a mixing process using solid elastomers and wet fillers (including, for example, fillers and liquids) that enables control of batch time and temperature beyond the range achievable with known dry mixing processes. Other advantages include the possibility of achieving improved filler dispersion and / or enhanced rubber-filler interactions and / or improved rubber compound properties during compounding and vulcanization, compared to conventionally mixed masterbatches. One or more properties, such as the ratio of tensile stress at 300% elongation to stress at 100% elongation (M300 / M100) and the tangent delta (tanδ) measured at 60°C, can be improved. Such wet mixing processes (one-stage or multi-stage mixing) can be used to prepare elastomer compositions, such as SBR, BR, natural rubber-based compositions, such as natural rubber / silica compositions, with enhanced reinforcing properties and / or reduced hysteresis loss at high temperatures, compared to rubber compositions produced by dry mixing processes.

[0018] Certain tire performance characteristics, such as wet traction or wet grip performance, can be improved by incorporating resins (e.g., tackifiers, traction resins, thermoplastic resins) into the rubber composition. The incorporation of certain resins in passenger car and truck treads, optionally containing BR in combination with SBR and / or NR, can improve wear performance without impairing wet traction.

[0019] Processes for mixing wet fillers, solid elastomers and one or more resins are disclosed herein. Furthermore, composites and vulcanized products produced from such processes are disclosed. Typically for tires, the glass transition temperature (T g There is a correlation between characteristics such as ) and wet grip performance. Appropriate T gBy selecting a specific resin with a certain value, the viscoelastic properties of the rubber composition can be modified, optimizing performance characteristics such as wet grip performance. The process of incorporating resin in a wet mixing method may produce an elastomer composition that can result in passenger car and light truck tire treads with improved tread wear and / or reduced rolling resistance.

[0020] One aspect relates to a method for manufacturing composites, which includes the following: (a) Put into the mixer at least a solid elastomer; filler and a wet filler containing a liquid present in an amount of at least 15% by mass based on the total mass of the wet filler; and a resin; (b) in one or more mixing steps, mixing at least a solid elastomer, a wet filler, and a resin to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; and (c) Discharge from the mixer a composite containing a filler dispersed in an elastomer at a filling amount of at least 20 phr, wherein the composite has a liquid content of 10% by mass or less based on the total mass of the composite.

[0021] The composite formed by the methods disclosed herein can be considered as an uncured mixture of fillers(s) and elastomers(s), for example, an uncured mixture of fillers(s), elastomers(s), and resins(s). The composite formed can be considered as a mixture or a masterbatch. The composite formed may optionally be an intermediate product that can be used in subsequent rubber compounding and one or more vulcanization processes. The composite may be subjected to additional processes prior to rubber compounding and vulcanization, such as one or more holding or further mixing steps, one or more additional drying steps, one or more extrusion steps, one or more calendering steps, one or more milling steps, one or more granulation steps, one or more baling steps, one or more twin-screw extrusion steps, or one or more rubber processing steps, to obtain a rubber compound or rubber article.

[0022] As described herein, resins may affect the viscoelasticity of rubber compositions and can improve properties such as wet traction performance. The resins disclosed herein are selected according to their compatibility with solid elastomers and desired applications. The resins have a glass transition temperature (T g ) and may be solids having certain desired properties of softening point. By selecting the Tg of the resin, the Tg of the resulting composite, and consequently the rubber compound (vulcanized product), can be changed. As an option, an appropriate T of the resin incorporated in the disclosed process gThe temperature may be at least 25°C, at least 30°C, at least 35°C, at least 40°C, or at least 50°C, or may be in the range of 25°C to 110°C, 35°C to 110°C, 40°C to 110°C, 25°C to 100°C, 35°C to 100°C, 40°C to 100°C, 25°C to 90°C, 35°C to 90°C, 40°C to 90°C, 25°C to 80°C, 35°C to 80°C, 40°C to 80°C, 25°C to 70°C, 35°C to 70°C, 40°C to 70°C, 25°C to 65°C, 35°C to 65°C, or 40°C to 65°C.

[0023] T g Another point to consider is the softening point of the resin, which can also affect viscoelasticity. The softening point is usually defined as the temperature at which the resin changes from a brittle or poorly flowing material to a softer, less viscous liquid. As outlined in ASTM E-28 (ring-ball softening point), the softening point of a resin can be determined using a ring-ball apparatus. A suitable softening point for a resin determined according to ASTM E-28 may be in the range of at least 50°C, at least 60°C, at least 70°C, or 50°C to 150°C, 60°C to 150°C, 70°C to 150°C, 80°C to 150°C, 50°C to 125°C, 60°C to 125°C, 70°C to 125°C, 80°C to 125°C, 50°C to 110°C, 60°C to 110°C, 70°C to 110°C, or 80°C to 110°C. The resin may be compatible or incompatible with the elastomer in the composition, depending on the desired performance characteristics.

[0024] The resin can be selected based on the application and / or elastomer type. A number of resin types are available, such as those derived from petroleum cracking processes, resins from wood raw materials, etc. Hydrocarbon resins are manufactured from petroleum raw materials and can be either aliphatic resins or aromatic resins. Examples of aliphatic resins include C5 resins having monomers with five carbon atoms. Examples of aromatic resins include C9 resins containing nine-carbon aromatic monomers or mixtures of C8 - C10 aromatic monomers. C5 / C9 resins are both aliphatic and aromatic resins because they have comonomers of both C5 and C9. In tire applications, C5, C9, and C5 / C9 resins can be used to improve wet grip performance. Commercially available C5, C9, and C5 / C9 resins include, for example, the trade name Impera TM resin or Picco TM resin, such as Impera TM R1607 resin (C5), Impera TM G1750 resin (C9), and Impera TM resins sold under D1606 resin (C5 / C9) (Eastman Chemical Co.). Rosin resins are derived, for example, from wood sources (such as trees) or the papermaking process. Commercially available rosin resins include, for example, the trade name Permalyn TM resin, such as Permalyn TMExamples include resins sold under 5095 Resin (Eastman Chemical Co.). Terpene resins are manufactured from terpene raw materials (e.g., wood, turpentine oil, etc.). Terpene resins can be modified with aromatic groups, such as C9 monomers, to form aromatically modified terpene resins. Rosin, terpenes, and aromatically modified terpene resins can improve wet grip performance and steering ability. Other suitable resins can be formed by dimerizing cyclopentadiene (dicyclopentadiene resins), by condensation of alkylphenol and formaldehyde (alkylphenol resins), or by condensation of alkylphenol and acetylene. Various combinations of resin types can also be used. Resins suitable for tire and other elastomer-based applications can also be found in the following literature: U.S. Patents 10,738,178, 10,745,545, and U.S. Patent Application Publication 2015 / 0283854 (these disclosures are incorporated herein by reference). As options, the resin may be selected from one or more of the following: C5 resin, C5 / C9 resin, C9 resin, rosin resin, terpene resin, aromatically modified terpene resin, dicyclopentadiene resin, alkylphenol resin, and combinations thereof (e.g., blends, mixtures).

[0025] The resin filling amount (for example, the amount of resin put into the mixer or the amount of resin present in the composite) may be at least 5 phr, at least 10 phr, at least 20 phr, and optionally up to 100 phr, for example, in the range of 5 phr to 100 phr, for example, 5 phr to 75 phr, 5 phr to 50 phr, 5 phr to 25 phr, 5 phr to 20 phr, or 5 phr to 15 phr.

[0026] A method for preparing a composite includes the step of introducing or adding at least one or more solid elastomers and a wet filler into a mixer. The combination of the solid elastomers and the wet filler forms a mixture during one or more mixing steps. The method further includes carrying out the mixing in one or more mixing steps, wherein at least a portion of the liquid is removed by evaporation or an evaporation process occurring during mixing. The liquid of the wet filler may be removed by evaporation (at least a portion may be removed under the requested mixing conditions) and may be a volatile liquid, for example, volatile at the bulk mixture temperature. For example, a volatile liquid can be distinguished from an oil (e.g., extender oil, process oil) that may be present for at least a portion of the mixing, because such oil is intended to be present in the composite being discharged and therefore will not evaporate during most of the mixing time.

[0027] The fillers introduced into the mixer include wet fillers. In their dry state, the fillers may contain little to no liquid (e.g., water or moisture) adsorbed on their surface. For example, carbon black may have 0% by mass, or 0.1% to 1% by mass, or up to 3% by mass, or up to 4% by mass of liquid, and precipitated silica may have a liquid (e.g., water or moisture) content of 4% to 7% by mass, for example, 4% to 6% by mass of liquid. Such fillers are referred to in this disclosure as dry fillers or unwetted fillers. Under certain conditions, for example, high humidity conditions, silica may have a water or moisture content of up to about 10%. Alternatively, dry fillers may have a liquid content of 10% by mass or less (e.g., in the range of 4% to 10% by mass) relative to the total mass of the filler and liquid. In other options, the dry filler has a liquid content of 8% by mass or less (e.g., in the range of 4% to 8% by mass), 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. For example, the filler is silica and has a liquid (e.g., water) content of 10% by mass or less (e.g., in the range of 4% to 10% by mass), or 6% by mass or less.

[0028] For existing wet fillers, a liquid or additional liquid can be added to the filler, which may be present on a substantial portion, or substantially all, of the filler's surface, including inner surfaces or pores accessible to the liquid. Thus, sufficient liquid is provided to wet a substantial portion, or substantially all, of the filler's surface before mixing with the solid elastomer. During mixing, the wet filler is dispersed in the solid elastomer, and at least a portion of the liquid may be removed by evaporation, thus making the filler's surface available for interaction with the solid elastomer. The wet filler has a liquid content of at least 15% by mass, or at least 20% by mass, relative to the total mass of the wet filler. For example, at least 25%, at least 30%, at least 40%, at least 50% by mass, or 20%~99%, 20%~95%, 20%~90%, 20%~80%, 20%~70%, 20%~60%, 30%~99%, 30%~95%, 30%~ The liquid content may be 90%, 30%~80%, 30%~70%, 30%~60%, 40%~99%, 40%~95%, 40%~90%, 40%~80%, 40%~70%, 40%~60%, 45%~99%, 45%~95%, 45%~90%, 45%~80%, 45%~70%, 45%~60%, 50%~99%, 50%~95%, 50%~90%, 50%~80%, 50%~70%, or 50%~60%. The liquid content of the filler can be expressed as a mass percentage: 100 × [mass of liquid] / [mass of liquid + mass of dry filler]. Alternatively, the amount of liquid can be determined based on the oil absorption rate (OAN) of the filler, where OAN is determined according to ASTM D2414. OAN is a measure of the filler structure and can be used to determine the amount of liquid needed to wet the filler. For example, wet fillers such as wet carbon black, wet silica (e.g., precipitated silica), or wet silicon-treated carbon black may have a liquid content determined according to the formula: k × OAN / (100 + OAN) × 100.In one embodiment, k is in the range of 0.3 to 1.1, or 0.5 to 1.05, or 0.6 to 1.1, or 0.7 to 1.1, or 0.8 to 1.1, or 0.9 to 1.1, or 0.6 to 1.0, or 0.7 to 1.0, or 0.8 to 1.0, or 0.8 to 1.05, or 0.9 to 1.0, or 0.95 to 1, or 0.95 to 1, or 1.0 to 1.1. Optionally, the wet filler has a liquid content in the range of 20% to 80%, 30% to 70%, 30% to 60%, 40% to 70%, or 40% to 60%.

[0029] As an option, the wet filler has the viscosity of a solid. As an option, the dry filler is wet only to the extent that the resulting wet filler maintains the form of a powder, granules, pellets, cake, or paste, or a similar viscosity, and / or has the appearance of a powder, granules, pellets, cake, or paste. The wet filler does not flow like a liquid (when the applied stress is 0). As an option, the wet filler, whether in the form of individual particles, aggregates, pellets, cake, or paste, can maintain its shape at 25°C if molded into such a form. The wet filler is not a composite produced by a liquid masterbatch process, nor is it another pre-blended composite of fillers dispersed in a solid elastomer (from a liquid elastomer) where the elastomer is a continuous phase. The wet filler is not a slurry of fillers and does not have the viscosity of a liquid or slurry.

[0030] The liquid used to wet the filler may be an aqueous liquid or contain an aqueous liquid, for example, water or contain an aqueous liquid, but is not limited to the following. The liquid may contain at least one other component, for example, a base (or more), an acid (or more), a salt (or more), a solvent (or more), a surfactant (or more), a coupling agent (or more) (for example, if the filler further contains silica), and / or a processing aid (or more), and / or any combination thereof, but is not limited to the following. More specific examples of components are NaOH, KOH, acetic acid, formic acid, citric acid, phosphoric acid, sulfuric acid, or any combination thereof. For example, the base may be selected from NaOH, KOH and mixtures thereof, or the acid may be selected from acetic acid, formic acid, citric acid, phosphoric acid or sulfuric acid and combinations thereof. The liquid may be a solvent (or more) that is immiscible with the elastomer used (for example, an alcohol such as ethanol), or contain an aqueous solvent (or more). Instead, the liquid consists of approximately 80% to 100% water, or 90% to 99% water, based on the total mass of the liquid.

[0031] In the methods disclosed herein, at least a solid elastomer, a wet filler, and a resin are introduced into a mixer (e.g., supplied, introduced). The introduction of the solid elastomer and / or filler and / or resin can be carried out in one or more steps, or additionally. The introduction can be carried out in any form, and specific examples, but are not limited to, conveying, metering, dumping, and / or supplying the solid elastomer and wet filler to the mixer in batch, semi-continuous, or continuous flow. The solid elastomer and wet filler are not introduced into the mixer as a premixture, where premixture means a mixture prepared by means other than combining the solid elastomer and wet filler. The solid elastomer and wet filler can be added together, but not as a mixture prepared by means other than combining the solid elastomer and wet filler (except, for example, when the wet filler is pre-dispersed into the elastomer by means other than combining the solid elastomer and wet filler (where the elastomer is a continuous phase)). A mixture or premix or preblend of solid elastomers, wet fillers, and resins can be placed in a mixer, which can be prepared, for example, in a mixer or container by any known method.

[0032] The addition of the solid elastomer, wet filler, and resin may be done all at once, sequentially, or in any order. The addition may include separate additions of the solid elastomer, resin, and wet filler. Alternatively, the addition may include adding a mixture containing the wet filler and resin. For example, (a) adding all the solid elastomer first, (b) adding all the wet filler first (alone or as a mixture with the resin), (c) adding all the solid elastomer first together with some of the wet filler and resin, then adding one or more of the remaining wet filler and resin, (d) adding some of the solid elastomer, then some of the wet filler and / or resin (e.g., a mixture of wet filler and resin), (e) adding at least some of the wet filler first, then at least some of the solid elastomer and / or resin, (f) adding some of the solid elastomer, some of the wet filler and some of the resin simultaneously or almost simultaneously, so as to be introduced into the mixer separately, or (g) adding at least some of the solid elastomer and at least some of the wet filler in any order, in one or more parts, mixing at least some of the solid elastomer and at least some of the wet filler, introducing at least some of the resin into the mixer, and mixing the solid elastomer, wet filler and resin to form a mixture.

[0033] Other applicable methods for introducing solid elastomers and wet fillers into a mixer are disclosed in PCT Publication No. WO2020 / 247663, which is incorporated herein by reference.

[0034] With respect to a mixture comprising a wet filler and a resin, the mixture may be a particulate mixture of the wet filler and the resin (e.g., a powder). The resin may be coated with the wet filler or combined with it by a solution or dispersion (e.g., an aqueous solution or aqueous dispersion). The powder may be fed directly into a mixer or formed into pellets, i.e., pellets which are the mixture containing the resin. Alternatively, a solution or dispersion containing the resin may be combined with a filler (e.g., fluffy carbon black, silica, silicon-treated carbon black, and / or other filler types). In addition to combining, the solution may further include wetting the filler to form a wet filler. The resulting wet filler can then be fed into a pin pelletizer and pelletized by the method disclosed herein.

[0035] Generally, the filler may be any conventional filler used with the elastomer, such as a reinforcing filler, and examples include, but are not limited to, carbon black, silica, carbon black-containing fillers, silica-containing fillers, and / or any combination thereof. The filler may be particulate, fibrous, or plate-like. For example, particulate fillers consist of individual particles. Such fillers may often have an aspect ratio (e.g., length to diameter) of 3:1 or less, or 2:1 or less, or 1.5:1 or less. Fibrous fillers may have an aspect ratio of 2:1 or more, 3:1 or more, 4:1 or more, or greater. Typically, fillers used to reinforce elastomers have microscopic (e.g., several hundred microns or less) or nanoscale (e.g., less than 1 micron) dimensions. In the case of carbon black, the individual particles of particulate carbon black refer not to the primary particles themselves, but to aggregates or aggregates formed from primary particles. In other embodiments, the filler may have a plate-like structure such as graphene and reduced graphene oxide.

[0036] The filler may be selected from carbonaceous materials, carbon black, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolysis carbon, recycled carbon, recovered carbon black (e.g., rCB as defined in ASTM D8178-19), graphene, graphene oxide, reduced graphene oxide (e.g., reduced graphene oxide worm disclosed in PCT publication no. WO2019 / 070514A1 (the disclosure of which is incorporated herein by reference)), or high-density reduced graphene oxide granules disclosed in U.S. Patent Provisional Application No. 62 / 857,296 filed June 5, 2019 and PCT publication no. 2020 / 247681 (the disclosure of which is incorporated herein by reference), carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, or corresponding coated materials of these (e.g., silicon-treated carbon black) or chemically treated materials (e.g., chemically treated carbon black). Other suitable fillers include carbon nanostructures (CNSs, singular CNS) and multiple carbon nanotubes (CNTs), which are crosslinked in the polymer structure, for example, by branching in a dendritic manner, combining with one another, entanglement, and / or sharing a common wall. CNS fillers are described in U.S. Patent No. 9,447,259 and PCT Application No. PCT / US2021 / 027814 (their disclosures are incorporated herein by reference). Blends of fillers, such as blends of silica and carbon black, blends of silica and silicon-treated carbon black, and blends of carbon black and silicon-treated carbon black can also be used. Fillers can be chemically treated (e.g., chemically treated carbon black, chemically treated silica, silicon-treated carbon black) and / or chemically modified. Fillers may be or contain carbon black to which one or more organic groups are bonded. The filler may have one or more coatings present on it (e.g., silicon-coated material, silica-coated material, carbon-coated material).The filler may be oxidized and / or have other surface treatments. There are no restrictions on the type of filler that can be used (e.g., silica, carbon black, or other fillers).

[0037] As mentioned above, fiber fillers can also be incorporated in the manner disclosed herein, examples of which include natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nano-sized carbon filaments), such as the short fibers described in PCT publication number WO2021 / 153643 (the disclosure of which is incorporated herein by reference). Other fiber fillers include poly(p-phenylene terephthalamide) pulp (commercially available as Kevlar® pulp (DuPont)).

[0038] Other suitable fillers include bio-based materials (derived from biosources), recycled materials, or other fillers that are considered renewable or sustainable, such as hydrothermal carbon (HTC, where the filler includes lignin treated by hydrothermal carbonization as described in U.S. Patents 10,035,957 and 10,428,218 (their disclosures are incorporated herein by reference)), rice husk silica, methane pyrolysis-derived carbon, nanocrystalline cellulose starch particles, polysaccharides, glucans, dextran, microfibrillated cellulose, artificial polysaccharide particles, starch, diatomaceous earth, crumb rubber, and functionalized crumb rubber. Examples of artificial polysaccharides are described in U.S. Patent Publication Nos. 2020 / 0181370 and 2020 / 0190270 (their disclosures are incorporated herein by reference). For example, polysaccharides can be selected from: polyalpha-1,3-glucan; polyalpha-1,3-1,6-glucan; water-insoluble alpha-(1,3-glucan) polymers having 90% or more α-1,3-glycosidic bonds, less than 1% by mass of alpha-1,3,6-glycosidic branching points, and a number-average degree of polymerization in the range of 55 to 10,000; dextran; compositions containing polyalpha-1,3-glucan ester compounds; and water-insoluble cellulose having a weight-average degree of polymerization (DPw) of about 10 to about 1000 and a cellulose II crystalline structure.

[0039] The carbon black may be furnace black, gas black, thermal black, acetylene black or lamp black, plasma black, recovered carbon black (as defined in ASTM D8178-19, for example), or carbon products containing silicon-containing and / or metal-containing species. The carbon black used in any method disclosed herein may be any grade of reinforcing carbon and semi-reinforcing carbon black. Examples of ASTM grade reinforcing grades are N110, N121, N134, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, and N375 carbon blacks. Examples of ASTM-grade semi-reinforced grades include N539, N550, N650, N660, N683, N762, N765, N774, N787, N990 carbon black, and / or N990 grade thermal black.

[0040] Carbon black, 20m 2 / g~250m 2 The carbon black may have any statistical thickness surface area (STSA), such as in the range of / g or larger. The STSA (statistical thickness surface area) is determined based on ASTM test procedure D-5816 (measured by nitrogen adsorption). The carbon black may have a compressible oil absorption rate (COAN) in the range of approximately 30 mL / 100g to approximately 150 mL / 100g. The compressible oil absorption rate (COAN) is determined according to ASTM D3493. As an option, the carbon black may be 20m 2 / g~180m 2 / g, or 60m 2 / g~150m 2 It may have STSA in the range of / g and COAN in the range of 40mL / 100g to 115mL / 100g, or 70mL / 100g to 115mL / 100g.

[0041] As stated above, the carbon black may be rubber black, and in particular may be a reinforced or semi-reinforced grade of carbon black. Carbon black sold under the trademarks Regal®, Black Pearls®, Spheron®, Sterling®, Propel®, Endure®, and Vulcan® (available from Cabot Corporation), the trademarks Raven®, Statex®, Furnex®, and Neotex®, as well as the CD and HV lines (available from Birla Carbon (formerly available from Columbia Chemicals)), and the trademarks Corax®, Durax®, Ecorax®, and Purex® and the CK line (available from Orion Engineered Carbons (formerly available from Evonik and Degussa Industries)), as well as other fillers suitable for use in rubber or tire applications, may also be utilized for use in a variety of applications. Suitable chemically functionalized carbon blacks include those disclosed in WO96 / 18688 and US2013 / 0165560, which are incorporated herein by reference. A mixture of any of these carbon blacks may be used. Carbon blacks having surface area and structure exceeding typical values ​​selected for ASTM grade and rubber mixtures, such as those described in U.S. Patent Application Publication 2018 / 0282523 (whose disclosure is incorporated herein by reference), may be used in wet fillers and in composites manufactured by any of the methods disclosed herein.

[0042] As an option, with respect to the filler, which is at least silica, one or more types of silica, or any combination of silica(s), may be used in any embodiment disclosed herein. Silica may include precipitated silica, fumed silica, silica gel, and / or colloidal silica, or be precipitated silica, fumed silica, silica gel, and / or colloidal silica. Silica may be untreated silica and / or chemically treated silica, or may include such silica. Silica may be suitable for reinforcing elastomer composites, and about 20 m 2 / g ~ approx. 450m 2 / g; approx. 30m 2 / g ~ approx. 450m 2 / g; approx. 30m 2 / g~about 400m 2 / g; or approximately 60ml 2 / g ~ approx. 250m 2 / g, approx. 60m 2 / g ~ approx. 250m 2 / g, approx. 80m 2 / g~about 200m 2 The Brunaur Emmett Teller surface area (multipoint BET nitrogen adsorption, BET as determined by ASTM D1993) per gram may be used as a characteristic. Silica is approximately 80 m². 2 / g~250m 2 / g, for example, about 80mg 2 / g~200m 2 / g, or 90m 2 / g~200m 2 / g, 80m 2 / g~175m 2 / g, or 80m 2 / g~150m 2STSA may be in the range of / g. Highly dispersible precipitated silica can be used as a filler in this method. Highly dispersible precipitated silica ("HDS") is understood to mean any silica that has sufficient ability to disaggregate and disperse in the matrix of the elastomer. The determination of such dispersion may be observed by known methods by electron or optical microscopy on a thin section of the elastomer composite. Examples of commercially available grades of HDS include Perkasil® GT 3000GRAN silica from WR Grace & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165MP, 1115MP, Premium, and 1200MP silica from Solvay SA, Hi-Sil® EZ 160G silica from PPG Industries, Inc., and Zeopol® 8741 or 8745 silica from Evonik Industries. Conventional non-HDS precipitated silica can also be used. Conventional commercially available grades of precipitated silica include Perkasil® KS 408 silica from WR Grace & Co., Zeosil® 175GR silica from Solvay SA, Ultrasil® VN3 silica from Evonik Industries, and Hi-Sil® 243 silica from PPG Industries, Inc. Precipitated silica containing surface-adhered silane coupling agents can also be used. Examples of commercially available grades of chemically treated precipitated silica include Agilon® 400, 454, or 458 silica from PPG Industries, Inc., and Coupsil silica (e.g., Coupsil® 6109 silica) from Evonik Industries.

[0043] The amounts of liquid in the filler described above can also be applied equally to silica, but as a more specific example, when silica is used as a wetting filler in part or whole, the silica as a wetting filler may have liquid present in an amount of about 25% to about 75% by mass, for example, about 30% to about 75%, about 40% to about 75%, about 45% to about 75%, about 50% to about 75%, about 30% to about 70%, about 40% to about 70%, about 45% to about 70%, about 50% to about 70%, about 30% to about 65%, about 40% to about 65%, about 45% to about 65%, about 50% to about 65%, about 30% to about 60% by mass, about 40% to about 60%, about 45% to about 60%, or about 50% to about 60% by mass, based on the mass of the total wetting filler or the mass of only the wet silica present.

[0044] Typically, silica (e.g., silica particles) all have a silicon content of at least 20% by mass, at least 25% by mass, at least 30% by mass, at least 35% by mass, at least 40% by mass, at least 50% by mass, at least 60% by mass, at least 70% by mass, at least 80% by mass, at least 90% by mass, or almost 100% by mass, or 100% by mass, or about 20% to about 100% by mass, based on the total mass of the particles. Any silica(s) can be chemically functionalized to have, for example, bonded or adsorbed chemical groups, or for example, bonded or adsorbed organic groups. Any combination of silica(s) can also be used. Silica may have a partially or entirely hydrophobic surface, or may become hydrophobic by making the surface of the silica hydrophobic through treatment (e.g., chemical treatment). A hydrophobic surface can be obtained by chemically modifying silica particles with a hydrophobic silane that does not have ionic groups, for example, bis-triethoxysilylpropyltetrasulfide. Suitable hydrophobic surface-treated silica particles for use in this disclosure can be obtained from commercially available products such as Agilon® 454 silica and Agilon® 400 silica from PPG Industries. Silica with a low surface silanol density, for example, silica obtained by dehydroxylation at temperatures above 150°C, for example, via a calcination process, can be used in this disclosure. Intermediate forms of silica obtained from the precipitation process in the form of a cake or paste, without drying (silica that has never been dried), can be added directly to the mixer as a wet filler, thus eliminating the complex drying and other downstream processing steps used in the conventional production of precipitated silica.

[0045] Carbon black may be a multiphase aggregate containing at least one carbon phase and at least one metal-containing species phase or silicon-containing species phase, i.e., silicon-treated carbon black. In silicon-treated carbon black, silicon-containing species, such as silicon oxides or carbides, are dispersed in at least a portion of the carbon black aggregate as an inherent part of the carbon black. Although silicon-treated carbon black is not a coated or otherwise modified carbon black aggregate, it actually represents a two-phase aggregate particle. One phase is carbon, which still exists as graphite crystals and / or amorphous carbon, while the second phase is silica, and possibly other silicon-containing species. Thus, the silicon-containing species phase of silicon-treated carbon black is an inherent part of the aggregate, and it is dispersed in at least a portion of the aggregate. Ecoblack TM Siliconized carbon black is available from Cabot Corporation. The manufacturing and properties of these siliconized carbon blacks are described in U.S. Patent No. 6,028,137 (the disclosure of which is incorporated herein by reference).

[0046] Silicon-treated carbon black may contain silicon-containing regions that are still part of the carbon black, primarily on the surface of the carbon black aggregates, and / or silicon-treated carbon black may contain silicon-containing regions dispersed throughout the carbon black aggregates. Silicon-treated carbon black may be oxidized. Silicon-treated carbon black may contain approximately 0.1% to 50% silicon by mass, based on the mass of the silicon-treated carbon black. For example, it may contain approximately 0.1% to 46.6%, 0.1% to 46%, 0.1% to 45%, 0.1% to 40%, 0.1% to 35%, 0.1% to 30%, 0.1% to 25%, 0.1% to 20%, 0.1% to 15%, 0.1% to 10%, 0.1% to 5%, or 0.1% to 2% by mass. These amounts may all be approximately 0.5% to 25% by mass, approximately 1% to 15% by mass of silicon, approximately 2% to 10% by mass, approximately 3% to 8% by mass, approximately 4% to 5% by mass, or approximately 6% by mass, based on the mass of silicon-treated carbon black.

[0047] In any embodiment and any step, the coupling agent may be introduced at any step (or at any step or location) as long as there is an opportunity for the coupling agent to be dispersed in the composite. The coupling agent may be one or more silane coupling agents, one or more zirconate coupling agents, one or more titanate coupling agents, one or more nitro coupling agents, or any combination thereof, or may include such a combination. The coupling agents are bis(3-triethoxysilylpropyl)tetrasulfane (e.g., Si 69 from Evonik Industries, Struktol SCA98 from Struktol Company), bis(3-triethoxysilylpropyl)disulfane (e.g., Si 75 and Si 266 from Evonik Industries, Struktol SCA985 from Struktol Company), 3-thiocyanatopropyl-triethoxysilane (e.g., Si 264 from Evonik Industries), gamma-mercaptopropyl-trimethoxysilane (e.g., VP Si 163 from Evonik Industries, Struktol SCA989 from Struktol Company), gamma-mercaptopropyl-triethoxysilane (e.g., VP Si Si 263) Zirconium dineoalkanolatodi(3-mercapto)propionato-O,N,N'-bis(2-methyl-2-nitropropyl)-1,6-diaminohexane, S-(3-(triethoxysilyl)propyl)octanthioate (e.g., NXT coupling agent from Momentive, Friendly, WV), and / or coupling agents having one or more chemically similar or identical chemical groups, or including such coupling agents. Additional specific examples of coupling agents include, but are not limited to, VP Si 363 from Evonik Industries under trade names, and NXT Z and NXT Z-50 silanes from Momentive.Other compounds that can function as coupling agents include compounds having nitroxide radicals, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) disclosed in U.S. Patents 6,084,015, 6,194,509 and 8,584,725 and U.S. Patent Publication 2009 / 0292044 (their disclosures are incorporated by reference into this disclosure), or nitrile oxides, nitrile imines, and nitrone 1,3-dipole compounds disclosed in U.S. Patents 10,239,971, 10,202,471 and 10,787,471 and U.S. Patent Publication 2020 / 0362139 (their disclosures are incorporated by reference into this disclosure). The coupling agents described in this disclosure can be used in any process disclosed in this disclosure to provide hydrophobic surface modification to silica before using silica (pre-coupling treated or pre-treated silica). It should be recognized that any combination of elastomers, additives, and additional composites may be added to the elastomer composite, for example, in a compounding machine.

[0048] Alternatively, mixing (for example, when the filler contains silica and / or silicon-treated carbon black) can be carried out without a coupling agent. Optionally, a coating agent (filler coating agent) may be introduced at any step (or multiple steps or location) before discharge. Methods of mixing without a coupling agent and / or with a coating agent (including exemplary coating agents) are disclosed in PCT publication number WO2022 / 125675, which is incorporated herein by reference.

[0049] As an alternative, the wet filler can be generated in a mixer, for example, by introducing a dry filler into a mixer and wetting it by adding a liquid (e.g., water, sequentially, simultaneously, or nearly simultaneously) to form a wet filler in the mixer, and then adding a solid elastomer to the mixer. The introduction of the dry filler to be wetted can be carried out with all or part of the filler intended to be used (e.g., one or more additional portions of the wet filler are further added to the mixer to obtain the intended total amount of the starting wet filler). The amount of liquid introduced into the mixer is at least 15% by mass, or at least 20% by mass, or other amounts disclosed in this disclosure with respect to the preparation of the wet filler.

[0050] The input of at least fillers and liquids into a mixer can be carried out in many ways. In one example, the fillers and liquids can be added as separate inputs, for example, by adding the fillers first and then the liquids, or vice versa. In another example, at least some or all of the fillers and liquids are pre-combined in an external container (e.g., a holding container, bottle, table, conveyor, etc.) or in a separate mixer, and then transferred or conveyed to the mixer into which the solid elastomer is input. For example, the fillers may be a blend of fillers, where one type of filler (first filler) is pre-combined with the liquid (wet filler), while another type of filler (second filler) is directly added to the mixer as a dry filler to produce a filler blend. Thus, the input of fillers and liquids into a mixer involves pre-combining the fillers and liquids before transferring them to the mixer.

[0051] In addition to the wet filler, the mixture may optionally further contain one or more non-wet fillers (e.g., any filler that is not wet as described in this disclosure, such as dry fillers, such as fillers having 10% by mass or less of liquid). If non-wet fillers are present, the total amount of filler may be such that at least 50% by mass or at least 60% by mass, at least 70% by mass, at least 80% by mass, at least 90% by mass, or at least 95% by mass of the total mass of filler is wet filler, for example, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, or 95% to 99% of the total amount of filler is wet filler, and the remainder of the filler is either not wet or not considered wet filler.

[0052] The amount of filler to be added to the mixture (e.g., wet filler alone, or wet filler and other fillers) should be at least 20 phr, at least 30 phr, at least 40 phr, or 20 phr-250 phr, 20 phr-200 phr, 20 phr-180 phr, 20 phr-150 phr, 20 phr-100 phr, 20 phr-90 phr, 20 phr-80 phr, 30 phr-200 phr, 30 phr The target can be in the range of r~180phr, 30phr~150phr, 30phr~100phr, 30phr~80phr, 30phr~70phr, 40phr~200phr, 40phr~180phr, 40phr~150phr, 40phr~100phr, 40phr~80phr, 35phr~65phr, or 30phr~55phr, or any other amount within or outside one of these ranges. In certain applications, for example, a high silica content may be required to further improve wet traction performance. For example, the amount of silica to be added to the mixture (present in the composite) can be targeted at at least 50 phr, at least 60 phr, at least 70 phr, for example, 50 phr to 250 phr, 50 phr to 200 phr, 50 phr to 150 phr, or 50 phr to 100 phr. The above phr amounts can also be applied to the filler dispersed in the elastomer (filler filler amount). Other filler types, blends, and combinations can be used, for example, those disclosed in PCT Publication No. WO2020 / 247663 (the disclosure of which is incorporated herein by reference).

[0053] In certain embodiments where the filler is electrically conductive (e.g., carbon black), this method of wet mixing with a resin can yield a rubber compound with increased electrical resistivity. This increased electrical resistivity may be an indicator of improved fine dispersion of the filler. For example, the electrical resistivity of a rubber compound prepared by mixing a wet filler with a solid elastomer may be increased by at least 10% compared to an equivalent rubber compound (e.g., with the same elastomer, filler, filler amount, and formulation) prepared by dry mixing (mixing a dry filler with a solid elastomer).

[0054] With respect to the solid elastomer used and mixed with the wet filler, the solid elastomer may be considered as a dry elastomer or a substantially dry elastomer. The solid elastomer may have a liquid content (e.g., solvent or water content) of 5% by mass or less, for example, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.1% to 5% by mass, 0.5% to 5% by mass, 1% to 5% by mass, 0.5% to 4% by mass, etc., based on the total mass of the solid elastomer. The solid elastomer (e.g., starting solid elastomer) may be an elastomer overall (containing a starting liquid, e.g., water, in a content of 5% by mass or less), and may further contain one or more fillers and / or other components. For example, the solid elastomer may be 50% to 99.9% by mass of elastomer and 0.1% to 50% by mass of fillers pre-dispersed in the elastomer (the pre-dispersed fillers are added to the wet filler). Such elastomers can be prepared by a dry mixing process between a non-wetting filler and a solid elastomer. Alternatively, a composite prepared by mixing a wet filler and a solid elastomer (for example, according to the process disclosed herein) can be used as the solid elastomer, which may be further mixed with a wet filler according to the process disclosed herein. However, the solid elastomer is not a composite, mixture, or compound prepared by a liquid masterbatch process, nor is it any other pre-blended composite of fillers dispersed in an elastomer while the elastomer is in a liquid state, e.g., latex, suspension, or solution.

[0055] Any solid elastomer can be used in this method. Examples of elastomers include natural rubber (NR), synthetic elastomers such as styrene-butadiene rubber (SBR, e.g., solution SBR (SSBR), emulsion SBR (ESBR), or oil-extracted SSBR (OESSBR)), polybutadiene (BR), polyisoprene rubber (IR), functionalized SBR, functionalized BR, functionalized NR, ethylene-propylene rubber (e.g., EPDM), isobutylene-based elastomers (e.g., butyl rubber), halogenated butyl rubber, polychloroprene rubber (CR), nitrile rubber (NBR), and hydrogenated nitrile rubber (H Examples of synthetic polymers that can be used in this method (whether alone or in blends) include hydrogenated SBR and thermoplastic block copolymers (e.g., reusable ones). Examples of synthetic polymers include NBR, fluoroelastomers, perfluoroelastomers, and silicone rubbers, such as natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, nitrile rubber, hydrogenated nitrile rubber, and blends thereof, or, for example, a blend of a first solid elastomer and a second solid elastomer. Other synthetic polymers that can be used in this method (whether alone or in blends) include hydrogenated SBR and thermoplastic block copolymers (e.g., reusable ones). Examples of synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene, and isoprene. Other synthetic elastomers include those synthesized by metallocene chemistry, where the metal is selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Co, Ni, and Ti.Polymers made from bio-based monomers, such as those containing modern carbon as defined by ASTM D6866, may also be used, for example, polymers made from bio-based styrene monomers as disclosed in U.S. Patent No. 9,868,853 (the disclosure of which is incorporated herein by reference), or polymers made from bio-based monomers such as butadiene, isoprene, ethylene, propylene, farnesene, and their comonomers. When two or more elastomers are used, the two or more elastomers may be added to the mixer simultaneously as a blend (as one or two or more additions), or the elastomers may be added separately in any order and amount. For example, a solid elastomer may include natural rubber blended with one or more of the elastomers disclosed herein (e.g., butadiene rubber and / or styrene-butadiene rubber, or SBR blended with BR). For example, additional solid elastomers can be added to the mixer separately, and natural rubber can be added to the mixer separately.

[0056] The solid elastomer may be or contain natural rubber. If the solid elastomer is a blend, it may contain at least 50% by mass, or at least 70% by mass, or at least 90% by mass, natural rubber. The blend may further contain synthetic elastomers such as styrene-butadiene rubber, functionalized styrene-butadiene rubber, and polybutadiene rubber, and / or one or more of any other elastomers disclosed herein.

[0057] Natural rubber may be chemically modified in several ways. For example, it may be treated to chemically or enzymatically modify or reduce various non-rubber components, or the rubber molecules themselves may be modified with various monomers or other chemical groups such as chlorine. Other examples include epoxidized natural rubber and natural rubber with a nitrogen content of up to 0.3% by mass, as described in PCT publication number WO2017 / 207912.

[0058] Other exemplary elastomers include, but are not limited to, rubber; polymers such as 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene (where alkyl may be methyl, ethyl, propyl, etc.), acrylonitrile, ethylene, and propylene (e.g., homopolymers, copolymers, and / or terpolymers).

[0059] Other applicable solid elastomers that can be used in the manner disclosed herein are disclosed in PCT Publication No. 2020 / 247663 (the disclosure of which is incorporated herein by reference).

[0060] With respect to mixers that can be used in any of the methods disclosed herein, any suitable mixer capable of combining fillers with solid elastomers (e.g., mixing or compounding them together) may be used. The mixer(s) may be a batch mixer or a continuous mixer. The mixer and process combination may be used in any of the methods disclosed herein, and the mixer may be used sequentially, in tandem (e.g., a tandem mixer), and / or integrated with other processing equipment. The mixer may be an internal mixer, a closed mixer, an open mixer, an extruder, a continuous compounder, a kneading mixer, or a combination thereof. The mixer may be capable of incorporating fillers and resins into a solid elastomer and / or dispersing fillers and resins in the elastomer and / or distributing fillers and resins in the elastomer.

[0061] A mixer may have one or more rotors (at least one rotor). The at least one rotor or one or more rotors may be a screw rotor, a mesh rotor, a tangential rotor, a kneading rotor(s), a rotor used in an extruder, a roll mill that provides a large total specific energy, or a creping mill. Typically, one or more rotors are used in a mixer; for example, a mixer may incorporate one rotor (e.g., a screw rotor), two, four, six, eight, or more rotors. The set of rotors may be arranged in parallel and / or in a continuous direction within a given mixer configuration.

[0062] With regard to mixing, mixing can be carried out in one or more mixing steps. Mixing begins when at least the solid elastomer and wet filler are introduced into the mixer, and energy is applied to the mixing system, which drives one or more rotors of the mixer. One or more mixing steps may be performed after the introduction step is completed, or may overlap with the introduction step for any length of time. For example, one or more portions of the solid elastomer and / or wet filler may be introduced into the mixer before or after mixing has started. Then, one or more additional portions of the solid elastomer and / or filler and / or resin may be introduced into the mixer. For batch mixing, the mixing steps are completed after the introduction steps are completed.

[0063] As an option, regardless of the mechanism, controlling the mixer surface temperature can provide an opportunity for longer mixing or residence times compared to a mixing process without temperature control of at least one mixer surface, thereby resulting in improved filler dispersion and / or improved rubber filler interaction and / or consistent and / or efficient mixing.

[0064] The temperature control means may be the flow or circulation of a heat transfer fluid through channels within one or more parts of the mixer, but is not limited to the following. For example, the heat transfer fluid may be water or heat transfer oil. For example, the heat transfer fluid may flow through the rotor, mixing chamber walls, ram, and drop door. In other embodiments, the heat transfer fluid may flow within a jacket (e.g., a jacket having fluid flow means) or within coils around one or more parts of the mixer. Alternatively, the temperature control means (e.g., heat supply) may be an electrical element embedded in the mixer. The system providing the temperature control means may further include means for measuring either the temperature of the heat transfer fluid or the temperature of one or more parts of the mixer. Temperature measurements can be supplied to a system used to control the heating and cooling of the heat transfer fluid. For example, a desired temperature of at least one surface of the mixer can be controlled by setting the temperature of a heat transfer fluid located in channels adjacent to one or more parts of the mixer (e.g., walls, doors, rotor, etc.).

[0065] The temperature of at least one temperature control means may be set and maintained by, for example, one or more temperature control units ("TCU"). This set temperature or TCU temperature is referred to as "T" in this disclosure. z It is also called "heat transfer fluid." In the case of a temperature control means incorporating a heat transfer fluid, T z This indicates the temperature of the fluid itself.

[0066] As options, the temperature control means can be 30°C to 150°C, 40°C to 150°C, 50°C to 150°C, or 60°C to 150°C, for example, 30°C to 155°C, 30°C to 125°C, 40°C to 125°C, 50°C to 125°C, 60°C to 125°C, 30°C to 110°C, 40°C to 110°C, 50°C to 110°C, 60°C to 110°C, 65°C to 110°C, 30°C to 100°C, 40°C to 100°C, 50°C to 100°C. Temperature range T: 60℃~100℃, 65℃~100℃, 30℃~95℃, 40℃~95℃, 50℃~95℃, 60℃~95℃, 30℃~90℃, 40℃~90℃, 50℃~90℃, 65℃~95℃, 60℃~90℃, 65℃~90℃, 70℃~110℃, 70℃~100℃, 70℃~95℃, 70℃~90℃, 75℃~110℃, 75℃~100℃, 75℃~95℃, or 75℃~90℃. z It may be set to this range. Other ranges are possible with the devices available in this field.

[0067] Under similar conditions for filler-type, elastomer-type, and mixer-type mixtures, this process can enable higher energy input compared to dry mixing. Controlled removal of water from the mixture allows for longer mixing times and thus improves the dispersion of the filler. As described in this disclosure, this process provides operating conditions that balance longer mixing times with evaporation or removal of water within a reasonable amount of time.

[0068] Other operating parameters to consider include the maximum usable pressure. Pressure affects the temperature of the filler and rubber mixtures. If the mixer is a batch mixer with a ram, the pressure inside the mixer chamber may be affected by the control of the pressure applied to the ram cylinder.

[0069] Another option is to optimize the rotor tip speed. The energy input to the mixing system is, at least in part, a function of the speed and rotor type of at least one rotor. The tip speed, considering the rotor diameter and rotor speed, can be calculated according to the following formula. Tip velocity, m / s = π × (rotor diameter, m) × (rotational speed, rpm) / 60

[0070] Since the tip velocity may change during mixing, as an option, a tip velocity of at least 0.5 m / s or at least 0.6 m / s is achieved over at least 50% of the mixing time, e.g., at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or substantially all of the mixing time. The tip velocity may be at least 0.6 m / s, at least 0.7 m / s, at least 0.8 m / s, at least 0.9 m / s, at least 1.0 m / s, at least 1.1 m / s, at least 1.2 m / s, at least 1.5 m / s, or at least 2 m / s over at least 50% of the mixing time or over the other parts of the mixing listed above. The tip velocity can be selected to minimize the mixing time, or the tip velocity may be 0.6 m / s to 10 m / s, 0.6 m / s to 8 m / s, 0.6 to 6 m / s, 0.6 m / s to 4 m / s, 0.6 m / s to 3 m / s, 0.6 m / s to 2 m / s, 0.7 m / s to 4 m / s, 0.7 m / s to 3 m / s, 0.7 m / s to 2 m / s, 0.7 m / s to 10 m / s, 0.7 m / s to 8 m / s, 0.7 to 6 m / s, 1 m / s to 10 m / s, 1 m / s to 8 m / s, 1 m / s to 6 m / s, 1 m / s to 4 m / s, 1 m / s to 3 m / s, or 1 m / s to 2 m / s (for example, over at least 50% of the mixing time or other mixing times described herein).

[0071] Any one or more commercially available mixers comprising one or more rotors, temperature control means and other components, and related mixing methods for producing rubber compounds may be used in this method, for example, those disclosed in PCT Publication No. WO2020 / 247663 (the disclosure of which is incorporated herein by reference).

[0072] "One or more mixing steps" is understood to mean that the steps disclosed herein may be a first mixing step, followed by a further mixing step before discharge. One or more mixing steps may be a single mixing step, for example, the mixing may be a one-stage or single-stage mixing step or process carried out under one or more of the following conditions: at least one of the mixer temperatures is controlled by a temperature control means, one or more rotors operate at a tip speed of at least 0.6 m / s for at least 50% of the mixing time, and / or at least one temperature control means is set to a temperature Tz of 65°C or higher, and / or continuous mixing; each of these is described in further detail herein. In certain cases, in a single-stage or single-stage mixing step, the composite may be discharged with a liquid content of 10% by mass or less. In other embodiments, two or more mixing steps or stages may be carried out, as long as one of the mixing steps is carried out under one or more of the conditions described herein.

[0073] As suggested, in any method disclosed herein, during one or more mixing steps, at least some of the liquid present in the mixture and / or wet filler being introduced is at least partially removed by evaporation. Alternatively, one or more mixing steps or stages may further remove some of the liquid from the mixture by squeezing, compression, and / or squeezing, or any combination thereof. Alternatively, some of the liquid may be discharged from the mixer after or during the discharge of the composite.

[0074] During the mixing cycle, after most of the liquid has been released from the composite and incorporated fillers, the mixture experiences a temperature increase. It is desirable to avoid excessive temperature increases that degrade the elastomer. Discharge (e.g., "dumping" in batch mixing) can be carried out based on time, temperature, specific energy, or power parameters selected to minimize such degradation.

[0075] In any method disclosed herein, a discharge step is performed from the mixer to obtain a composite containing the filler dispersed in the elastomer with a total filling amount of at least 20 phr, at least 30 phr, at least 40 phr, at least 50 phr, e.g., 20 to 250 phr, or other filling amounts disclosed herein. Optionally, the discharge is performed based on a specified mixing time. The mixing time between the start of mixing and the discharge may be about 1 minute or more, e.g., about 1 to 40 minutes, about 1 to 30 minutes, about 1 to 20 minutes, or 1 to 15 minutes, or 3 to 30 minutes, 3 to 20 minutes, 3 to 15 minutes, 3 to 10 minutes, 3 to 9 minutes, 3 to 8 minutes, 3 to 7 minutes, 3 to 6 minutes, 5 to 30 minutes, or 5 to 20 minutes, or 5 to 15 minutes, 5 to 10 minutes, or 1 to 12 minutes, or 1 to 10 minutes, or other times. Alternatively, for batch internal mixers, ram stop time can be used as a parameter to monitor batch mixing time (e.g., the time the mixer operates with the ram in its lowest position (e.g., fully seated) or with ram deflection (as described in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated into this disclosure by reference)). Ram stop time may be in the range of less than 30 minutes, less than 15 minutes, less than 10 minutes, less than 9 minutes, less than 8 minutes, less than 7 minutes, less than 6 minutes, or 3 to 30 minutes, 3 to 20 minutes, 3 to 15 minutes, 3 to 12 minutes, 3 to 10 minutes, 3 to 9 minutes, 3 to 8 minutes, 3 to 7 minutes, 3 to 6 minutes, or 5 to 15 minutes, or 5 to 10 minutes. Alternatively, discharge may be performed based on discharge temperature or discharge temperature. For example, the mixer may have an emission temperature in the range of 120°C to 190°C, 130°C to 180°C, for example, 140°C to 180°C, 150°C to 180°C, 130°C to 170°C, 140°C to 170°C, 150°C to 170°C, or other temperatures within or outside these ranges.

[0076] The method further includes discharging the formed composite from the mixer. The discharged composite may have a liquid content of 10% by mass or less based on the total mass of the composite, which is outlined in the following formula: Composite liquid content % = 100 × [Mass of liquid] / [Mass of liquid + Mass of dry composite]

[0077] In any method disclosed herein, the discharged composite may have a liquid content of 10% by mass or less based on the total mass of the composite, for example, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 2% by mass or less, or 1% by mass based on the total mass of the composite. This amount may be in the range of 0.1% to 10%, 0.5% to 9%, 0.5% to 7%, 0.5% to 5%, or 0.5% to 3% by mass based on the total mass of the composite discharged from the mixer at the end of the process. In any method disclosed herein, the liquid content (e.g., “water content”) may be a measured mass percentage of liquid present in the composite based on the total mass of the composite.

[0078] In any method disclosed herein, the liquid content in the composite may be measured as a mass percentage of the liquid present in the composite based on the total mass of the composite. Numerous instruments for measuring the liquid (e.g., water) content in rubber materials are known in the art, such as the Karl Fischer coulometric titration system or the moisture balance from Mettler (Toledo International, Inc., Columbus, Ohio).

[0079] In any method disclosed herein, the discharged composite may have a liquid content of 10% by mass or less, while optionally, there may be liquid (e.g., water) present in the mixer that is not retained in the discharged composite. This excess liquid is neither part of the composite nor part of any liquid content calculated for the composite.

[0080] In any method disclosed herein, the total liquid content (or total water content or total moisture content) of the material fed into the mixer is higher than the liquid content of the composite discharged at the end of the process. For example, the liquid content of the discharged composite may be 10% to 99.9% (mass% to mass%), 10% to 95%, or 10% to 50% lower than the liquid content of the material fed into the mixer.

[0081] Optionally, the process further includes adding the resin and optionally a degradation inhibitor during the loading or mixing process, i.e., during one or more mixing steps. In any embodiment disclosed herein, as an alternative option, after mixing of at least the solid elastomer and the wet filler has begun and before the discharge step, the method further includes adding the resin and optionally at least one degradation inhibitor to the mixer, so that the resin and at least one degradation inhibitor are mixed with the solid elastomer and the wet filler.

[0082] As an option, the mixture comprises, essentially comprises, a solid elastomer, a wetting filler, and a resin; the mixture comprises, essentially comprises, a solid elastomer, a wetting filler, a resin, and a degradation inhibitor; the composite comprises, essentially comprises, a filler dispersed in the elastomer; the composite comprises, essentially comprises, a filler dispersed in the elastomer and a degradation inhibitor; the composite comprises, essentially comprises, a filler dispersed in the elastomer and a resin; the composite comprises, essentially comprises, a filler dispersed in the elastomer and a degradation inhibitor. Alternatively, the addition of the resin and degradation inhibitor(s) may be carried out before the composite is formed, and the water content is 10% by mass or less or 5% by mass or less.

[0083] The addition of the resin and optional degradation inhibitors (one or more) may be performed at any time before the discharge step, for example, before or after the mixer reaches a specified mixer temperature of 120°C or higher. This specified mixer temperature can be measured by a temperature measuring device in the mixing cavity. The specified mixer temperature may be the same as the highest temperature the mixture or composite reaches during the mixing stage (which can be determined by removing the composite from the mixer and inserting a thermocouple or other temperature measuring device into the composite), or it may differ from the highest temperature by 30°C or less, or 20°C or less, or 10°C or less (or 5°C or less, 3°C or less, or 2°C or less). In this mixing method, optionally, the resin and optional degradation inhibitors may be added to the mixer when the mixer reaches a temperature of 120°C or higher. In other embodiments, the specified temperature may be in the range of 120°C to 190°C, 125°C to 190°C, 130°C to 190°C, 135°C to 190°C, 140°C to 190°C, 145°C to 190°C, 150°C to 190°C, 120°C to 180°C, 125°C to 180°C, 130°C to 180°C, 135°C to 180°C, 140°C to 180°C, 145°C to 180°C, 150°C to 180°C, 120°C to 170°C, 125°C to 170°C, 130°C to 170°C, 135°C to 170°C, 140°C to 170°C, 145°C to 170°C, 150°C to 170°C, etc.

[0084] An example of a degradation inhibitor that can be introduced is N-(1,3-dimethylbutyl)-N'-phenyl-paraphenylenediamine (6PPD), and others are described in other sections of this disclosure. Degradation inhibitors can be introduced in amounts ranging from 1% to 5%, 0.5% to 2%, or 0% to 3% by mass, based on the mass of the composite to be formed. Degradation inhibitors added during the input or mixing process may help prevent the degradation of the elastomer during mixing; however, the presence of water in the mixture slows the rate of elastomer decomposition compared to a dry mixing process, which may delay the addition of degradation inhibitors.

[0085] After the composite has been formed and discharged, the method may include a further optional step of mixing the composite with an additional elastomer to form a composite comprising the elastomer blend. The “additional elastomer” or second elastomer may be an additional natural rubber, or an elastomer other than natural rubber such as any elastomer disclosed herein, e.g., synthetic elastomers (e.g., styrene-butadiene rubber (SBR such as SSBR and ESBR), polybutadiene (BR) and polyisoprene rubber (IR), ethylene-propylene rubber (e.g., EPDM), isobutylene elastomers (e.g., butyl rubber), polychloroprene rubber (CR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers and silicone elastomers). Blends of synthetic rubber and natural rubber, or blends of two or more types of elastomers, such as a blend of a first elastomer and a second elastomer, can also be used.

[0086] A composite blend can be formed by feeding two or more different elastomers into a mixer. For example, a natural rubber that has never been dried and at least one additional elastomer, which is also a coagulated or solid elastomer (e.g., having less than 5% water), can be fed into the mixer. Alternatively, an elastomer blend can be fed into the mixer. Another option is for the process to involve mixing the discharged composite with additional elastomers to form a blend. The discharged composite (e.g., after single-stage, two-stage, or multi-stage mixing) may have a water content of 5% or less, 3% or less, and 2% or less by mass relative to the mass of the composite when blended with one or more additional elastomers (e.g., a composite containing fillers (e.g., carbon black, silica, and / or silicon-treated carbon black)), and the natural rubber may be blended with synthetic elastomers such as BR or SBR. Furthermore, both elastomers and fillers (wet or dry, for example, wet or dry carbon black and / or silica and / or silicon-treated carbon black) can be combined with the composite.

[0087] Alternatively, a composite containing a filler (e.g., carbon black and / or silica and / or silicon-treated carbon black) and natural rubber, prepared according to the methods disclosed herein, can be combined with a masterbatch containing natural rubber and / or a synthetic polymer, prepared by any method known in the art, such as a known dry mixing process or a solvent masterbatch process. For example, the silica / elastomer masterbatch may be prepared as described in U.S. Patents 9,758,627 and 10,125,229, or may be a masterbatch from neodymium-catalyzed polybutadiene as described in U.S. Patent 9,758,646 (their disclosures are incorporated by reference into this disclosure). The masterbatch may have a fiber filler, for example, poly(p-phenylene terephthalamide) pulp as described in U.S. Patent 6,068,922 (its disclosure is incorporated by reference into this disclosure). The masterbatch may contain fillers such as graphene, graphene oxide, reduced graphene oxide or high-density reduced graphene oxide granules, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanostructures, the latter of which are disclosed in U.S. Patent No. 9,447,259 and PCT application number PCT / US2021 / 027814 (their disclosures are incorporated herein by reference). Other suitable masterbatches include composites prepared from a mixture of wet fillers and solid elastomers as described in PCT publication number WO2020 / 247663 (their disclosures are incorporated herein by reference). For example, the masterbatch may contain fillers such as carbon black and / or silica, and elastomers such as SBR and / or butadiene rubber. A commercially available masterbatch is, e.g., Emulsil. TM Silica masterbatch or Emulblack TM Commercially available masterbatches, such as carbon black masterbatches (both available from the Dynasol group), can also be used.

[0088] Exemplary masterbatches containing elastomer blends include: blends of natural rubber with synthetic elastomers, bio-derived elastomers, and / or functionalized elastomers (e.g., SSBR, ESBR, and BR), where the filler can be selected from one or more of carbon black, silica, and silicon-treated carbon black.

[0089] In addition to the solid elastomer, wet filler, and resin, one or more inputs of at least one additional elastomer can be added to the mixer to form a composite blend. Alternatively, the process may include mixing the discharged composite with the additional elastomer to form a blend. The at least one additional elastomer may be the same as or different from the solid elastomer.

[0090] Alternatively, the discharged composite may contain at least one additive selected from degradation inhibitors and coupling agents (for example, if the wet filler further contains silica, or if dry silica is added to the mixer), which may be added at any time during addition or mixing.

[0091] For multi-stage processes, a method for preparing a composite includes the step of adding or introducing to a first mixer at least (a) one or more solid elastomers, (b) one or more fillers, wherein at least one filler or a portion of at least one filler is a wet filler as described herein (e.g., a wet filler comprising a filler and a liquid present in an amount of at least 15% by mass based on the total mass of the wet filler), and optionally (c) a resin. Combining the solid elastomer with the wet filler and optionally the resin forms a mixture or composite during this mixing step(s), which can be considered a first mixing step or stage. The method further includes mixing the mixture in this first mixing step to such an extent that at least a portion of the liquid is removed by evaporation or by an evaporation process occurring during mixing. This first mixing step or stage (in one or more mixing steps) is carried out using one or more of the above processes for forming the composite, with the understanding that the liquid content of the mixture discharged from the mixer after the first mixing step (e.g., the discharged mixture) does not need to be 10% by mass or less. In other words, in a multi-step process, the mixture obtained by the completion of the first mixing from the first mixer (or first mixing step) may have a liquid content greater than 10% by mass, but has a reduced liquid content (in mass%) compared to the liquid content of the combined solid elastomer and wet filler at the start of the first mixing step.

[0092] As a further option, before the first mixer or another mixer is used in the second mixing step, there may be a resting period during which the composite formed from the first mixer or another container or location (e.g., mixing, stopping, and subsequent further mixing) is allowed to rest, cool, or both. For example, this resting period may be such that the mixture reaches a material temperature (also called probe temperature) of less than 180°C before the further mixing step begins (e.g., the discharged mixture may have a material temperature in the range of about 100°C to about 180°C, about 70°C to 179°C, or about 100°C to about 170°C, or about 120°C to about 160°C). Alternatively, the resting period before the start of further or second mixing steps may be about 1 minute to 60 minutes or longer. The material temperature can be obtained by numerous methods known in the art, e.g., by inserting a thermocouple or other temperature measuring device into the mixture or composite.

[0093] The method then includes mixing or further mixing the mixture in at least a second mixing step or stage utilizing the same mixer (i.e., the first mixer) and / or a second mixer (one or more) different from the first mixer. In a multi-stage mixing process, there is an option to introduce the resin into either or both of the first and second mixers.

[0094] Following the first mixing, any further mixing steps(s) performed with respect to multi-stage mixing may utilize any or more of the mixing procedures, parameters, or steps used in the first mixing step as described in this disclosure. Therefore, when performing further mixing steps or stages, the same or different mixer design and / or the same or different operating parameters as those used in the first mixing step may be used in the further mixing steps. The mixers and their options described above with respect to the first mixing step, and / or the operating parameters described above with respect to the mixing steps, may be optionally used in further or second mixing steps (for example, among other parameters disclosed in this disclosure or PCT publication number WO2020 / 247663 (the disclosure of which is incorporated into this disclosure by reference), including a tip velocity of at least 0.5 m / s for at least 50% of the time, or at least 0.6 m / s for at least 50% of the time, and / or a Tz of 65°C or higher, as described in this disclosure).

[0095] In a multi-stage process, a second mixing stage (second-stage mixing) may also include adding other components to the mixer in addition to the mixture discharged from the first mixing stage. For example, if the resin is not added to the first mixer, the resin may be added to the second mixer, for example, as a separate addition or as a mixture (particulate mixture or co-pellet), together with fillers (wet or dry fillers, the same or different fillers as those added to the first mixer). In addition or instead, for example, the method may include adding additional fillers, such as dry fillers, wet fillers, or blends thereof, before or during the second mixing stage. The additional fillers may be the same as or different from the fillers already present in the mixture. For example, the mixture discharged from the first mixer can be considered a masterbatch, all or part of which is combined with the additional fillers. For example, wet or dry carbon black, silica, silicon-treated carbon black (and blends thereof) may be added to a mixture discharged from the first mixing stage, such as a mixture containing carbon black and natural rubber.

[0096] For a multi-stage mixing process (one or more), at least one option is used in a further mixing step (one or more). If this option is used, the second mixer may have the same or different design as the first mixer and / or the same or one or more different operating parameters as the first mixer. Specific examples are provided below with respect to the options for the first and second mixers, without meaning to be limiting. For example, the first mixer may be a tangential mixer or an intermesh mixer, and the second mixer may be a tangential mixer, an intermesh mixer, an extruder, a kneader, or a roll mill. For example, the first mixer may be an internal mixer, and the second mixer may be a kneader, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous blender, or a roll mill. For example, the first mixer may be a first tangential mixer, and the second mixer may be a second (different) tangential mixer. For example, the first mixer operates with a ram, and the second mixer operates without a ram. For example, the second mixer is used and operates with a filling rate of the mixture in the range of 25% to 70%, 25% to 60%, 25% to 50%, 30% to 50% on a dry mass basis, or other filling rates described herein.

[0097] As an option, the method includes mixing or further mixing the mixture in at least a second mixing step or stage using the same mixer as the first mixer (i.e., the first mixer) and / or a second mixer (one or more) different from the first mixer. Mixing by the second mixer may be such that the second mixer or the second mixer operates under at least one of the following conditions: (i) a ram pressure of 5 psi or less, and / or (ii) raising the ram to at least 75% of the ram's highest level (e.g., at least 85%, at least 90%, at least 95%, or at least 99%, or 100% of the ram's highest level), and / or (iii) operating the ram in floating mode, and / or (iv) positioning the ram so that it does not substantially come into contact with the mixture; and / or (v) a ramless mixer; and / or (vi) a filling density of the mixture in the range of 25% to 70%. As an option, the second mixer can operate with a filling rate of the mixture in the range of 25%-70%, 25%-60%, 25%-50%, or 30%-50% on a dry mass basis. As an option, mixing by the second mixer can be carried out under at least one of the following conditions (i)-(vi) for 0%-100% of the mixing time, e.g., 10%-100%, 20%-100%, 30%-100%, 40%-100%, or the second mixer operates under at least one of the following conditions (i)-(vi) for at least 50% of the mixing time, e.g., 50%-100%, 60%-100%, 70%-100%, 80%-100%, or 90%-100% of the mixing time.

[0098] The method then includes discharging the composite from the last used mixer, which is formed to have a liquid content of 10% by mass or less, based on the total mass of the composite. A method for operating a suitable second mixer is described in PCT Publication No. WO2020 / 247663 (the disclosure of which is incorporated herein by reference).

[0099] Composites prepared by any method disclosed herein may consist of natural rubber and fillers, i.e., no rubber chemicals are present. Alternatively, in addition to the fillers and natural rubber, the composite may contain at least one additive selected from degradation inhibitors and coupling agents. Alternatively, the composite may contain one or more rubber chemicals. In another alternative, the composite may be a curing agent-containing composition.

[0100] Additives may also be incorporated in the mixing and / or compounding process (e.g., single-stage mixing, or the second or third stage of multi-stage mixing); typical additives include degradation inhibitors, coupling agents, and one or more rubber chemicals that enable the dispersion of fillers into the elastomer. Examples of rubber chemicals, as provided in this disclosure, include one or more: processing aids (to facilitate mixing and processing of rubber, e.g., various oils and plasticizers, waxes), activators (to activate the vulcanization process, e.g., zinc oxide and fatty acids), accelerators (to accelerate the vulcanization process, e.g., sulfenamides and thiazoles), vulcanizing agents (or curing agents that crosslink the rubber, e.g., sulfur, peroxides), and other rubber additives, for example, retarders, co-agents, peptides, etc., but not limited to those listed below. The rubber chemicals include tackifiers (e.g., the use of cobalt salts to facilitate adhesion of steel cords to rubber-based elastomers, as described in U.S. Patent No. 5,221,559 and U.S. Patent Publication No. 2020 / 0361242, whose disclosures are incorporated herein by reference), resins (e.g., tackifiers, traction resins), flame retardants, colorants, foaming agents, additives to reduce heat buildup (HBU), and binders, as described in U.S. Provisional Application No. 63 / 123,386, whose disclosures are incorporated herein by reference). Optionally, the rubber chemicals may include processing aids and activators. Alternatively, one or more other rubber chemicals may be selected from zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, and process oils.

[0101] Any method for manufacturing the composites disclosed herein may further include one or more of the following steps after the formation of the composite: - One or more holding steps; - The composite can be further dried using one or more drying steps to obtain a dried composite; - One or more extrusion steps; - One or more calendering processes; - One or more grinding steps to obtain a ground composite; - One or more granulation steps; - One or more cutting steps; - One or more baling steps to obtain a baled product or mixture; - The bale of a mixture or product can be broken apart to form a particulate mixture; and / or - One or more mixing or blending steps; and / or - One or more sheeting processes.

[0102] As a further example, after the composite is formed, the following steps can be performed in this order, and each step can be repeated any number of times (with the same or different settings): - One or more holding processes to develop further elasticity - One or more cooling steps - Further drying the composite to obtain an even drier composite; - Mixing or compounding composites to obtain a blended mixture; - Grinding a compound to obtain a ground mixture (e.g., in a roll mill); - Granulating a ground mixture; - After granulation, optionally baling the mixture to obtain a baled mixture; - The selective breaking up and mixing of a bale of a mixture.

[0103] In addition, or instead, the composite may be compounded with one or more degradation inhibitors, zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, process oils, and / or curing agents, and then vulcanized to form a vulcanized product. Such a vulcanized compound may have one or more improved properties, such as improved hysteresis, for example, wear resistance and / or rolling resistance in tires, or improved mechanical strength and / or tensile strength, or improved tandelta and / or improved tensile stress ratio, but are not limited to the following.

[0104] For example, in the compounding process, components other than sulfur or other crosslinking agents and accelerators are combined with the net composite in a mixing apparatus (non-curing agents and / or degradation inhibitors are often pre-mixed and collectively referred to as "smalls"). The most common mixing apparatus is an internal mixer, e.g., a Banbury or Bravender mixer, but other mixers such as a continuous mixer (e.g., an extruder) may also be used. Subsequently, in the latter or a second compounding process, crosslinking agents, e.g., sulfur and accelerators (if necessary) (collectively referred to as curing agents) are added. Alternatively, compounding may involve combining the composite with one or more of the following in a single compounding stage or process: degradation inhibitors, zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, process oils, and curing agents, for example, the curing agent may be added together with the smalls in the same compounding stage. The compounding process is often carried out in the same type of apparatus as the mixing process, but may be carried out in a different type of mixer or extruder or roll mill. Those skilled in the art will recognize that once the curing agent is added, vulcanization begins when the appropriate activation conditions for the crosslinking agent are achieved. Therefore, when sulfur is used, the temperature during mixing is preferably maintained substantially below the curing temperature.

[0105] Furthermore, disclosed herein are methods for producing vulcanized products. The methods may include a step of curing at least one composite in the presence of at least one curing agent. As is known in the art, curing can be achieved by applying heat, pressure, or both.

[0106] With respect to this vulcanized material, the vulcanized material may have one or more elastic properties. For example, a silica-containing vulcanized material may have a tensile stress ratio M300 / M100 of at least 4.3, at least 4.5, at least 5.0, or in the range of 4.3 to 5.5. A carbon black-containing vulcanized material may have a tensile stress ratio M300 / M100 of at least 5.9 as evaluated by ASTM D412, for example, at least 6.0, at least 6.1, or at least 6.2, where M100 and M300 refer to the tensile stress at 100% and 300% elongation, respectively.

[0107] Alternatively, or in addition, the vulcanized product may have a maximum tanδ (at 60°C) of 0.22 or less, for example, 0.21 or less, 0.2 or less, 0.19 or less, 0.18 or less, for example, 0.16 or less, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, or 0.11 or less.

[0108] This composite (whether single-stage or multi-stage, T zA vulcanized product prepared from a composite (produced by any process disclosed herein, which involves mixing a wet filler, a solid elastomer, and a resin under the disclosed mixing conditions of tip velocity) may exhibit improved properties. For example, a vulcanized product prepared from this composite may have improved properties compared to a vulcanized product prepared from a composite produced by dry mixing a solid elastomer, a non-wet filler, and a resin ("dry-mixed composite"), particularly a dry-mixed composite having the same composition ("dry-mixed equivalent"). Therefore, comparisons between dry mixing and this mixing process are made between equivalent fillers, elastomers, filler loads (e.g., ±5% by mass, ±2% by mass), and compound formulations (including resin), and optionally, curing additives. Under these conditions, the vulcanized product has a tanδ value lower than that of a vulcanized product prepared from a dry-mixed composite having the same composition. In addition, or alternatively, the vulcanized material has a tensile stress ratio M300 / M100 greater than that of a vulcanized material prepared from a dry mixed composite having the same composition, where M100 and M300 refer to the tensile stress at 100% and 300% elongation, respectively.

[0109] Furthermore, disclosed herein are articles manufactured from or containing composites or vulcanized products disclosed herein.

[0110] Composites can be used to manufacture products containing elastomers or rubber. Alternatively, elastomer composites can be used or manufactured to form vulcanized products that can be incorporated into various parts of a tire, such as the tire tread (including the cap and base, such as road or off-road tire treads), undertread, inner liner, tire sidewall, tire carcass, tire sidewall insert, tire wire skim, and cushioning gum for retreaded tires, in pneumatic and non-pneumatic or solid tires. Alternatively, or in addition, elastomer composites (and subsequent vulcanized products) can be used in hoses, seals, gaskets, weatherstrips, windshield wipers, automotive parts, liners, pads, housings, wheels and track elements, tire sidewall inserts in pneumatic and non-pneumatic or solid tires, tire wire skim, and cushioning gum for retreaded tires. Alternatively, or in addition, elastomer composites (and subsequent vulcanization products) are used in hoses, seals, gaskets, vibration damping products, track pads for truck-propeller equipment such as trucks and bulldozers, engine mounts, seismic stabilization devices, mining equipment such as sieves, mining equipment linings, conveyor belts, chute liners, slurry pump liners, slurry pump components such as impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, slurry mixing impellers and slurry pump impellers. It can be used in a variety of applications, including impellers, grinding mill liners, cyclones and liquid cyclones, expansion joints, marine equipment such as linings for pumps (e.g., dredging pumps and outboard motor pumps), hoses (e.g., dredging hoses and outboard motor hoses), and other marine equipment, shaft seals for marine, oil, aerospace, and other applications, propeller shafts, linings for piping for transporting oil sands and / or tar sands, and other applications where wear resistance and / or enhanced dynamic properties are desired.Furthermore, elastomer composites, especially vulcanized elastomer composites, can be used for rollers, cams, shafts, pipes, bearing tubes for vehicles, or other applications where wear resistance and / or enhanced dynamic properties are desired.

[0111] Accordingly, articles include vehicle tire treads including caps and bases, sidewalls, undertreads, inner liners, wire skim components, tire carcasses, engine mounts, bearing cylinders, conveyor belts, vibration damping devices, weatherstrips, windshield wipers, automotive parts, seals, gaskets, hoses, liners, pads, housings, and wheels or track elements. For example, an article may be a multi-component tread, as disclosed in U.S. Patents 9,713,541, 9,713,542, 9,718,313 and 10,308,073 (their disclosures are incorporated herein by reference).

[0112] For example, a rubber compound (vulcanized product) derived from the composites disclosed herein (composites prepared by the methods disclosed herein) can be used for truck treads or passenger car and light truck (PC / LT) treads, such as electric vehicle (EV) treads. For example, the elastomer in the rubber compound (or composite) may be SBR (e.g., SSBR, functionalized SBR, etc.) or a blend of SBR and BR, and the filler may be silica or a silica / carbon black blend. For example, the filler may be mainly silica, for example, at least 50% silica by mass, at least 75% silica, at least 90% silica, and at least 95% silica by mass, relative to the total mass (dry basis) of the filler, with the remainder being carbon black. As another example, the elastomer may be natural rubber, and the filler may be silica or a silica / carbon black blend disclosed herein. As disclosed herein, the silica may have a filler content of at least 20 phr, or a higher filler content, for example, at least 50 phr as disclosed herein (e.g., at least 60 phr, at least 70 phr, etc.). Epoxy-refined natural rubber and polyisoprene can be used in combination with silica and resin in a wet mixing process to prepare rubber compositions for passenger car and light truck tire tread applications. Resins can be selected to improve wet traction and optionally steering ability. For example, if the rubber compound contains natural rubber and silica (and optionally a small amount of carbon black), the resin may be a C5 resin. As another example, if the rubber compound contains SBR (e.g., functionalized SBR) and silica (and optionally a small amount of carbon black), the resin may be a C9 resin. As yet another example, if the rubber compound contains an SBR / BR blend and silica (and optionally a small amount of carbon black), the resin may be a C5 / C9 resin. [Examples]

[0113] example The example illustrates the preparation of elastomer composites and corresponding vulcanized products from various elastomers and fillers.

[0114] All mixing and blending was performed using a BR-1600 Banbury® mixer ("BR1600"; manufacturer: Farrel), which operates with a 2-blade, tangential rotor (2WL) and provides a 1.6L capacity.

[0115] The water content in the discharged composite was measured using a moisture balance (model: HE53, manufacturer: Mettler Toledo NA, Ohio). The composite was sliced ​​into small pieces (size: length, width, height < 5 mm), and 2-2.5 g of the material was placed on a disposable aluminum disc / plate and placed in the moisture balance. The weight loss was recorded at 125°C for 30 minutes. After 30 minutes, the water content of the composite was recorded as follows:

number

[0116] A small amount of organic volatile matter (<0.1% by mass) may be included in this moisture test value.

[0117] The following tests were used to obtain performance data for each vulcanized product: - The tensile stress at 100% elongation (M100) and 300% elongation (M300) were evaluated using ASTM D412 (Test Method A, Die C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. Tensile strain was measured using an extensometer. The M300 / M100 ratio is called the tensile stress ratio (or modulus ratio). - Maximum tanδ was measured using an ARES-G2 rheometer (manufacturer: TA Instruments) in torsional mode with an 8 mm diameter parallel plate shape. The vulcanized specimen had a diameter of 8 mm and a thickness of approximately 2 mm. The rheometer was operated at a constant temperature of 60°C and a constant frequency of 10 Hz. Strain sweeps were performed with strain amplitudes from 0.1 to 68%. Measurements were obtained at 10 points every 10, and the maximum measured tanδ ("maximum tanδ") was reported, referred to as "tanδ" unless otherwise specified. Maximum G''Tg was measured using the same apparatus in torsional mode with an 8 mm diameter parallel plate shape. The vulcanized specimen had a diameter of 8 mm and a thickness of approximately 2 mm. The rheometer was operated at a constant frequency of 10 Hz. Temperature sweeps were performed from 80 to -110°C. The temperature at the maximum value of G'' was reported as maximum G''Tg. - The tear strength of Die B was measured according to ASTM D624, using a notched specimen and pulled at 500 mm / min from a tensile testing machine at 23°C. The maximum force required to tear the specimen is used to calculate the tear strength. - Volume resistivity (ohms-cm) measurements were performed on 2mm thick rubber sheets cut from a sheet using a 2-inch x 5-inch resistive die. Conductive silver paint 187 (Electron Microscopy Sciences) was applied to both sides of the sheets at both ends (approximately 5 inches apart) and allowed to dry overnight. A resistive clamp was attached to the painted end, and the voltage was measured using a Wavetek® meter. For resistance readings exceeding 2000M ohms, measurements were performed using a Dr. Kamphausen Milli-TO 2 meter.

[0118] Example 1 This example illustrates the preparation of composites and corresponding vulcanized products containing elastomers, silica, and resins. The composites were prepared by dry and wet mixing methods, in which a solid elastomer was mixed with a wet filler. Each mixing method was performed with and without the resin.

[0119] The elastomers used were functionalized solution SBR (HPR950, JSR), butadiene rubber ("BR"; BUNA® CB 24 butadiene rubber, Lanxess, Germany), and natural rubber (RSS3 "NR"; Hokson Rubber, Malaysia). The silica used was ZEOSIL® Z1165 MP precipitated silica from Solvay USA Inc. (Cranberry, New Jersey). The coupling agent was Si-69 silane coupling agent ("Si69"; Evonik Instruments). The silane coupling agent was added together with the first part of the silica. Dry silica with a water content of 7.5% by mass was fed into a continuous FEECO pin mixer at a rate of 460 lbs / hour. Water was sprayed using two fan nozzles in the pin mixer located immediately after the dry silica entered the pin mixer. The water spray rate was 486 lbs / hour. Uniform wet silica pellets between 60 and 120 mesh were discharged containing 53% by mass water. The properties of the elastomer are shown in Table 1. [Table 1]

[0120] The resin used is Impera TM R1607 resin ("R1607"), Impera TM D1606 resin (“D1606”), Impera TM G1750 resin ("G1750") and Permalyn TM The resin used was 5095 resin ("5095") (all manufactured by Eastman Chemical Co.). The properties of the resin are shown in Table 2 below. [Table 2]

[0121] f-SSBR / BR blends in a 70 / 30 ratio with or without resin, and with silica filler content of (50-70 phr), were included as reference for PC or light track treads. For comparison with rubber compositions derived from a wet mixing process, natural rubber / silica compositions with varying silica (50-70 phr, all dry basis) and resin (0.13 and 25 phr) filler content were prepared via conventional dry mixing at equal compound Shore A hardness. A silane coupling agent filler content of 10% by mass of the silica filler content was used for all compounds. Furthermore, a 4 phr filler content of carbon black (CB) (ASTM grade N134, supplied as VULCAN® 10H carbon black) was present in each rubber compound.

[0122] SBR / BR and NR dry mixes (reference) and a comparative compound were prepared according to a three-stage mixing protocol. The first-stage mixing protocols for the reference and comparative compounds, as well as the example compounds, are shown in Tables 3 and 4, respectively. A TCU temperature of 80°C, a rotor speed of 70 rpm, and a fill density of 70% were applied in the first-stage dry mixing, while a TCU temperature of 90°C, a rotor speed of 100 rpm, and a fill density of 70% were applied in the first-stage wet mixing. For the dry mixing process, as shown in Table 3, ZnO (3 phr), stearic acid (2 phr), 6PPD (1.5 phr), TMQ (1.5 phr), and wax (1.5 phr) were added during the first-stage mixing along with the coupling agent and resin (if any). The time interval refers to the period from the start of mixing, defined as "0 s". After the first-stage mixing, the water content of the composite was less than 2.0 mass%. [Table 3] [Table 4]

[0123] As shown in Table 5, both dry-mixed and wet-mixed rubber compounds (Tables 5 and 6, respectively) were prepared using the same second and third-stage protocols as the wet-mixed composite, except that ZnO (3 phr), stearic acid (2 phr), 6PPD (1.5 phr), TMQ (1.5 phr), and wax (1.5 phr) were added during the second-stage mixing. The conditions for the second stage were as follows: TCU temperature = 50°C; rotor speed = 80 rpm; ramp pressure = 2.8 bar; fill density = 68%. The conditions for the third stage were as follows: TCU temperature = 50°C; rotor speed = 60 rpm; ramp pressure = 2.8 bar; fill density = 65%. In the final stage of mixing, curing agents (sulfur and TBBS) were added. The TBBS content was adjusted based on the silica fill content in the compound formulation (see Tables 7-10 for actual addition amounts). [Table 5] [Table 6]

[0124] After the final stage, the composite was sheeted in a 2-roll mill operating at approximately 22 rpm at 50°C, and then passed through a nip gap of approximately 5 mm six times. The final compound was sheeted to a thickness of 2.4 mm in a 2-roll mill operating at 50°C. The final compound was cured by heat pressing (2500 lbs) at 150°C for 30 minutes.

[0125] Tables 7-10 show the properties of cured rubber compounds containing C5, C5 / C9, C9, and rosin resin, respectively, along with comparative samples prepared by dry mixing with and without resin, and by wet mixing without resin. "OL" indicates that the load cell limit was exceeded, meaning the compound was too rigid. [Table 7] [Table 8] [Table 9] [Table 10]

[0126] Table 7 shows that the wet mixing process resulted in an NR / silica / C5 resin composition with increased M300 / M100 values ​​and reduced hysteresis loss tanδ at 60°C compared to the NR / silica / resin dry mixed composition. The dry-mixed NR / silica compound showed a higher hysteresis loss tandelta at 60°C compared to the fSSBR / BR compound. The wet-mixed NR / silica compound showed a hysteresis loss tandelta at 60°C that matched that of the fSSBR / BR compound. The introduction of resin into the NR / silica composition resulted in an increase in Tg (temperature of maximum G'' by temperature sweep), which indicates an improvement in the wet traction performance of the tire. The NR / silica composition with or without resin also showed a much increased die B tear strength compared to the fSSBR / BR / silica composition with or without resin, which indicates better tire performance under more demanding usage conditions such as high load and high stress.

[0127] Table 8 shows that the wet mixing process resulted in an NR / silica / C5 / C9 resin composition with increased M300 / M100 values ​​and reduced hysteresis loss tanδ at 60°C compared to a dry-mixed NR / silica / resin composition. Increasing the silica / resin filler amount increased the M300 / M100 ratio at 60°C. The wet-mixed NR / silica compound showed a hysteresis loss tandelta at 60°C that matched that of the f-SSBR / BR compound. The introduction of resin into the NR / silica composition resulted in an increase in Tg (temperature of maximum G'' by temperature sweep), which indicates an improvement in the wet traction performance of the tire. The NR / silica composition with or without resin also showed significantly increased die B tear strength compared to the fSSBR / BR / silica composition with or without resin, which indicates better tire performance under more demanding usage conditions such as high load and high stress.

[0128] Table 9 shows that the wet mixing process resulted in an NR / silica / C9 resin composition with increased M300 / M100 values ​​and reduced hysteresis loss tanδ at 60°C compared to a dry-mixed NR / silica / resin composition. Increasing the silica / resin filler amount increased the M300 / M100 ratio at 60°C. The wet-mixed NR / silica compound showed a hysteresis loss tandelta at 60°C that matched that of the fSSBR / BR compound. The introduction of resin into the NR / silica composition resulted in an increase in Tg (temperature of maximum G'' by temperature sweep), which indicates an improvement in the wet traction performance of the tire. The NR / silica composition with or without resin also showed significantly increased die B tear strength compared to the fSSBR / BR / silica composition with or without resin, which indicates better tire performance under more demanding usage conditions such as high load and high stress.

[0129] Table 10 shows that the wet mixing process resulted in an NR / silica / rosin resin composition with increased M300 / M100 values ​​and reduced hysteresis loss tan delta at 60°C compared to a dry-mixed NR / silica / resin composition. The wet-mixed NR / silica compound showed a hysteresis loss tan delta at 60°C that matched that of the fSSBR / BR compound. The introduction of resin into the NR / silica composition resulted in an increase in Tg (temperature of maximum G'' by temperature sweep), which indicates an improvement in the wet traction performance of the tire. The NR / silica composition with or without resin also showed significantly increased die B tear strength compared to the fSSBR / BR / silica composition with or without resin, which indicates better tire performance under more demanding usage conditions such as high load and high stress.

[0130] These results demonstrate that a wet mixing process can yield a resin-containing natural rubber / silica composition with properties comparable to silica compositions containing functionalized SSBR. The wet-mixed NR / silica / resin composition exhibits improved mechanical performance and significantly enhanced hysteresis properties, making it a promising candidate material for tire tread compounds, particularly suitable for electric vehicles (PC or light trucks), as it is expected to improve tread wear and reduce rolling resistance. Due to its low resin content of approximately 10-15 phr, the rubber composition can also be used in track treads with improved wet traction.

[0131] Example 2 This example illustrates the preparation of composites and corresponding vulcanized products containing natural rubber, carbon black, and resin. The composites were prepared by dry and wet mixing methods, in which a solid elastomer was mixed with a wet filler. Each mixing method was performed with and without resin.

[0132] The carbon black used was Propel® X25 carbon black ("X25"; Cabot Corporation). The elastomer used was SMR20 natural rubber (Hokson Rubber, Malaysia). Technical details of these natural rubbers are widely available, for example, in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA). Wet carbon black was prepared by grinding dry carbon black pellets using an 8” model microjet mill to produce fuzzy carbon black particles with a particle diameter of less than 10 μm for 99.0%. This fuzzy carbon black was then wet-pelletized in a pin pelletizer. The resulting wet carbon black (re-wet carbon black) had a moisture content of 57%. The resin used was Oppera® PR373 modifier resin (C5 / C9 resin, Tg=44°C, ring-spherical softening point 89°C) from ExxonMobil.

[0133] Dry-mixed (reference) and wet-mixed compounds were prepared according to a three-stage mixing protocol. The first-stage mixing protocols for the dry-mixed and wet-mixed compounds are shown in Tables 11 and 12, respectively. A TCU temperature of 50°C, a rotor speed of 80 rpm, and a fill density of 70% were applied to the first-stage dry mixing, while a TCU temperature of 85°C, a rotor speed of 105 rpm, and a fill density of 70% were applied to the first-stage wet mixing. For the dry mixing process, the resin was added to the elastomer during the first-stage mixing, as shown in Table 11. The time interval refers to the period from the start of mixing, defined as "0 s". [Table 11] [Table 12]

[0134] The second and third-stage protocols shown in Tables 5 and 6 were performed for both dry-mixed and wet-mixed rubber compounds. As shown in Table 5, for the wet-mixed composite, ZnO (3 phr), stearic acid (2 phr), 6PPD (0.5 phr), TMQ (1.5 phr), and wax (1.5 phr) were added during the second-stage mixing. For the final-stage mixing, the curing agent (1.2 phr of sulfur and 1.4 phr of TBBS) was added according to Table 6. Table 13 shows the properties of the cured rubber compound. [Table 13]

[0135] From the data in Table 13, it can be further understood that the wet-mixed rubber compound provided reduced hysteresis, reflected by increased M300 / M100 values ​​and lower tanδ values, compared to the dry-mixed equivalent. It can also be further understood that the wet-mixed rubber compound showed increased electrical resistivity compared to the dry-mixed equivalent. Example 29, a dry-mixed compound without resin, has the lowest electrical resistivity value (log resistivity -= 2.5). Adding 10 phr of resin increases the resistivity of the dry-mixed sample (Example 31). The wet-mixed examples give increased electrical resistivity, particularly for the resin-added sample (see Examples 35 and 36). This increase in resistivity may indicate improved fine dispersion of the filler due to the wet-mixing process.

[0136] The use of the terms “a,” “an,” and “the” should be interpreted as covering both singular and plural forms unless otherwise suggested in this disclosure or expressly refuted by the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., “including, but not limited to”) unless otherwise indicated in this disclosure. The description of value ranges in this disclosure is intended only as a way of omitting individual references to each distinct value included within the range, unless otherwise suggested in this disclosure, and each distinct value is incorporated herein as if it were individually enumerated in this disclosure. All methods described in this disclosure may be performed in any appropriate order unless otherwise suggested in this disclosure or expressly refuted by the context. Any and all examples or illustrative words provided in this disclosure (e.g., “such as”) are intended solely to clarify the invention and, unless otherwise stated in the claims, do not imply any limitation on the scope of the invention. No language in this specification should be construed as indicating any element not described in the claims that is essential to the practice of the invention. This disclosure also includes the following: <1> (a) Put into the mixer at least a solid elastomer; filler and a wet filler containing a liquid present in an amount of at least 15% by mass based on the total mass of the wet filler; and a resin; (b) in one or more mixing steps, mixing at least the solid elastomer, the wet filler, and the resin to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; and (c) Discharge from the mixer a composite containing a filler dispersed in an elastomer at a filling amount of at least 20 phr, wherein the composite has a liquid content of 10% by mass or less based on the total mass of the composite. A method for preparing a composite containing [a specific substance]. <2> The resin is at least 25°C T g The method according to embodiment 1 above, having the following characteristics. <3> The resin is in the range of 25°C to 110°C. g The method according to embodiment 1 above, having the following characteristics. <4> The method according to any one of embodiments 1 to 3, wherein the resin has a softening point of at least 50°C as determined in accordance with ASTM E-28. <5> The method according to any one of embodiments 1 to 3, wherein the resin has a softening point in the range of 50°C to 150°C, as determined according to ASTM E-28. <6> The method according to any one of embodiments 1 to 5 above, wherein the resin is selected from one or more of the following: C5 resin, C5 / C9 resin, C9 resin, rosin resin, terpene resin, aromatically modified terpene resin, dicyclopentadiene resin, alkylphenol resin, and combinations thereof. <7> The method according to any one of embodiments 1 to 6, wherein the input includes inputting the resin and the wet filler separately into the mixer. <8> The method according to any one of embodiments 1 to 7, wherein the addition includes multiple additions of the solid elastomer, the wet filler, and / or the resin. <9> The method according to any one of embodiments 1 to 8, wherein the mixing is carried out in a single mixing step. <10> The method according to any one of embodiments 1 to 8, wherein the mixing is carried out in two or more mixing steps. <11> The method according to embodiment 10, wherein the mixing in (b) is a second mixing step, and the first mixing step includes mixing at least a portion of the solid elastomer with at least a portion of the wet filler, and then introducing the resin into the mixer. <12> The method according to any one of embodiments 1 to 11, wherein the addition in (a) includes adding a mixture containing the resin and the wet filler to the mixer. <13> The method according to any one of embodiments 1 to 11, wherein the input in (a) includes inputting a copellet containing the resin and the wet filler into the mixer. <14> The method according to any one of embodiments 1 to 13, wherein in at least one of the mixing steps, the method includes carrying out the mixing, wherein the mixer has at least one temperature control means set to a temperature Tz of 65°C or higher. <15> The method according to any one of embodiments 1 to 14, wherein in at least one of the mixing steps, the method includes carrying out the mixing by one or more rotors of the mixer operating at a tip speed of at least 0.6 m / s for at least 50% of the mixing time. <16> The method according to any one of embodiments 1 to 15, wherein the wetting filler is selected from carbonaceous materials, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolysis carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, as well as coated materials thereof and at least one material selected from these treated materials. <17> The method according to any one of embodiments 1 to 16, wherein the wetting filler contains silica. <18> The method according to any one of embodiments 1 to 17, wherein the wet filler contains silica in an amount of at least 50% by mass relative to the total mass of the filler, and the wet filler further contains carbon black and / or silicon-treated carbon black. <19> The method according to any one of embodiments 1 to 18, wherein the wetting filler has a liquid present in an amount ranging from 20% to 80% by mass, based on the total mass of the wetting filler. <20> The method according to any one of embodiments 1 to 19, wherein the wet filler is in the form of a powder, paste, pellets, or cake. <21> The method according to any one of embodiments 1 to 20, wherein the input includes introducing a dry filler into the mixer, and the dry filler is moistened by adding a liquid to form a moist filler in the mixer. <22> The method according to any one of embodiments 1 to 21, wherein the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomer, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, silicone elastomer, and blends thereof. <23> The method according to any one of embodiments 1 to 21, wherein the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, and blends thereof. <24> The method according to any one of embodiments 1 to 23, wherein the one or more mixing steps are a continuous process. <25> The method according to any one of embodiments 1 to 23, wherein the one or more mixing steps are batch processes. <26> (a) Putting into the first mixer at least a solid elastomer; and a wet filler comprising a filler and a liquid present in an amount of at least 20% by mass based on the total mass of the wet filler; (b) in one or more mixing steps, mixing at least the solid elastomer and the wet filler to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; (c) Discharge from the first mixer a mixture containing a filler dispersed in an elastomer at a filling amount of at least 20 phr, having a liquid content reduced to a smaller amount than the liquid content at the start of step (b), and having a material temperature in the range of 100°C to 180°C; (d) Mix the mixture from (c) in a second mixer to obtain a composite; and (e) Discharge from the second mixer a composite having a liquid content of less than 3% by mass based on the total mass of the composite. A method for preparing a composite including, A method in which the resin is introduced into the first mixer, the second mixer, or both the first mixer and the second mixer. <27> The method according to embodiment 26, wherein the resin is introduced into the first mixer, and step (b) includes mixing at least the solid elastomer, the wet filler, and the resin to form the mixture. <28> The method according to embodiment 26 or 27, wherein the resin is introduced into the second mixer, and step (d) is to mix the mixture from (c) and the resin in the second mixer to obtain the composite. <29> The method according to any one of embodiments 26 to 28, wherein the first mixer and the second mixer are the same. <30> The method according to any one of embodiments 26 to 28, wherein the first mixer and the second mixer are different. <31> The method according to any one of embodiments 26 to 30, wherein the second mixer operates under at least one of the following conditions. (i) Ram pressure of 5 psi or less; (ii) Increase the ram to at least 75% of its maximum level; (iii) The RAM operates in floating mode; (iv) The ram is positioned so as not to come into contact with the mixture; (v) The mixer is without a ram; and (vi) The filling density of the mixture is in the range of 25% to 70%. <32> The method according to embodiment 31, wherein the second mixer operates under at least one of conditions (i) to (vi) for at least 50% of the mixing time. <33> A method for preparing a vulcanized product, comprising curing a composite prepared by any of the methods described in embodiments 1 to 32 above in the presence of at least one curing agent to form a vulcanized product. <34> An article comprising a vulcanized product prepared by the method described in embodiment 33 above.

Claims

1. (a) Put into the mixer at least a solid elastomer; a wet filler containing a liquid present in an amount of at least 15% by mass based on the total mass of the wet filler; and a resin, and optionally a degradation inhibitor and a coupling agent. Here, no rubber chemicals are added to the mixer, and the resin is selected from one or more of the following: C5 resin, C5 / C9 resin, C9 resin, rosin resin, terpene resin, aromatically modified terpene resin, dicyclopentadiene resin, alkylphenol resin, and combinations thereof; (b) in one or more mixing steps, mixing at least the solid elastomer, the wetting filler, and the resin, and optionally a degradation inhibitor and a coupling agent to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation; and (c) Discharge from the mixer a composite containing a filler dispersed in an elastomer at a filling amount of at least 20 phr, wherein the composite has a liquid content of 10% by mass or less based on the total mass of the composite. A method for preparing a composite, comprising a rubber chemical selected from processing aids and activators.

2. The resin is at least 25°C T ｇ The method according to claim 1, comprising:

3. The method according to claim 1, wherein the resin has a softening point of at least 50°C, as determined according to ASTM E-28.

4. The method according to any one of claims 1 to 3, wherein the mixing is carried out in a single mixing step.

5. The method according to any one of claims 1 to 3, wherein the mixing is carried out in two or more mixing steps.

6. The method according to any one of claims 1 to 3, wherein in at least one of the mixing steps, the method includes carrying out the mixing, wherein the mixer has at least one temperature control means set to a temperature Tz of 65°C or higher.

7. The method according to any one of claims 1 to 3, wherein in at least one of the mixing steps, the method includes carrying out the mixing by one or more rotors of the mixer operating at a tip speed of at least 0.6 m / s for at least 50% of the mixing time.

8. The method according to any one of claims 1 to 3, wherein the wetting filler is selected from carbonaceous materials, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolysis carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, as well as at least one material selected from these, and treated materials.

9. The method according to any one of claims 1 to 3, wherein the wetting filler comprises silica.

10. The method according to any one of claims 1 to 3, wherein the wetting filler has a liquid present in an amount ranging from 20% by mass to 80% by mass, based on the total mass of the wetting filler.

11. The method according to any one of claims 1 to 3, wherein the wet filler is in the form of a powder, paste, pellets, or cake.

12. The method according to any one of claims 1 to 3, wherein the input includes introducing a dry filler into the mixer, and the dry filler is moistened by adding a liquid to form a moist filler in the mixer.

13. The method according to any one of claims 1 to 3, wherein the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomer, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, silicone elastomer, and blends thereof.

14. The method according to claim 5, wherein the two or more mixing steps are carried out by a first mixer and a second mixer, and the second mixer operates under at least one of the following conditions. (i) Ram pressure of 5 psi or less; (ii) Raise Ram to at least 75% of its maximum level; (iii) RAM operates in floating mode; (iv) The ram is positioned so as not to come into contact with the mixture; (v) The mixer is without a ram; and (vi) The packing density of the mixture is in the range of 25% to 70%.

15. The method according to claim 14, wherein the second mixer operates under at least one of conditions (i) to (vi) for at least 50% of the mixing time.

16. A method for preparing a vulcanized product, comprising curing a composite prepared by any one of claims 1 to 3 in the presence of at least one curing agent to form a vulcanized product.

17. A method for producing an article comprising a vulcanized product prepared by the method described in claim 16.

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