Stored elastomeric composites

Abstract

The present invention discloses elastomeric composites stored in a container or packaging. The composite is uncured and comprises at least one elastomer and at least one filler. The packaging or container includes at least one wall surrounding the composite, in which at least one wall comprises at least one oxygen barrier layer. Containers or packagings having this oxygen barrier wall have an oxygen transmission rate not exceeding 100 cm³ / (m²·day·atm) at 23°C and 0% relative humidity. It also discloses methods for storing elastomeric composites with the packaging or containers disclosed herein.

Description

Title of the invention: Stored elastomeric composites FIELD OF THE INVENTION

[0001] The present invention discloses elastomeric composites which are stored or packaged in a container or packaging having an oxygen barrier wall. CONTEXT

[0002] Many commercially relevant products are formed from elastomeric compositions in which a reinforcing filler is dispersed in any of various synthetic elastomers, natural rubber, or elastomer blends. Carbon black and silica, for example, are widely used to reinforce natural rubber and other elastomers. It is common to produce a masterbatch, namely a premix of reinforcing filler, elastomer, and various optional additives, such as a diluent oil. These masterbatches are then compounded with processing and curing additives and, upon curing, generate many commercially relevant products.Such products include, for example, pneumatic and non-pneumatic tires or solid tires for vehicles, including the tread portion (top and bottom), the depth under the tread, the inner lining, the sidewall, the metallic rubber layer, the casing, and other components. Other products include, for example, engine mounts, bushings, conveyor belts, windshield wipers, rubber components for aerospace and marine equipment, vehicle track components, seals, linings, trims, wheels, bumpers, anti-vibration systems, and the like.

[0003] Good dispersion of reinforcing filler in rubber compounds has been recognized as a factor in achieving consistent mechanical strength and performance of both the elastomeric composite and the rubber compound. Rubber compounds are prepared from elastomeric composites, which are an uncured mixture of filler(s) and elastomer(s), optionally with one or more additives. An elastomeric composite, also known as a masterbatch, can be compounded with additional additives and curing agents and then subjected to one or more vulcanization processes. As such, elastomeric composites may be more susceptible to degradation than (cured) rubber compounds, which poses a challenge when they are stored and / or shipped prior to vulcanization.Consequently, there is a need to prevent significant degradation of elastomeric composites during long-term storage. SUMMARY

[0004] An aspect is a packaged elastomeric composite, comprising: a sealed package containing the composite in an atmosphere having a partial pressure of oxygen less than 21 kPa (for example, less than 20 kPa, less than 15 kPa, less than 10 kPa, less than 7 kPa or less than 5 kPa), in which the composite is uncured and comprises at least one elastomer and at least one filler, in which: the package comprises at least one wall surrounding the composite in which at least one wall comprises at least one oxygen barrier layer such that the package has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23°C and 0% relative humidity (RH).

[0005] Another aspect is a method for storing an elastomeric composite, comprising: sealing the elastomeric composite in a container and storing the composite in the sealed container for a period of time of at least 5 days, wherein: the elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and the container comprises at least one wall surrounding the composite, in which at least one wall comprises at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23°C and 0% relative humidity.

[0006] Another aspect is a method for maintaining or improving at least one property of an elastomeric composite or a compound formed from the composite, comprising: the storage of the elastomeric composite in a sealed container for a period of time of at least 5 days, in which: The elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and the container includes at least one wall surrounding the composite in which at least one wall includes at least one oxygen barrier layer such that the packaging has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23°C and 0% relative humidity.

[0007] With respect to any aspect, process, or embodiment disclosed herein, if any, the packaged elastomeric composite or the processes disclosed herein (for example, processes for storing an elastomeric composite or processes for maintaining or improving at least one property of an elastomeric composite or a compound formed from the composite) may further include any or more of the following embodiments: the atmosphere in the package or container has a partial pressure of oxygen not exceeding 7 kPa or not exceeding 5 kPa; the atmosphere in the package or container comprises at least 90% of at least one gas that is non-reactive with the elastomeric composite; the at least one gas that is non-reactive with the elastomeric composite is chosen from nitrogen, argon, helium, xenon and carbon dioxide; the sealed package or container is under vacuum.

[0008] With respect to any aspect, process, or embodiment disclosed herein, as appropriate, the packaged elastomeric composite or the processes disclosed herein may further comprise any or more of the following embodiments; at least one oxygen barrier layer comprises a material selected from polyamide, polyethylene, polyethylene terephthalate, polyethylene naphthalate, aluminum, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, and mixtures thereof and metallized layers thereof; at least one oxygen barrier layer comprises a material selected from polyamide, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, metals, and mixtures thereof and metallized layers thereof; at least one oxygen barrier layer comprises a metallized layer or a metallic layer;at least one wall does not contain a metallized or metallic layer; at least one oxygen barrier layer comprises a material selected from metals, metallic alloys, carbon-based ceramic nanomaterials and melamine-based materials; at least one wall is a single-layer wall which is the oxygen barrier layer; at least one wall comprises two or more layers, at least one of the layers being the oxygen barrier layer; at least one wall is flexible; at least one wall is rigid; the interior of the packaging has a volume of at least 10 L or at least 50 L.

[0009] With respect to any aspect, process, or embodiment disclosed herein, as appropriate, the packaged elastomeric composite or the processes disclosed herein may further include any or more of the following embodiments: the composite includes a protective agent present in an amount of at least 0.5%, for example, an amount from 0.5% to 10% or an amount from 0.5% to 3%, or other ranges disclosed herein; the composite is substantially free of protective agents; the composite has a moisture content from 3% to 20% by weight relative to the total weight of the composite; the package further contains at least one deoxygenating agent; the at least one deoxygenating agent is contained in an oxygen-permeable sachet; the sachet is glued to an inner wall of the package;at least one deoxygenating agent is chosen from metallic powders, ascorbic acids and salts thereof, and catechol.

[0010] With respect to any aspect or process or embodiment disclosed herein, as appropriate, the packaged elastomeric composite or the processes disclosed herein may further comprise any or more of the following embodiments: at least one filler is selected from carbon materials, carbon black, silica, fillers of biological origin, clays, nanoclays, metal oxides, metal carbonates, pyrolytic carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, regenerated carbon or combinations thereof, and materials of these coated and chemically treated; at least one filler is selected from rice hull silica, lignin, nanocellulose and hydrothermal carbon; at least one filler is selected from carbon black, silica and silicon-treated carbon black.

[0011] With respect to any aspect, process, or embodiment disclosed herein, as appropriate, the packaged elastomeric composite or processes disclosed herein may further comprise any or more of the following embodiments: at least one 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 mixtures thereof; at least one elastomer is selected from diene-based elastomers;at least one elastomer is selected from natural rubber, polyisoprene rubber, butadiene rubber and mixtures thereof; the composite comprises at least one elastomer comprising at least 30% natural rubber and at least one filler comprising at least 50% carbon black; the composite further comprises curing agents.

[0012] With respect to any aspect or process or embodiment disclosed herein, if any, the packaged elastomeric composite or the processes disclosed herein may further include any or more of the following embodiments: the composite has a Payne ratio of at least 1.1, in which the Payne ratio is G'(0.3%) / G'(51.5%), in which G'(0.3%) is a dynamic storage modulus measured at a strain amplitude of 0.3% and G'(51.5%) is a dynamic storage modulus measured at a strain amplitude of 51.5%; the composite exhibits a macrodispersion d90 not exceeding 80 pm, in which d90 is the equivalent surface diameter (pm) of particles of the filler in the composite.

[0013] With respect to any aspect or process or embodiment disclosed herein, if any, the packaged elastomeric composite or the processes disclosed herein may further include any or more of the following embodiments: the composite is a heat-treated composite; an amount of oxygen in the atmosphere of the package or container does not exceed 75 mmol / kg of elastomeric composite; the composite has been packaged or stored or aged for a period of time of at least 5 days or at least 14 days or other periods of time disclosed herein.

[0014] With respect to any aspect, process, or embodiment disclosed herein, as appropriate, the packaged elastomeric composite or the processes disclosed herein may further include any or more of the following embodiments: before sealing the package or container, the inside of the package or container is rinsed with at least one gas that is non-reactive with the composite and / or subjected to a vacuum; before sealing the package or container, the composite is heat-treated at a temperature of at least 40°C; at the time of sealing the package or container housing the composite, the composite has a probe temperature of at least 40°C; the composite is prepared by combining at least one solid elastomer and a wet filler comprising a filler and a liquid, in which the liquid is present in an amount of at least 15% by weight based on the total weight of the wet filler.

[0015] With respect to any aspect or process or embodiment disclosed herein, if any, the packaged elastomeric composite or the processes disclosed herein may further include any or more of the following embodiments: the stored elastomeric composite or a compound formed from the stored elastomeric composite has a Payne ratio that is reduced by at least 10% compared to the Payne ratio of the composite before packaging sealing, wherein the Payne ratio is G'(0.3%) / G'(51.5%), in which G'(0.3%) is a dynamic storage modulus measured at a strain amplitude of 0.3% and G'(51.5%) is a dynamic storage modulus measured at a strain amplitude of 51.5%; the compound formed from the stored elastomer composite has a maximum tan θ value which is reduced by at least 10% compared to the maximum tan θ value of the composite before sealing the package.

[0016] With respect to any aspect, process, or embodiment disclosed herein, if applicable, the packaged elastomeric composite or the processes disclosed herein may further comprise any or more of the following embodiments: the composite is the product formed by incorporating at least one bonding agent during the mixing of at least one elastomer with at least one filler; the composite is the product formed by incorporating at least one bonding agent during the mixing of at least one elastomer with at least one filler; the composite further comprises at least one bonding agent. DETAILED DESCRIPTION

[0017] Elastomers (e.g., diene-based elastomers) are known to degrade in the presence of air / oxygen. Degradation can take the form of polymer chain cleavage and / or crosslinking, which can affect the properties of the rubber. Elastomeric composites can be cured in the presence of curing agents, such as sulfur, to effect crosslinking, resulting in a vulcanizate that is hardened (relative to the composite) and exhibits greater stability against degradation; degradation of vulcanizates can still occur but may have less influence on certain performance attributes compared to the influence resulting from the degradation of uncured composites. However, it may be necessary to store (and / or transport) uncured elastomeric composites for long periods of time (e.g., 3, 6, 9 months, or 1 or 2 years).Furthermore, the increased temperatures often present in warehouses or during transport (trucks, shipping containers) can accelerate the rate of degradation. To slow this rate, composites can be stored in refrigerators or under air conditioning. However, these storage solutions require significant refrigeration equipment and result in excessive energy costs.

[0018] It had not been recognized until now that materials forming a high oxygen barrier could provide an atmosphere with a low oxygen content for a sufficient period of time such that the properties of the rubber in uncured composites comprising rubber and a filler, and of compounds formed from these composites, are effectively preserved or even, in some examples, surprisingly improved. As such, it is not common practice in industry to store these elastomers or composites in an oxygen-poor environment. The improvement can result in rubber properties that are enhanced by at least 5% or at least 10%, where the enhancement can be an increase in value (e.g., tensile stress ratio) or a decrease in value (e.g., hysteresis as indicated by a maximum tan θ, a Payne effect, and / or a Payne ratio).

[0019] The present invention discloses packaged elastomeric composites (or stored or aged elastomeric composites) and methods for storing and / or packaging these composites, and methods for preserving and / or enhancing (improving) at least one rubber property of the composite or of the rubber compound formed from these stored or packaged composites. The rubber properties indicated herein may be those of the composite itself or of a compound of rubber formed from the composite, in which the rubber compound comes from the vulcanization of the elastomer composite (vulcanizate), i.e. from the hardening of the composite in the presence of hardening agents (hardeners) such as sulfur, peroxides, etc.

[0020] The present invention discloses a packaged elastomeric composite, comprising: a sealed package containing the composite in an atmosphere having a partial pressure of oxygen less than 10 kPa, in which the composite is uncured and comprises at least one elastomer and at least one filler, in which: the package comprises at least one wall surrounding the composite in which the at least one wall comprises at least one oxygen barrier layer such that the package has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23° C and 0% relative humidity.

[0021] Accordingly, one aspect provides for a composite sealed in a container or package containing or housing the composite, wherein the container or package comprises at least one wall surrounding the composite and at least one wall comprises at least one oxygen barrier layer such that the container or package maintains a low oxygen content over a period of time. A wall may comprise a single layer that is the oxygen barrier layer or may comprise multiple layers (two or more layers), at least one of which is the oxygen barrier layer. An oxygen barrier layer substantially reduces the rate of oxygen transport from outside the container to inside the container.By limiting the amount of oxygen exposed to the composite via the container(s) or packaging(s) having an oxygen barrier wall (including at least one oxygen barrier layer), the degradation of the composite can be substantially interrupted.

[0022] The composites disclosed herein are stored and / or packaged and / or contained in one or more containers or packages that surround and house the elastomeric composite and may be of any shape or size as long as they provide the desired oxygen barrier properties. The container may be a package (e.g., box, crate, bag) or any compartment, including a glove box, a room, etc., of any volume in which (molecular) oxygen can be retained in a desired quantity. In one aspect, the container or package has an oxygen transmission rate (OTR) not exceeding 100 cm³ / (m²-day-atm) at standard temperature and pressure. The oxygen transmission rate of the container or package can be determined from the oxygen barrier properties of the wall that comprises the oxygen barrier layer (oxygen barrier wall).Oxygen transmission rates. These values ​​can be determined according to ASTM D3985, and can be performed under conditions such as 73°F and 0% relative humidity at sea level. In other variations, the oxygen transmission rate can be determined or reported at 50% relative humidity, or at 65% relative humidity. As an option, at least one wall may have an oxygen transmission rate not exceeding 100 cm3 / (m2-day-atm) at 23°C (73°F) and 0% relative humidity (RH), for example, not exceeding 50, not exceeding 10, not exceeding 5, not exceeding 1, not exceeding 0.5, not exceeding 0.1, not exceeding 0.05, not exceeding 0.01, not exceeding 0.005 or not exceeding 0.001 cm3 / (m2-day-atm) at 23°C (0% relative humidity).

[0023] The wall of the container or packaging may comprise one or more sections which, when sealed, form the container. For example, a typical box typically contains top and bottom wall sections plus four side wall sections. It is understood that the number of wall sections may vary; for example, a single cylindrical side wall section sealed to top and bottom wall sections, or a continuous wall constructed to fold along indentations to form the container, or further assembled with one or more wall sections. Any number of side wall sections may be used (hexagonal boxes or containers, wedge-shaped boxes or containers, etc.).A bag or pouch will ordinarily contain one or more wall sections, for example two or more flexible wall sections which are joined together by means of corresponding edges to form one or more side wall sections (and optionally a bottom wall section) so that at least two unsealed edges form an opening which can be sealed (for example, hermetically sealed) during packaging.

[0024] By way of more specific illustration, a flexible package may comprise two flexible wall sections with similar length and width dimensions, each having four edges to form a square or rectangular wall section. The two flexible wall sections may be bonded together by sealing three of their corresponding edges, leaving the fourth edge unsealed to provide an opening for inserting the elastomeric composite into the package. Ordinarily, all wall sections of a container (side wall section, top and / or bottom wall section) are made of the same materials; the oxygen barrier properties of the wall (and the package) can then be determined from the oxygen transmission rate of any wall section.Variations may occur, for example, a lower wall section may include one or more structural support layers to provide strength. Additionally, a top or side wall section may be constructed to facilitate opening the container and / or sealable layers (e.g., heat-sealable) or adhesives may be used to seal (hermetically seal) the package. Consequently, these sections may exhibit varying oxygen barrier properties. Therefore, the oxygen transmission rate of the packaging can be a surface-weighted average over the entire surface of the container.

[0025] With regard to seals, sealing refers to airtight seals that provide the package with oxygen barrier properties such that the oxygen transmission rate from the outside to the inside of the package does not exceed 100 cm³ / (m²-day-atm) at 23°C and 0% relative humidity, or other quantities disclosed herein. Airtight seals, for example, may be formed by heat-sealing two sealable layers together, such as heat-sealing the edges of a side wall. A package that is hermetically sealed (for example, edge-sealed) may have an oxygen transmission rate similar or substantially the same as that of an oxygen barrier wall.

[0026] A container or package having more than one wall may consist of two or more containers, for example, a first container surrounding a second container which surrounds and houses the elastomeric composite. Each container would include a wall, which may be a single-layer or multi-layer wall. For example, a first container may have a wall with a first oxygen barrier property, and a second container may have a wall with a second oxygen barrier property. As a specific example, a container (a wall) may include a flexible film (for example, a coating) that surrounds and optionally conforms to the shape of the material to be packaged, resulting in a coated or wrapped material or a shrink-wrapped material.A second container (or second wall) may include a less flexible or rigid material surrounding the coated material to provide protection against breakage and / or deformation during storage (which may include transport). In any case, whether multiple walls or multiple containers are involved, each container may have oxygen barrier properties such that the elastomeric composition is subjected to the desired oxygen barrier properties, for example, an oxygen transmission rate not exceeding 100 cm³ / (m²-day-atm) at 23°C and 0% relative humidity, or other values ​​disclosed herein. For example, a composite may be housed within two walls, each having oxygen barrier properties; for example, one wall that is a coating enveloping the elastomeric composite, and a second wall that is a container housing the encased composite. The rate... The oxygen transmission rate of each wall (of each container) cannot be less than 100 cm³ / (m²-day-atm), but combined, the container comprising two walls (e.g., the lining and the packaging) can achieve the desired oxygen transmission rate not exceeding 100 cm³ / m²-day-atm. For more than one container (or more than one wall), the overall oxygen transmission rate (OTR) can be determined from the equation: TTO = 1 / {(1 / TTOparoil) + (l / TTOparoi2) + ...} where "TTOp a roi i" and "TTOp a ro; 2" denote the respective oxygen transmission rate of each container (each wall). The equation can be applied to multiple walls or multiple oxygen barrier layers within a wall (for example, shrink-wrapped packaging or other shape-conforming coating that repeatedly surrounds the composite can be considered as multiple walls or multiple layers within a wall).

[0027] Optionally, one or more containers that do not have oxygen barrier properties may be used to house the elastomeric composite in addition to the container(s) having the oxygen barrier wall. For example, the additional container may be a mesh or a flexible bag to support or maintain the shape of the composite, for example, when the composite is in the form of fragments, granules, or the like. Alternatively, the additional container may be a box made of wood, paper, or corrugated cardboard without oxygen barrier properties or with poor oxygen barrier properties (or other non-barrier material), or sheets or grids, or may be fibrous, such as fabric.The additional container(s) may be positioned either outside or inside (or both) the oxygen barrier container (i.e., the container with the oxygen barrier wall) to provide additional structural support and / or otherwise facilitate shipping and / or handling.

[0028] The containers or packages disclosed herein may be of any desired volume or size. The interior of the container may have a volume (internal volume) of at least 1 L, 10 L, 20 L, or 50 L. The container may be as small, as large, or as wide as a sealed shipping container or enclosure, for example, ranging from 1 L to 40,000 L, 1 L to 20,000 L, 1 L to 10,000 L, 1 L to 2,000 L, 1 L to 100 L, 1 L to 50 L, 1 L to 20 L, or 1 L to 10 L. For two or more containers where one is housed inside the other, the volume is that of the largest oxygen barrier container. For example, a shipping container can have a volume of up to 20,000 L or 40,000 L, and a crate can have a volume of up to 1,500 L or 2,000 L.

[0029] In another aspect, the oxygen barrier properties of at least one wall can be chosen by limiting the amount of oxygen exposed to the elastomeric composite over a certain period of time to prevent significant degradation of the composite. For example, knowing the weight of the elastomeric composite present in the packaging or container, a maximum amount of oxygen relative to the amount of composite by weight can be calculated.As an option, the container or packaging includes at least one wall comprising at least one oxygen barrier layer such that the amount of oxygen in the packaging does not exceed 75 mmol / kg of elastomeric composite, for example, does not exceed 60 mmol / kg of elastomeric composite, does not exceed 50 mmol / kg of elastomeric composite, does not exceed 40 mmol / kg of elastomeric composite, does not exceed 30 mmol / kg of elastomeric composite, does not exceed 20 mmol / kg of elastomeric composite, does not exceed 15 mmol / kg of elastomeric composite, does not exceed 10 mmol / kg of elastomeric composite, does not exceed 6 mmol / kg of elastomeric composite, does not exceed 5 mmol / kg of elastomeric composite, does not exceed 4 mmol / kg, does not exceed 3 mmol / kg, does not exceed 2 mmol / kg, or does not exceed 1 mmol / kg of elastomer composite.The amount of oxygen present in a sealed container or package can be measured with an oxygen sensor (many types of which are commercially available) either when the package is sealed or afterward. For example, the headspace of the container can be measured with a sensor that has a needle that pierces the package through a resealable septum, which can be glued to the outside of the package or built into the wall, or with an adhesive sensor that can be inserted and mounted in the package before sealing. Examples of oxygen sensors include CheckPoint® or OpTech® optical oxygen sensors, commercially available from Ametek Mocon (Minnesota, USA). From the respective volumes of the container and the composite, as well as the weight of the composite, the amount of oxygen in the container (e.g., in mmol) can be determined per weight of composite (e.g., kg).As an option, the package volume is at least 1 L, or at least 10 L, or other volumes disclosed herein. As an option, the disclosed quantity of oxygen per composite by weight in the container or package is maintained for a period of time of at least 5 days (e.g., from the time of sealing), or at least 7 days, at least 1 month, at least 3 months, at least 6 months, or at least 1 year, for example, from 5 days to 1 year. In other words, at any time period of at least 5 days or more (e.g., up to one year), the quantity of oxygen present in the container is minimized to levels disclosed herein, for example, not exceeding 20 mmol / kg of composite, or even less.

[0030] The number of moles of oxygen in a closed container can be calculated according to equation (1): ([O2]mes. * Væ / 100) * (273 K / Tcontainer) * (Pcontainer / 101.3 kPa) / 22.4 L (1) where [O2]mes. is the measured oxygen concentration (%), Vair is the volume of air in the container (L), Tcontainer is the temperature inside the container at the time of the oxygen concentration measurement K=(K), and Pcontainer is the pressure inside the container at the time of the oxygen concentration measurement (kPa).

[0031] For a container holding a composite, Vair can be determined by subtracting the volume of the composite from the volume of the container, where the volume of the composite can be calculated as the weight of the composite divided by its relative density. From the result of equation (1) and knowing the weight of the composite, the oxygen content per composite by weight (mmol / kg of composite) can be determined. In some cases where the container is a flexible bag, storing the container under vacuum or partial vacuum can give the container the shape of the composite. In this situation, the volume of the container can be determined by methods well known in the art. For example, the volume of the container can be considered to be the same as the volume of the composite.

[0032] As an option, the oxygen content may be indicated as the partial pressure of oxygen. The partial pressures disclosed herein refer to values ​​measured under ambient conditions, for example at sea level and 20°C. Under ambient conditions, the partial pressure of oxygen is calculated from the atmospheric pressure (101.3 kPa at sea level) multiplied by the atmospheric oxygen percentage (21%).

[0033] As an option, the atmosphere initially present in the container or packaging at the time of sealing has a low oxygen content (for example, at the time the packaging is hermetically sealed or immediately before). For example, the atmosphere in the container can be modified to reduce the oxygen content inside the packaging; that is, the atmosphere in the container is a modified atmosphere. As an option, the inside of the container or packaging has a partial pressure of oxygen of less than 21 kPa, less than 20 kPa, less than 19 kPa, less than 18 kPa, less than 17 kPa, less than 16 kPa, less than 15 kPa, less than 12 kPa, less than 10 kPa, less than 9 kPa, less than 8 kPa, less than 7 kPa, less than 5 kPa, less than 4 kPa, less than 3 kPa, less than 2 kPa or less than 1 kPa, which is indicative of a modified atmosphere.As an option, a modified atmosphere (e.g. low partial pressure of oxygen) can be achieved by subjecting the inside or interior of the packaging to a vacuum so that the atmosphere in the container has a absolute pressure not exceeding 90 kPa, for example, not exceeding 80 kPa, not exceeding 70 kPa, not exceeding 60 kPa, not exceeding 50 kPa, not exceeding 40 kPa, not exceeding 30 kPa, not exceeding 20 kPa, not exceeding 10 kPa, or not exceeding 5 kPa. As an alternative, the atmosphere in the container can be modified by rinsing with a non-reactive gas (for example, non-reactive with the composite). Examples of non-reactive gases include inert gases such as nitrogen, argon, helium, and xenon. Other non-reactive gases include carbon dioxide. The atmosphere can be modified with one or more rinsing steps (for example, two or three or more rinsing steps). As an alternative, the atmosphere can be modified with a combination of one or more vacuum and rinsing steps to achieve the low oxygen content values ​​disclosed herein.

[0034] Alternatively, a low oxygen content of the atmosphere inside the packaging or container can be determined from a difference in partial pressure of oxygen between the outside of the container or packaging and the inside of the packaging, where the atmosphere outside would be higher than that inside. For example, the difference in partial pressure of oxygen between the outside and inside of the container or packaging may be at least 1 kPa, at least 2 kPa, at least 3 kPa, at least 4 kPa, at least 5 kPa, at least 6 kPa, at least 7 kPa, at least 8 kPa, at least 9 kPa, at least 10 kPa, at least 11 kPa, at least 12 kPa, at least 13 kPa, at least 14 kPa, at least 15 kPa, at least 16 kPa, at least 17 kPa or at least 18 kPa.

[0035] As an alternative, a low oxygen content in the packaging (inside the packaging) can be indicated by the amount of (molecular) oxygen in the packaging, for example, the number of moles (e.g., mmol) of oxygen per weight of elastomeric composite (e.g., not exceeding 75 mmol / kg of elastomeric composite as shown herein), the volume of oxygen (or volume of oxygen per kg of composite), or as the concentration of oxygen present in the atmosphere inside the container, for example, less than 7%, less than 5%, less than 3%, less than 2%, or less than 1%. Oxygen concentrations can be measured with an oxygen sensor as shown herein.

[0036] As an option, the oxygen content of the container or packaging at the time of sealing can be modified by including at least one oxygen-removing agent inside the container. Oxygen-removing agents eliminate (trap, recover) oxygen from the atmosphere of a closed container and thus lower the oxygen content. Oxygen-removing agents can eliminate oxygen by reaction (for example, by means of an oxidation reaction) or by trapping oxygen. In another embodiment, the atmosphere inside the container or packaging can be modified with a vacuum and / or a non-reactive gas, and the elastomeric composite is further packaged. with at least one deoxygenating agent. The oxygen content achieved through the use of deoxygenating agents depends on the amount of deoxygenating agent used; the oxygen content achieved may be any value disclosed herein, for example, levels below 21 kPa, or other levels disclosed herein. Deoxygenating agents may be packaged with the composite, for example, contained or enclosed in a sachet. The sachet, which must be oxygen-permeable, may be placed adjacent to the composite or adhered to an internal wall (the inside) of the container or package. Examples of deoxygenating agents include metals such as metal powders, iron filings, ascorbic acid and salts thereof, any of the protective agents (for example, antioxidants) disclosed herein, catechol, and other deoxygenating agents known in art.Protective agents can be combined with the elastomer during the mixing of the elastomer with the filler, as known in the art. For example, the composite may include one or more protective agents as described herein. As another example, at least one wall of the packaging may include a deoxygenating material. Examples of deoxygenators, oxygen barrier packaging, and deoxygenating agents, including packaging walls that incorporate deoxygenating materials, can be found in Ahmed et al., Food Control, Volume 82, pp. 163-178 (2017), the disclosure of which is cited for reference. Alternatively, the only deoxygenator present may be a protective agent dispersed within the composite, as described herein.

[0037] The at least one wall (oxygen barrier wall) may comprise one or more layers, for example, one or more laminates of sheets, films, coatings, panels, etc. The wall may be a single-layer wall, which comprises a material conferring appropriate oxygen barrier properties (oxygen barrier material), or a multi-layer wall (two or more layers) in which at least one of the layers comprises an oxygen barrier material, i.e., the layer is an oxygen barrier layer. The layer(s) of a wall may be a film, a panel, or a laminate. Multi-layer walls may be formed by extrusion or co-extrusion, extrusion coating, lamination (for example, adhesive lamination), the use of adhesive, or the deposition of one layer upon another, the use of bonding layers, or metallization.

[0038] Oxygen barrier walls (or layer(s)) can comprise a number of materials, the most common including polymers and / or metals. Polymer materials forming oxygen barriers include polyamide (PA), polyethylene terephthalate (PET) and modified PET (e.g., glycol-modified PET), polyethylene naphthalate (PEN), poly(ethylene vinyl alcohol) (EVOH), poly(vinylidene chloride) (PVdC), polyacrylonitrile, Polyvinyl alcohol (PVOH), methyl acrylate, acrylonitrile-methyl acrylate copolymers (e.g., Barex® resins, which are an acrylonitrile-methyl acrylate copolymer grafted with nitrile rubber), cyclo-olefin copolymer (COC), and mixtures thereof. Multilayer walls may include one or more oxygen barrier layers. One or more barrier layers or walls may be oriented biaxially, e.g., stretched along transverse directions to make the polymer chains aligned with the plane of the layer or wall. Biaxial orientation can provide additional strength, hardness, compressive strength, etc. (improved tensile properties) when the film is stretched to orient the chains.

[0039] Other oxygen barrier materials include those containing metals, for example, metallized layers. Metallized layers (designated by the prefix "m", such as mPET) can be formed by a process known as metallization. During metallization, metals can be deposited onto substrates by a number of processes where the substrate can be a polymer material having the desired flexibility or rigidity. For example, metallization can involve the evaporation of metals such as aluminum and subsequent deposition (e.g., vacuum deposition, chemical vapor deposition) onto a substrate film onto which thin metallized layers are deposited. Other processes for depositing metallized layers include sputtering and electroplating. Alternatively, thin metallized layers can be formed and the metallized layer bonded to one or more polymer layers.Metals that can be used as metallic or metallized layers include aluminum, tin, nickel, iron, silver, and alloys thereof, for example, aluminum-zinc alloys, silver-zinc-aluminum alloys, copper-zinc alloys, etc. Other materials that can be deposited on polymer films in addition to metals include ceramics (e.g., metal oxides such as silicon oxides (SiOx) such as silica, aluminum oxides, zinc oxides, magnesium oxides, titanium oxides, kaolinites, glass, and clays), carbon-based materials such as carbon nanomaterials (e.g., carbon nanotubes and graphene materials including graphene, graphene oxides, reduced graphene oxides), and melamine-based coating materials.Materials such as metals, ceramics, and carbon-based coatings can also be deposited as particles with submicron dimensions, for example, ranging from 1 nm to 1000 nm, 1 nm to 500 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. As another variant, at least one wall contains neither a metallized nor a metallic layer.

[0040] Metal containers that can be assembled / welded to form a hermetic seal can also provide oxygen barrier properties, for example, stainless steel, tin, and aluminum. Containers comprising metals can also include other materials, such as glass, ceramics, plastics, etc., for example, a glove box or an enclosure or other chamber. Rigid containers can be formed from thermoplastic elastomers and thermoplastic vulcanizates. Thermoplastic elastomers (TPEs) contain more than one type of polymer: an elastomer (providing elastic properties) and a second polymer that provides strength. Examples of TPEs include styrene block copolymers, such as styrene-butadiene-styrene block copolymers, and ethylene-acrylic copolymers.Thermoplastic vulcanizates (TPVs) are a class of thermoplastic elastomers prepared by vulcanization or crosslinking, combining the properties of crosslinked rubbers with the melt-processability of thermoplastics to create a material that can exhibit high compression and resistance to heat deformation. Examples of TPVs include Santoprene™ thermoplastic vulcanizates (ExxonMobil), a vulcanized ethylene propylene diene rubber (EPDM) in a thermoplastic polypropylene (PP) matrix. Rigid containers can be sealed with adhesive material, gaskets, O-rings, or similar seals (e.g., nitrile rubber, butyl rubber, and similar materials).

[0041] The oxygen barrier wall or layer may optionally contain oxygen-depleting materials integrated into the layer itself. These oxygen-depleting barrier layers are usually sandwiched between protective layers, which may act as structural and / or sealable layers. Alternatively, the film is deoxygenating, i.e., oxygen depleting agents are integrated into the oxygen barrier material, or the film is composed of a material that can ensure deoxygenation.

[0042] The appropriate oxygen barrier properties of at least one wall can be obtained by one or more factors, including the type of wall or layer material or the layer arrangement (for a multilayer wall). For multilayer walls, typical layered arrangements include a sealing layer as the innermost layer (e.g., polyethylenes such as polypropylene, LDPE, LLDPE, or vinyl-ethylene acetate (EVA)), followed by the oxygen barrier layer (e.g., PET, polyethylene) as the outermost layer.

[0043] The wall and layer thicknesses can also be chosen to provide oxygen barrier properties (and other properties) of at least one wall while taking into account the overall package weight to reduce shipping costs. Wall thicknesses can be at least 10 µm and up to 10 cm, for example, Up to 5 cm for rigid packaging. For flexible packaging, wall thicknesses can range from 10 µm to 250 µm, for example, from 10 µm to 50 µm. For example, PVdC-coated films, EVOH-based films, polyamide films (e.g., nylon), and metallized polymer films can have thicknesses ranging from 10 µm to 30 µm, for example, from 15 µm to 30 µm. The oxygen barrier wall can have a thickness ranging from 5 µm to 50 µm, from 5 µm to 40 µm, from 5 µm to 40 µm, from 5 µm to 30 µm, or from 5 µm to 20 µm. Rigid packaging can have thicknesses of at least 250 µm, for example, or at least 500 µm.

[0044] Single-layer walls can be provided in the form of a flexible film, for example, a shrink-wrap or a shrink-wrap, or can be a rigid film (for example, metal containers, ceramic containers). Examples of flexible films include shrink-wrap / stretchable PVdC films such as shrink-wraps, for example, having a thickness of at least 30 µm to 100 µm, 30 µm to 75 µm, or 30 µm to 50 µm.

[0045] For multilayer walls, any number of layers can be used, such as 2, 3, 4, 5, 6, 7, etc., up to 10 or 12 layers or more (e.g., up to 20 layers or more). These layers can impart a number of properties, including structural properties, odor and / or moisture barriers, oxygen barriers, sealable layers (e.g., heat-sealable layers), and combinations thereof, chosen to provide the desired level of flexibility or rigidity, transparency, and oxygen barrier. Regardless of the number of layers, the resulting wall has the required oxygen barrier properties.

[0046] Regarding properties other than oxygen barrier properties, one or more layers may provide strength and / or rigidity and / or structural support, for example, to prevent deformation or destruction of the oxygen barrier wall (e.g., puncture resistance). Some materials may provide several functions. These layers include, for example: - polyesters such as polyethylene terephthalate and polycarbonate, - polyethylenes (PE), such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), very-low-density polyethylene (LVDPE), ultra-low-density polyethylene (ULDPE), or linear low-density polyethylene (LLDPE), and mixtures thereof, - polypropylenes - polyvinyl chloride (PVC) - polylactic acid (PLA) - ethylene-(meth)acrylic acid copolymers (for example Surlyn® resins from DuPont) - acid copolymer resins (for example, Dow's NUCREL™ resins, which are terpolymers of ethylene, methacrylic acid and acrylate], and - mixtures of these.

[0047] For the aforementioned purposes, corresponding metallic or metallized layers may also be used, whether by adhesion, vacuum vapor deposition, CVD, spraying, electroplating or any other process of adhesion of a thin metallic film to a polymer.

[0048] One or more layers of the multilayer wall may be a sealing or sealable layer (sealing agent). The sealable layer may allow panels (for example, one or more of the top, side, and bottom panels) to be joined to one another along their edges. As an option, the sealable layer is a heat-sealable layer in which the application of heat deforms or melts the polymer, enabling adhesion. Alternatively, the sealable layer may be a laminate that bonds the layers together. In a multilayer wall, the sealable layer is often positioned on one or both outer edges of the wall; for example, the sealable layer may be the innermost layer (forming the inner wall) or the outermost layer (forming the outer wall). Sealable layers include, for example: - Polyesters such as PET and metallized coatings (e.g., mPET) - Polyethylenes as disclosed above, such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and HDPE, and metallized coatings, e.g., mVLDPE - Polypropylenes - ethylene-acrylic acid copolymers (e.g., NUCREL™ resins), - ethylene-(meth)acrylic acid copolymers (e.g., Surlyn® resins), - ethylene-vinyl acetate (EVA), and - mixtures thereof.

[0049] Alternatively, adhesives can be coated or laminated onto the layers to improve adhesion between the layers (such as adhesives coating oxygen barrier layers and / or structural layers).

[0050] The sealable layer can assemble or otherwise adhere to one or more adjacent sealable layer(s) to form a hermetic seal that provides barrier properties similar to those of the barrier wall. Alternatively, the sealing layer can be a layer that exhibits good adhesion to and supports an adhesive. Some sealable layers can also serve as structural layers, for example, polyesters, polyethylenes (e.g., LDPE, LLDPE, HDPE), polypropylenes, ethylene-(meth)acrylic acid copolymers (EVA), and others known in art.

[0051] One or more layers in a multilayer wall can act as a moisture barrier to prevent the penetration or release of water (depending on the elastomeric composite), for example, LDPE, LLDPE. Other types of layers can be used to prevent the penetration of other chemical vapors and / or light and / or other undesirable elements (for example, polyamide or EVOH). Processability, color / transparency, and odor barriers are also other factors in layer selection.

[0052] For example, multilayer walls may include the following layer arrangements (from inside the container to outside the container, from left to right; "I" denotes the interface between layers): (i) sealable layer I barrier to 1' O21 sealable layer (ii) structural layer I barrier to 1' O2 I sealable layer (iii) sealable layer I barrier to 1' O21 structural layer (iv) 1st barrier to 1' O21 structural layer I 2nd barrier to 1' O21 sealable layer (v) structural and / or sealable layer 1st barrier to 1'O21 2nd barrier to 1'O21 structural and / or sealable layer (vi) structural and / or sealable layer I O21 barrier moisture barrier (vii) structural and / or sealable layer I O21 barrier moisture barrier I structural and / or sealable layer (viii) structural and / or sealable layer I O2 barrier + moisture barrier

[0053] Although three- or four-layer arrangements are illustrated, one or more additional layers may be provided to complement any of the above arrangements. For example, adhesive or laminated layers may be added between the oxygen barrier layers and the structural and / or sealable layers. Any number of layers for oxygen barrier walls is known in the art, for example, single-layer, two-layer, three-layer, four-layer, five-layer, six-layer, seven-layer, or more walls, for example, ten-layer, or even twenty-layer (or more).

[0054] A multilayer wall may comprise several O2 barrier layers (for example, 1st and 2nd O2 barrier layers, or even 3rd or 4th oxygen barrier layers or more). Where there are two or more O2 barrier layers, the materials forming each O2 barrier layer may be identical or different. For example, each of the O2 barrier layers may be (or comprise) polyamide (PA), poly(ethylene vinyl alcohol) (EVOH), poly(vinylidene chloride) (PVdC), polyvinyl alcohol (PVOH), methyl acrylate, or metallized layers such as mPET, mPA, mPE and mixtures thereof, or metallic layers (for example, an aluminum layer); the structural layer may be of HDPE, LDPE, VLDPE, ULDPE, LLDPE, polypropylene, PVC, PET and mixtures thereof; the sealable layer may be of LDPE, LLDPE, HDPE, polypropylene and EVA.

[0055] As an option, any one or all of the layers, or the oxygen barrier layer, may be oriented biaxially (“Bo”).

[0056] Specific examples include: PA I PE I aluminum foil I PE I LLDPE PE I EVOH I PE LLDPE I Nylon I EVOH I Nylon I LLDPE EVAI PA IEVA EVAI PA I mPET EVA I PA I mPP I LLDPE BoPP | LDPE | mBoPP | SURLYN where "BoPP" refers to biaxially oriented polypropylene, "m" refers to metallized layers, and "SURLYN" refers to Surlyn® resins. One or more additional layers may be provided to complement any of the above arrangements.

[0057] The desired partial pressures of oxygen in the sealed container can be achieved in various ways. Methods for removing oxygen from sealed containers (or containers to be sealed) are known in the art. As an option, the inside of the container (or the internal contents or the inside of the container) or the packaging can be subjected to a vacuum, rinsed with a non-reactive gas (e.g., an inert gas), exposed to deoxygenating agents, and combinations thereof. For example, the container or packaging can be vacuum-sealed with a device constructed to subject the internal contents to a vacuum and then seal the packaging. Vacuum sealing machines (vacuum sealers) or vacuum heat-sealing machines (vacuum heat sealers) are known in the packaging art, such as flexible packaging.An example of a vacuum sealer includes two surface elements that can open and close to clamp a substantially flat packaging opening. The surface elements may include a bar that rises and falls against a platform, where the open end of the packaging is inserted between the bar and the platform. Alternatively, two bars may be used, for example, an upper bar pivotally mounted on a lower bar. In any option, one or both bars may include heating and / or pressure elements to perform the sealing. Between the two surface elements are one or more nozzles connected to a vacuum pump and optionally to an inert gas source. After the packaging is filled with the elastomeric composite, the edges... Unsealed portions of the package can be inserted between two bars of the vacuum sealer while at least one retractable nozzle is inserted into the package opening. Clamping or interlocking the two bars effectively seals the package opening and ensures a tight fit around at least one nozzle. A vacuum can be applied and optionally cycled with an inert gas rinse. After vacuum application, the nozzle can be retracted and removed from the package opening. Immediately afterward, heat can be applied via heating and / or pressure elements to seal the package. For heating elements, the heat can soften a sealing layer on the package wall and / or an adhesive applied to the sealing layer.Alternatively, the package can be contained within a chamber suitable for vacuum and / or an inert gas atmosphere. This chamber contains bars that clamp and seal the edges of the opened package. Examples of such vacuum heat sealers include those sold by AmeriVacs (San Diego, CA), such as the retractable nozzle vacuum sealer with gas purging. As an alternative to heat and pressure, welding processes can be used. For example, CO2 lasers can be used to heat and melt polymer layers, causing them to fuse together.

[0058] As another example (for example, generally for more rigid containers but also applicable to flexible containers), the container or packaging may have one or more openings or outlets providing gaseous communication between the inside of the packaging and a vacuum pump. The opening may extend through a wall of the packaging and may include a collar (for example, a substantially circular collar) on the outer wall of the packaging (surface of the outer wall) to fit tightly to the hose or tube extending to the vacuum pump. The opening may further include a valve, for example, a non-return valve, through which air or other gases may be removed from the inside of the container during operation of the vacuum pump. As an option, the valve may be a two-way valve for filling a bag with nitrogen after the contents have been evacuated.When a desired vacuum level or partial pressure of oxygen is reached, the pump stops and the valve opens to limit the entry of air or oxygen into the container. Optionally, a cap or similar closure or sealing element can be tightly fitted to the collar to prevent further oxygen entry into the package, for example, at an oxygen transmission rate higher than that of the wall. The cap can be made of an oxygen barrier material and can be attached to the collar with an adhesive material (e.g., glue). Alternatively, the valve area can be covered with adhesive if no cap is used.

[0059] Methods for storing or aging an elastomeric composite are also disclosed herein. The storage of sealed containers or packages may take place in a warehouse or similar facility and may include shipping / transportation processes. The method may include storing the elastomeric composite in the sealed containers disclosed herein, for example, containers or packages comprising at least one wall surrounding the composite, in which at least one wall includes at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm³ / (m²-day-atm) at 23°C and 0% relative humidity and / or an oxygen content in the package not exceeding 75 mmol / kg of elastomeric composite, or other ranges as disclosed herein.As disclosed herein, at least one wall is an oxygen (O2) barrier wall comprising at least one layer that is an oxygen barrier. The processes disclosed herein may enable the elastomeric composite to retain or even enhance at least one rubber property. Thus, processes for maintaining or enhancing at least one rubber property of an elastomeric composite or a compound formed from the composite are also disclosed herein, including storing the composite in a sealed container for a period of time of at least 5 days, or at least 14 days, or other periods of time disclosed herein. For example, storage may be carried out under a low-oxygen atmosphere in one or more sealed containers having an oxygen barrier wall.

[0060] The following are disclosed herein: methods for storing an elastomeric composite, comprising: sealing the elastomeric composite in a container and storing the composite in the sealed container for a period of time of at least 5 days, wherein: the elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and the container includes at least one wall surrounding the composite in which at least one wall includes at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23°C and 0% relative humidity.

[0061] Also disclosed herein are methods for preserving and enhancing at least one property of an elastomeric composite or a compound formed from the composite, including: the storage of the elastomeric composite in a sealed container for a period of time of at least 5 days, in which: The elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and the container includes at least one wall surrounding the composite in which at least one wall includes at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm3 / (m2 •day-atm) at 23°C and 0% relative humidity.

[0062] Before sealing (and storage), the process may include subjecting the composite in the container or packaging to at least one step that modifies the atmosphere inside the container to obtain an atmosphere with a low oxygen content. As an option, the atmosphere is modified by rinsing the inside of the container with at least one gas that is non-reactive with the composite (a non-reactive gas), for example, a gas that contains less than 10% oxygen, less than 7%, less than 5%, less than 2%, or less than 1% oxygen. Examples of non-reactive gases include inert gases such as nitrogen, argon, helium, xenon, or other non-reactive gases such as carbon dioxide, including mixtures of these gases. The rinsing involves replacing at least a portion of the air present in the packaging with at least one non-reactive gas (for example, nitrogen, argon, etc.).) such that the atmosphere contains at least 90% of the non-reactive gas, for example, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% of the non-reactive gas. In other words, the atmosphere contains at least 90% (or other quantities disclosed herein) of at least one gas that is non-reactive with the elastomeric composite.

[0063] As another option, the atmosphere is modified by removing a significant amount of oxygen from the container, for example by evacuating the interior of the container (or by applying a vacuum to the interior of the container) by any of the methods disclosed herein or known in the art. The interior of the container may be placed at any desired level of vacuum as disclosed herein where the evacuated container may have an absolute pressure not exceeding 90 kPa, for example, not exceeding 80 kPa, not exceeding 70 kPa, not exceeding 60 kPa, not exceeding 50 kPa, not exceeding 40 kPa, not exceeding 30 kPa, not exceeding 20 kPa, not exceeding 10 kPa, not exceeding 5 kPa or not exceeding 1 kPa.In addition to gas rinsing and / or vacuum rinsing, or as an alternative, a sachet containing a deoxygenating agent can be placed in the container where, over time, the deoxygenating agent removes oxygen from the inside and thus reduces the oxygen content inside the container.

[0064] As an option, the atmosphere is modified by subjecting the composite in the container (the interior of the container that houses the composite) to at least one step of: rinsing the interior of the container with at least one gas that is non-reactive with the composite and application of a vacuum inside the container. The modification of the atmosphere may include one or a combination of these steps. For example, after the composite is placed inside the container, the inside of the container may be rinsed with a non-reactive gas(s), followed or preceded by the application of a vacuum inside the container, where this rinsing sequence with an inert gas / vacuum may be repeated as needed, for example, one, two, three, four, or more rinsing sequences of the inside of the container (of the composite in the container) with a non-reactive gas followed by the application of a vacuum inside the container, or one, two, three, four, or more vacuum application sequences inside the container followed by the rinsing of the inside of the container with a non-reactive gas.As an option, the final step after one or more sequences can be vacuum sealing of the container, for example, a vacuum-sealed container or package (regardless of the sequence(s) previously applied). Alternatively, the final step after one or more sequences can be rinsing the inside of the container with the non-reactive gas, leaving the composite sealed within the container under an atmosphere comprising at least 90% of at least one gas that is non-reactive with the elastomeric composite. As an alternative, a single or multiple steps of applying a vacuum inside the container (without rinsing with a non-reactive gas) followed by sealing the container. Alternatively, a single or multiple rinsing steps with at least one non-reactive gas (without applying a vacuum) can be performed followed by sealing the container (without applying a vacuum).

[0065] The elastomeric composite in the sealed container or package may be stored for at least 5 days or other periods of time disclosed herein. The storage period may be determined from the time of sealing. As an option, the elastomeric composite may be stored for at least 7 days, at least 2 weeks (14 days), at least 1 month, at least 2 months, at least 3 months, at least 6 months, at least 9 months, or at least 1 year or two years or more, and potentially indefinitely.As another option, the elastomeric composite can be stored for a period of time ranging from 5 days to 2 years, from 5 days to 1 year, from 5 days to 6 months, from 5 days to 3 months, from 2 weeks (14 days) to 2 years, from 2 weeks (14 days) to 1 year, from 2 weeks (14 days) to 9 months, from 2 weeks (14 days) to 6 months, from 2 weeks (14 days) to 3 months, from 21 days to 1 year, from 21 days to 9 months, from 21 days to 6 months, from 21 days to 3 months, from 1 month to 1 year, from 1 month to 9 months, from 1 month to 6 months, from 1 month to 3 months, and other ranges in between.

[0066] As an option, the composite can be stored under low oxygen conditions (modified atmosphere) immediately after mixing or compounding (maximum 15 min. after the composite has been discharged from a mixer or compounder) or a maximum of 1 hour, 2 hours, 3 hours, 6 hours, 1 day, 1 week, or 1 month (30 days) after being unloaded from a mixer or compounder, provided that the composite's degradation is not significant. For example, the composite may be stored in air or under cool conditions prior to packaging or longer-term storage and transport. Alternatively, the composite may be transported in air to a facility where it can be transferred into packaging or other conditions providing low-oxygen storage. As another option, the composite is sealed in the container under air, where the high oxygen barrier wall prevents significant oxygen penetration into the container. Sealing may be carried out in air for a maximum of 1 hour, 2 hours, 3 hours, 6 hours, 1 day, 1 week, or 1 month (30 days) after unloading from a mixer or compounder.

[0067] The elastomeric composite can be stored in the packaging or container at any temperature from 20°C to 200°C. As an option, the packaged composite can be stored under ambient conditions (at temperatures from 20°C to 40°C or from 20°C to 30°C), whether in an air-conditioned environment or in a non-air-conditioned area (e.g. warehouse, truck).

[0068] As an option, the composite can be stored in the container for at least 5 days at elevated temperatures, for example, at a temperature of at least 40°C, such as temperatures ranging from 40°C to 200°C, from 40°C to 180°C, from 40°C to 150°C, from 40°C to 120°C, from 40°C to 100°C, from 40°C to 90°C, from 40°C to 75°C, from 50°C to 200°C, from 50°C to 180°C, from 50°C to 150°C, from 50°C to 120°C, from 50°C to 100°C, from 50°C to 90°C, from 50°C to 75°C, from 60°C to 200°C, 60°C to 180°C, 60°C to 150°C, 60°C to 120°C, 60°C to 100°C or 60°C to 90°C. In certain embodiments, the composite can be stored at elevated temperatures for at least 7 days, at least 2 weeks (14 days), at least 3 weeks (21 days) or at least 1 month up to 6 months or up to 1 year.As an option, storage at high temperatures is carried out for a maximum period of 1 month, a maximum period of 2 weeks or a maximum period of 1 week, for example, storage from 5 days to 1 month.

[0069] As an option, before storage, the composite can be heated, for example, a heat-treated composite under a substantially oxygen-free atmosphere, for example, under an inert gas or under vacuum, where the oxygen concentration in the atmosphere is less than 7%, less than 5%, less than 2%, or less than 1%. Under such conditions, the heat treatment can take place for a period of time of at least 15 min., at least 30 min., at least 1 hour, at least 2 hours, at least 3 hours, at least 6 hours, at least 12 hours, at least 18 hours, or at least 1 day. or for at least 2 days and up to 5 days. Heating may take place at the high temperatures disclosed herein, for example, at temperatures of at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, or at other high temperatures disclosed herein. The upper temperature limit may be determined by the composition of the composite and / or the container used. For example, depending on whether the composites include certain synthetic rubbers (or mixtures containing synthetic rubbers) or a major proportion of natural rubber, the composite may be heated to temperatures up to 200°C, 180°C, 160°C, or 150°C (for example, from 40°C to 160°C).

[0070] The heating or heat treatment may be carried out in a chamber having a substantially oxygen-free atmosphere (e.g., an oven, glove box) or in the container or packaging incorporating the oxygen barrier wall(s). The composite may be heat-treated in an oven, glove box, or other chamber and then transferred to the container or packaging for sealing and storage; the composite may be cooled to ambient temperature (e.g., from 20 to 40°C or from 20 to 30°C) before transfer to the container or transferred while the composite has a high temperature, as determined by the probe temperatures disclosed herein. Alternatively, the composite may be heat-treated in the packaging having the oxygen barrier wall and cooled in the packaging. Depending on the temperature of the composite, a temperature-stabilized vacuum package may be used.

[0071] Accordingly, prior to storage, the process includes the formation of a heat-treated elastomeric composite, comprising heating an uncured elastomeric composite in an oxygen barrier container or packaging, as disclosed herein, to a temperature of at least 40°C for a period of time not exceeding 5 days, wherein the elastomeric composite comprises at least one elastomer and at least one filler, and wherein at least one of the following applies: (i) the inside of the container has a partial pressure of oxygen less than 17 kPa, (ii) the inside of the container has an amount of oxygen not exceeding 10 mmol / kg of elastomeric composite, (iii) the inside of the container has an oxygen concentration of less than 7%, for example, less than 5%, less than 3%, less than 2% or less than 1%.

[0072] As another option, the composite is discharged from the mixer and sealed under a modified atmosphere, for example, having a partial pressure of oxygen below 21 kPa (or other ranges disclosed herein), for example, an atmosphere that contains at least 90% of the non-reactive gas such as an atmosphere nitrogen, or having an oxygen-to-elastomer ratio not exceeding 75 mmol / kg of elastomer composite, or under vacuum (the inside of the container has, for example, an absolute pressure not exceeding 90 kPa). The time period between discharge from the mixer and sealing under a modified atmosphere can be immediate (for example, a maximum of 5 min, 10 min, or 15 min) or not exceed 30 days, for example, not exceeding 2 weeks, not exceeding 1 week, not exceeding 1 day, not exceeding 12 h, not exceeding 6 h, not exceeding 3 h, not exceeding 2 h, not exceeding 1 h, or not exceeding 30 min. The time period is determined with respect to minimizing the amount of composite degradation.

[0073] As an alternative, the composite can be discharged from the mixer (e.g., into an inert gas atmosphere such as nitrogen) and stored or preserved under a modified atmosphere (e.g., discharged, transported, and sealed in packaging, all steps occurring under a modified atmosphere). The composite discharged from the mixer (whether discharged into the modified atmosphere or transferred to the modified atmosphere) can have a probe temperature of up to 200°C (e.g., immediately after discharge from a mixer), depending on the mixing conditions and / or whether the composite is cooled or not.

[0074] The composite probe temperature is usually an overall temperature of the composite and can be measured, for example, by inserting a thermocouple or other temperature measuring device into the composite. As an option, at the time of sealing in the container or packaging, the composite can have a probe temperature ranging from 20°C to 200°C, for example, from 20°C to 180°C, from 20°C to 100°C, from 40°C to 200°C, or from 40°C to 100°C. Typically, upon discharge, the composite can have a probe temperature ranging from 100°C to 180°C. Alternatively, the discharged composite can be subjected to cooling and can have a probe temperature ranging from 20°C to 60°C, for example, from 20°C to 50°C, from 20°C to 50°C, or from 20°C to 60°C.In other variants, the composite has a probe temperature ranging from 30°C to 100°C, for example, from 40°C to 100°C, from 50°C to 100°C, from 60°C to 100°C, from 30°C to 90°C, from 40°C to 90°C, from 50°C to 90°C, from 60°C to 90°C, from 30°C to 60°C, from 40°C to 60°C or from 30°C to 50°C or from 30°C to 40°C.

[0075] The composite elastomer can be considered as an uncured mixture (e.g., unvulcanized or pre-vulcanized) comprising one or more fillers and one or more elastomers, optionally with one or more additives, the additives of which are analyzed in more detail herein. The packaged composite can be considered as a mixture or masterbatch. The composite can optionally be an intermediate product that can be subjected to processes of subsequent hardening or vulcanization to obtain a rubber compound or rubber article.

[0076] The elastomeric composite comprises the filler dispersed in the elastomer. This composite can be prepared in a number of ways, including combining at least one elastomer with at least one filler in a mixer, such as an inter-mesh or tangential mixer (e.g., a Banbury or Brabender mixer), an extruder, a rolling mill, a continuous compounder, or other rubber mixing equipment. The filler(s) and / or the elastomer(s) can be combined in dry or wet form. Dry mixing processes involve mixing a solid elastomer with a filler in a dry state (without wetting or dispersion in a liquid).The combining step may involve or include the supply of a continuous pressurized flow of at least one first fluid that includes at least one filler (a slurry), and a continuous flow of at least one second fluid that includes an elastomeric latex; and the combination of the first and second fluid flows to distribute the filler within the elastomeric latex. The mixed latex and filler slurry may be coagulated to form a wet crust, which is subsequently dehydrated to form the composite. This is also known as the "wet mix" process, which is described in a number of references, including US patents Nos. 4,029,633; 3,048,559; 6,048,923; 6,929,783; 6,908,961; 4,271,213; 5,753,742; 6,521,691 and 8,586,651, whose disclosures are cited for reference. The mixer may be a continuous mixer or another type of mixer.

[0077] As another variant, PCT Publication No. WO 2020 / 247663 A1, the disclosure of which is cited by way of reference, describes a mixing process with a solid elastomer and a wet filler comprising a filler and a liquid. Under the conditions stated in PCT Publication No. WO 2020 / 247663 A1, the mixing results in a composite comprising the filler dispersed in the elastomer, where the liquid content is sufficiently low to permit compounding and optionally additional post-processing steps such as extrusion, calendering, kneading, granulation, baling, compounding, and sheeting. Such compounding and post-processing steps can be carried out on the elastomeric composite independently of the mixing process performed.

[0078] Composites can also be prepared by continuous mixing, as described in PCT publications No. WO 2018 / 219630, WO 2018 / 219631, WO 2020 / 001823 and WO 2020 / 247663, the disclosures of which are cited by way of reference.

[0079] In addition to the filler and the elastomer, the composite may include at least one additive selected from protective agents, coupling agents, adjuvants (to facilitate the mixing and processing of the rubber, for example, various oils and plasticizers, wax), activators (to activate the vulcanization process, for example zinc oxide and fatty acids), accelerators (to speed up the vulcanization process, for example sulfenamides and thiazoles), vulcanizing agents (or hardeners, to crosslink rubbers, for example sulfur, peroxides), and other rubber additives, such as, but not limited to, retarders, co-agents, peptizers, adhesion promoters, tack-giving agents, resins, flame retardants, colorants, and blowing agents.As an option, the composite may not include a vulcanizing agent; instead, the composite may include at least one additive selected from among protective agents, coupling agents, adjuvants, activators, accelerators, retarders, co-agents, peptizers, adhesion promoters (e.g., the use of cobalt salts to promote the adhesion of steel wire to rubber-based elastomers, such as those described in US Patent No. 5,221,559 and US Patent Publication No. 2020 / 0361242, the disclosures of which are cited by reference), resins (e.g., tack-giving agents, tensile resins), flame retardants, colorants, blowing agents, and heat-reducing additives (HBUs). As an option, the rubber chemicals may include adjuvants and activators.As an alternative, one or more rubber chemicals are selected from zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, and processing oil. Examples of resins include those selected from one or more C5 resins, C5-C9 resins, C9 resins, rosin resins, terpene resins, aromatic modified terpene resins, dicyclopentadiene resins, alkylphenol resins, and resins disclosed in US Patent Nos. 10,738,178, 10,745,545, and US Patent Publication No. 2015 / 02838554, the disclosures of which are cited by reference.

[0080] After initial composite formation, for example, with dry mixing, wet mixing, solid elastomer / wet filler mixing, or other mixing processes, the composites may optionally be compounded with additional ingredients such as one or more protective agents, zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, coupling agents, and processing oil. As an option, the composite, prior to compounding (if applicable), may contain protective agents that were added during the initial mixing processes in which a filler was mixed and dispersed within the elastomer. Because protective agents may react with oxygen to prevent rubber degradation, they may also be considered a type of deoxygenating agent.Protective agents (e.g., antioxidants) may be present in the composite in an amount ranging from 0.5% to 5%, 1% to 5%, 0% to 3%, 1% to 3%, 0% to 2%, 0.5% to 2% or 1% to 2% based on the weight of the composite. composite. In other words, protective agents (e.g., antioxidants) may be present in the composite (either after initial mixing or after compounding) in an amount ranging from 0.5 pcc to 3 pcc, from 0.5 pcc to 2 pcc, 1 pcc to 10 pcc, from 1 to 5 pcc, from 1 pcc to 3 pcc or from 1 pcc to 2 pcc.

[0081] As an option, the composite may include vulcanizing agents (or curing agents or hardeners, for crosslinking rubbers, for example, sulfur, peroxides) in addition to any other additive disclosed herein, for example, "green compounds." With or without the vulcanizing (curing) agents, the composite that is packaged according to the parameters and processes disclosed herein is considered uncured until it is subjected to vulcanizing processes.

[0082] As an option, storing or packaging the composite in the oxygen-barrier containers disclosed herein may allow the composite to be substantially free of any protective or antioxidant agent. Oxidation or reaction with oxygen is a factor in the degradation of elastomeric composites. The removal of oxygen may render the addition of protective or antioxidant agents unnecessary. As an option, the composite that is substantially free of any protective agent may contain a protective agent in an amount not exceeding 1% by weight of the composite, for example, not exceeding 0.5%, not exceeding 0.3%, not exceeding 0.2%, or not exceeding 0.1%, for example, from 0.1% to 1%, from 0.2% to 1%, from 0.1% to 0.5%, from 0.2% to 0.5%, from 0.1% to 0.3%, from 0.1% to 0.1% by weight of the composite.In other words, the composite contains one or more protective agent(s) in an amount ranging from 0 pc to 0.5 pc, from 0.1 pc to 0.5 pc, from 0.2 pc to 0.5 pc, from 0 pc to 0.3 pc, from 0.1 pc to 0.3 pc, from 0 pc to 0.2 pc, or from 0 pc to 0.1 pc. In formulations that are substantially free of protective agents (e.g., substantially free of antioxidants), the formulation may optionally include one or more other additives, such as zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, coupling agents, processing oils, and / or vulcanizing agents.

[0083] As an option, the uncured composite essentially consists of the filler dispersed in the elastomer, or the uncured composite essentially consists of the filler dispersed in the elastomer and the protective agent. As another option, the uncured composite essentially consists of the filler dispersed in the elastomer and the bonding agent, or the uncured composite essentially consists of the filler dispersed in the elastomer and the protective agent and the bonding agent.

[0084] In certain embodiments, the composite may have excessive moisture, such as composites manufactured according to PCT Publication No. WO 2020 / 247663. By For example, the composite may have a moisture content ranging from 3% to 20%, 4% to 20%, 5% to 20%, 3% to 10%, 4% to 10%, 5% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, or 3% to 5%. Without a protective agent, these composites are susceptible to mold growth. Containers and packaging with an oxygen barrier wall can allow the storage of these composites with excessive moisture (even when they are largely free of protective agents) since the low oxygen content inside the packaging can reduce the extent of mold growth (if any).

[0085] When packaging or storing the elastomeric composite in containers comprising the oxygen barrier walls disclosed herein, the composite may be stored for at least 5 days, at least 1 week, at least 2 weeks, at least 3 weeks, at least 4 weeks, at least 3 months, at least 6 months, at least 9 months (for example, from 5 days to 2 years or from 5 days to 1 year or other periods of time disclosed herein), where such composites may be designated as aged or stored composites.

[0086] The resulting stored or aged composite and / or rubber compounds made from the stored or aged composite may exhibit similar properties (retain at least one rubber property) or even enhanced or improved rubber properties after storage compared to the properties at the time of sealing (packaging) and / or compared to composites that have been stored or aged under ambient conditions (e.g., ambient partial pressure of oxygen, ambient absolute pressure, etc., such as composites stored in air). The corresponding compounds made from these stored composites may also provide similar or even enhanced properties compared to compounds made from composites at the time of sealing and / or compared to compounds made from composites that have been stored or aged under ambient conditions (e.g., stored in air).At the time of sealing, composite samples may be subjected to various measurement techniques or compounds to form rubber compounds whose properties are measured or obtained. These measured composite properties at the time of packaging would constitute a control sample (rubber compounds formed from the control sample composite would be a control rubber compound). After storage and aging for a period of time, such as the time periods disclosed herein, samples of the aged or stored composite may be used, and the properties of the resulting compound may then be measured or obtained.

[0087] In some cases, the properties of the rubber are maintained, for example, with a degradation of properties not exceeding 10%, 5%, 3%, 2%, or 1% of the value at the time of packaging or sealing. In other examples, the aged or stored composite and the corresponding compounds made from the aged or stored composite exhibit enhanced values. The enhancement can be seen as an increase in the properties of the rubber of at least 5% or at least 10% compared to the properties at the time of sealing or packaging and / or compared to composites that have been stored or aged under ambient conditions (as well as for corresponding compounds made from such composites).The reinforcement can be an advantageous decrease in value (e.g., Payne effect or Payne ratio of the composite or corresponding rubber compound or hysteresis of the rubber compound as indicated by a maximum tan θ value) or an advantageous increase in properties such as tensile strength, tensile stress or modulus ratio of the corresponding compound.

[0088] For example, the rheological properties of the composite (and of compounds formed from such composites) can be enhanced by storing the composite in the high oxygen barrier containers disclosed herein. An example of such a property is the Payne effect of the (unvulcanized) composite, which can be indicated by the Payne ratio or the Payne difference. The Payne ratio is defined as G'(0.3%) / G'(51.5%), where G'(0.3%) is a dynamic storage modulus measured at a strain amplitude of 0.3% and G'(51.5%) is a dynamic storage modulus measured at a strain amplitude of 51.5%. The Payne difference is the difference between G'(0.3%) and G'(51.5%). The rheological properties of the composite, such as the Payne ratio of the composite, can be measured before and after storage of the composite for different periods of time, provided that the measurement is carried out before vulcanization.In some cases, after a period of at least 5 days (for example, at least 14 days) from the sealing or storage of the packaging or container (or manufacture of the composite), for example, at temperatures of at least 25°C, or at least 30°C, at least 40°C, at least 50°C, or at least 60°C, the elastomeric composite has a Payne ratio, as defined by G'(0.3%) / G'(51.5%), which is reduced by at least 10% (for example, at least 15% or at least 20%) compared to the Payne ratio of the composite on day 0 of the packaging sealing. As an option, the composite has a Payne ratio of at least 1, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5 or at least 2, for example, a Payne ratio ranging from 1 to 15, from 1 to 12, from 1.5 to 15, from 1.5 to 12, from 2 to 15 or from 2 to 12.

[0089] For example, the properties of the hardened compound (formed from such aged or stored composites) can be enhanced as indicated by the properties of the rubber compound, for example, rheological properties such as a decrease in the Payne ratio (of at least 10%), defined above, or a decrease in the hysteresis (of at least 10%) of the rubber compound as indicated by the maximum tan θ value, or an increase of at least 10% in mechanical properties such as a modulus ratio or tensile stress ratio, which is the ratio of the tensile stress at 300% elongation (M300) to the tensile stress at 100% elongation (M100), i.e., M300 / M100.

[0090] The composite can be packaged after mixing and dispersing the filler in the elastomer or after additional mixing phases in which the composite is compounded with one or more additives (e.g., protective agents, coupling agents, adjuvants, activators, accelerators, vulcanizing agents, as described in more detail herein) as long as the composite is uncured. The composite can be packaged immediately after discharge from a mixer or after a period of time and at a temperature as disclosed herein, with minimal degradation.

[0091] When packaging composites exhibiting high overall and probe temperatures, the packaging or container may be chosen to withstand such hot-fill processes. Shrinkage or other deformation may occur when the composite cools within the packaging, particularly when the internal volume of the packaging is under reduced pressure, for example, under vacuum. Hot-fill packages are typically flexible and designed to deform upon cooling. A temperature-stabilized vacuum package may also be used. Alternatively, the packaging may be very rigid, such as a high-Tg plastic, or a thick-walled package (for example, walls more than 250 µm thick), or a metal container.

[0092] The filler(s) and the elastomer(s) that form the composite can be any filler and any elastomer known in the industry. Elastomers include natural rubber (NR), functionalized natural rubber, synthetic elastomers such as styrene-butadiene rubber (SBR, e.g., solution SBR (SSBR), emulsion SBR (ESBR) or oil-extended SSBR (OESSBR)), functionalized styrene-butadiene rubber, polybutadiene rubber (BR), functionalized polybutadiene rubber, polyisoprene rubber (IR), ethylene-propylene rubber (EPDM), isobutylene-based elastomers (e.g., butyl rubber), halogenated butyl rubber, polychloroprene rubber, nitrile rubbers (NBR), hydrogenated nitrile rubber (HNBR), polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, Silicone elastomers and mixtures thereof. Other synthetic polymers that may be used in these processes (alone or in mixtures) include hydrogenated SBR and thermoplastic block copolymers (e.g., such as those that are recyclable). Synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene, and isoprene. Other synthetic elastomers include those synthesized with a metallocene composition 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-derived monomers may also be used, such as contemporary carbon-containing monomers as defined by ASTM D6866, for example, polymers made from bio-derived styrene monomers disclosed in US patent no. 9,868,853, the disclosure of which is cited by reference, or polymers made from bio-derived monomers such as butadiene, isoprene, propylene, famesene and co-monomers thereof.

[0093] As an option, the composite may include at least one elastomer that is subject to degradation upon exposure to oxygen, such as diene-based elastomers, which include natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, and mixtures thereof. The composite may further include other elastomers that are not appreciably sensitive to oxygen, as known in the art. As another option, the at least one elastomer includes natural rubber (for example, at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% natural rubber) and may further include at least one synthetic elastomer.As an option, at least one elastomer comprises natural rubber and further comprises at least one additional elastomer such as styrene-butadiene rubber, butadiene rubber, isoprene rubber or any of the elastomers known in the art or disclosed herein.

[0094] Any filler known in the art of elastomeric composites may be used. The filler may be particulate, fibrous, or plate-like. For example, a particulate filler is composed of discrete bodies. 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, for example, an aspect ratio of 2:1 or more, 3:1 or more, or 4:1 or more, or higher.

[0095] The filler may comprise at least one material selected from carbonaceous materials, carbon black, silica, fillers of biological origin such as nanocellulose and lignin, clays, nanoclays, metal oxides, metal carbonates, fillers derived from recycled materials including pyrolytic carbon, reclaimed carbon and recovered carbon black (e.g., as defined in ASTM D8178-19, rCB), graphene, graphene oxides, reduced graphene oxide (e.g., reduced graphene oxide coils as disclosed in PCT Publication No. WO 2019 / 070514A1, or densified reduced graphene oxide granules as disclosed in US Provisional Patent Application No. 62 / 857,296 filed June 5, 2019, and PCT Publication No. WO 2020 / 247681, the disclosures of which are cited by reference), carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures (CNS), carbon nanostructure fragments, fractured multi-walled carbon nanotubes (as disclosed in PCT application no. PCT / US2021 / 27814, the disclosure of which is cited by reference) or combinations thereof,or corresponding coated materials or chemically treated versions thereof (e.g., chemically treated carbon black).

[0096] Other suitable fillers include carbon nanostructures (CNS, CNS singular), a plurality of carbon nanotubes (CNTs) that are cross-linked into a polymer structure by being branched, for example, dendrimerically, interdigitated, intertwined, and / or sharing common walls with one another. CNT fillers are described in US Patent No. 9,447,259 and PCT Publication No. WO 2021 / 247153, the disclosures of which are cited by reference. Filler mixtures may also be used, for example, mixtures of silica and carbon black, silica and silicon-treated carbon black, and carbon black and silicon-treated carbon black. The filler may be chemically treated (for example, chemically treated carbon black, chemically treated silica, silicon-treated carbon black) and / or chemically modified. The filler may be or include carbon black having one or more attached organic groups.The filler may have one or more coatings (e.g., silicon-coated materials, silica-coated materials, carbon-coated materials). The filler may be oxidized and / or have other surface treatments. There are no limits to the type of filler (e.g., silica, carbon black, or other filler) that can be used.

[0097] The filler may include a fibrous filler comprising natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nanometric carbon filaments), such as the short fibers disclosed in PCT Publication No. WO 2021 / 153643, the disclosure of which is cited by way of reference. Other fibrous fillers include poly(p-phenylene terephthalamide) pulp, commercially available as Kevlar® pulp (DuPont).

[0098] Other bio-based or biologically derived materials (derived from biological sources), recycled materials, or other fillers considered to be renewable or sustainable include hydrothermal carbon (HTC, where the filler comprises lignin that has been treated by hydrothermal carbonization as described in US patents Nos. 10,035,957 and 10,428,218, the disclosures of which are cited by reference), rice hull silica, carbon from methane pyrolysis, modified polysaccharide particles, starch, silica earth, rubber powder, and functionalized rubber powder. Examples of modified polysaccharides include those described in US patent publications Nos. 2020 / 0181370 and 2020 / 0190270, the disclosures of which are cited by reference.For example, the polysaccharides may be chosen from: poly alpha-1,3-glucan; poly alpha-1,3-1,6-glucan; a water-insoluble alpha-(l,3-glucan) polymer having 90% or more α,3-glycosidic linkages, less than 1% by weight of alpha-l,3,6-glycosidic branch points, and an average number degree of polymerization in the range of 55 to 10,000; dextran; a composition comprising a poly alpha-1,3-glucan ester compound; and water-insoluble cellulose having an average weight degree of polymerization (DPw) of about 10 to about 1,000 and a cellulose II crystal structure. As an option, at least one filler is chosen from rice hull silica, lignin, nanocellulose, and hydrothermal carbon.

[0099] There are no limitations as to the type of filler (e.g., silica, carbon black, or other filler disclosed herein) that may be used, including bio-based (derived from a biological source) and recycled (e.g., reclaimed carbon) materials. Examples of coated fillers include those described in US Patent No. 10,519,298, the disclosure of which is cited by reference. Examples of chemically treated fillers include fillers (e.g., carbon black) to which at least one organic group is attached (e.g., via a diazonium reaction) as described, for example, in US Patent Nos. 5,554,739; 5,630,868; 5,672,198; 5,707,432; 5,851,280; 5,885,335; 5,895,522; 5,900,029; 5,922,118, whose disclosures are cited for reference.

[0100] The filler may comprise silicon-treated carbon black, a silicon-containing species such as silicon oxide or silicon carbide, which is distributed throughout at least a portion of the carbon black aggregate as an intrinsic part of the carbon black. Silicon-treated carbon blacks are not carbon black aggregates that have been coated or otherwise modified, but are in fact two-phase aggregate particles. One phase is carbon, which will still be present as graphitic crystallite 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 intrinsic part of the aggregate, distributed throughout at least a portion of the aggregate. Ecoblack™ silicon-treated carbon blacks are available from Cabot Corporation. The manufacture and properties of these silicon-treated carbon blacks are described in U.S. Patent No. 6,028,137, the disclosure of which is cited herein by reference. Silicon-treated carbon black may include silicon-containing regions primarily at the aggregate surface of the carbon black, but still forming part of the carbon black, and / or silicon-treated carbon black may include silicon-containing regions distributed throughout the carbon black aggregate. Silicon-treated carbon black can be oxidized.

[0101] At least one filler (for example, carbon black, silica, silicon-treated carbon black, or any other fillers and combinations thereof disclosed herein) may be dispersed in at least one elastomer at a loading from 20 pcc to 250 pcc, for example, from 20 pcc to 240 pcc, from 20 pcc to 230 pcc, from 20 pcc to 220 pcc, for example from 20 pcc to 180 pcc, from 20 pcc to 150 pcc, from 20 pcc to 120 pcc, from 20 pcc to 100 pcc, from 20 pcc to 80 pcc, from 20 pcc to 60 pcc, from 30 pcc to 100 pcc, from 30 pcc to 80 pcc, from 30 pcc to 60 pcc, from 40 pcc to 100 pcc, from 40 pcc to 80 pcc or from 40 pcc to 60 pcc.Certain carbon-based nanomaterials, such as graphene, graphene oxides, reduced graphene oxide carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon nanostructure fragments, fractured multi-walled carbon nanotubes, may be dispersed in at least one elastomer at loadings of at least 0.1 pcc, alone or with one or more non-carbon-based nanomaterials, such as carbon black, silica, silicon-treated carbon black, and other fillers and combinations as disclosed herein.Carbon-based nanomaterials can be dispersed in at least one elastomer at loadings ranging from 0.1 pcc to 50 pcc, from 0.5 pcc to 50 pcc, from 0.5 pcc to 40 pcc, from 0.5 pcc to 30 pcc, from 0.5 pcc to 20 pcc, from 0.5 pcc to 10 pcc, from 0.5 pcc to 5 pcc, from 0.5 pcc to 3 pcc, from 0.5 pcc to 2 pcc, from 0.5 pcc to 1 pcc, from 1 pcc to 20 pcc, from 1 pcc to 10 pcc, from 1 pcc to 5 pcc, from 1 pcc to 3 pcc or from 1 pcc to 2 pcc. Other ranges may be considered, such as ranges disclosed in PCT Publication No. WO 2020 / 247663, PCT Publication No. WO 2019 / 070514A1, and PCT Application No. PCT / US2021 / 27814, the disclosures of which are cited by reference.

[0102] As an option, at least one elastomer in the elastomer composite comprises at least 30% natural rubber (for example, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% natural rubber) and at least one filler in the elastomer composite includes at least 50% carbon black (for example, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% carbon black).

[0103] When the filler includes carbon black, for example, at least 20% at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% carbon black, or when the filler is substantially entirely carbon black, the uncured composite may be the product formed by incorporating at least one bonding agent. For example, the composite may be prepared by mixing at least one filler, an elastomer (or latex elastomer), and at least one bonding agent, or the composite may further comprise at least one bonding agent.Composites prepared in the presence of certain bonding agents, such as those disclosed in PCT Application No. PCT / US21 / 62433, filed on December 8, 2021, the disclosure of which is cited by reference, may exhibit reduced degradation over time, for example, over at least 5 days, at least 1 week, at least 2 weeks, at least 1 month (at least 30 days), at least 2 months, at least 30 months, or even at least 6 months (at least 180 days) up to 1 year (12 months) or even up to 2 years at temperatures of at least 20°C. Such reduced degradation may be at least partially in addition to the benefits obtained from the storage / packaging processes disclosed herein.As an option, the composite further comprises at least one bonding agent, e.g., an uncured composite or masterbatch comprising a filler and an elastomer has been prepared according to any process known in the art and subsequently subjected to one or more compounding or other treatment steps with at least one bonding agent and optionally at least one additive (e.g., a protective agent or other additives disclosed herein) prior to vulcanizate formation.

[0104] As an option, the linking agent(s) may be chosen from compounds having at least two functional groups, in which: a first functional group is chosen from -NR*R2, -N(R')(R2)(R3)+A , -S-SO3M', and structures represented by formula (I) and formula (II), in which A is chloride, bromide, iodide, hydroxyl, nitrate, or acetate, X = NH₄⁺, O₂, or S, Y = H₂, OR₄, NR₄R₅, -SnR₄, and n is an integer chosen from 1 to 6, and a second functional group is chosen from thiocarbonyl, nitrile oxide, nitrone, nitrile imine, S-SO3M2, -Sx-R6, -SH, -C(R6)=C(R7)-C(O)R8, -C(R6)=C(R7)-CO2R8, -C(R6)=C(R7)-CO2M2 and R'-R8 are each independently chosen from H and CrC8 alkyl; M1 and M2 are each independently chosen from H, Na+, K+, Li+, N(R')4+ in which each R' is independently chosen from H and CrC2o alkyl, and x is an integer chosen from 1 to 8.

[0105] Regardless of any theory, it is estimated that while the mixing process with a wet filler can improve filler dispersion, the bonding agent can interact with the filler and / or the elastomer to create a stronger interaction between the filler and the elastomer. As an option, the bonding agent may have at least two functional groups, the first and second of which can interact with the elastomer and / or the filler. The interaction may involve adsorption or chemical bonding, for example, through ionic interactions, dipole-dipole interactions, hydrogen bonding, covalent bonding, etc. In the composite, the bonding agent may be present in the same form as that loaded onto the mixer or in a different form, for example, in the case of interaction with the filler and / or the elastomer through chemical bonding.

[0106] The liaison agent comprising at least two functional groups may include two, three, four or more functional groups. In any of these embodiments, the liaison agent comprises a first functional group which may be chosen from -NR'R2, -N^'XR^RVA, -S-SO3M', and structures represented by formula (I) and formula (II), in which A is chloride, bromide, iodide, hydroxyl, nitrate or acetate, X = NH, O or S, Y = H, OR4, NR4R5 or -SnR4, and n is an integer chosen from 1 to 6. In some aspects, the first functional group can be chosen from -NR'R2 (e.g., -NHR1 or -NH2), -CO2M' and -S-SO3M*.

[0107] The linker may further include a second functional group, which may be selected from thiocarbonyl, nitrile oxide, nitrone, nitrile imine, -S-SO3M2, -Sx-R6, -SH, -C(R6)=C(R7)-C(O)R8, -C(R6)=C(R7)-CO2R8, -C(R6)=C(R7)-CO2M2. In some aspects, the second functional group may be selected from -S-SO3M2 and -CR6=CR7-CO2M2. When the functional group is -CO2M' and -S-SO3M', -S-SO3 M2 and -CR6=CR7-CO2M2, these can be chosen from acids or salts of these, e.g., M1 and M2 are each independently chosen from H, Na+, K+, Li+ and N(R')4+ (e.g., ammonium salts where each R' is independently chosen from H and Ci-C20 alkyl, such as CrCi2 alkyl or Ci-C6 alkyl or C1-C4 alkyl, e.g., monoalkyl, dialkyl, trialkyl or tetralkyl ammonium salts).When the linker contains two or more M1 groups or two or more M2 groups, each M1 or M2 can be chosen independently from H, Na+, K+, Li+ and N(R')4+.

[0108] In the embodiments described herein, R'-R8 are each independently chosen from H and CrC8 alkyl; M1 and M2 are each independently chosen from H, Na+, K+, Li+, N(R')4+; and x is an integer chosen from 1 to 8.

[0109] As an option, the first functional group is capable of interacting with carbon black. The carbon black may have one or more types of surface functional groups such as, but not limited to, oxygen-containing groups such as carboxylic acids (and their salts), hydroxyl groups (e.g., phenols), esters or lactones, ketones, aldehydes, anhydrides, and benzoquinones. As another option, the second functional group is capable of interacting with the solid elastomer. The solid elastomers may be natural elastomers, synthetic elastomers, and mixtures thereof.For example, solid elastomers can be 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 mixtures thereof. As an option, the solid elastomer can be selected from natural rubber, styrene-butadiene rubber, and polybutadiene rubber. The solid elastomer may contain olefin groups and / or may be functionalized with a number of groups.

[0110] As an option, the first functional group can be chosen from -NR*R2 (for example, -NH2) and -S-SO3M' and the second functional group can be chosen from -S-SO3M2 and -CR3=CR4-CO2M2.

[0111] The linking agent may comprise more than two functional groups. With such linking agents, each additional functional group, for example, a third, a fourth, etc., functional group, may be selected from the list of first and second functional groups as disclosed herein. As an option, more than one type of linking agent may be used to prepare a composite.

[0112] The linker may further comprise at least one spacer between the first and second functional groups. For example, one or more spacers may be linked to each other and ultimately to the first and second functional groups. As an option, the at least one spacer is chosen from -(CH2)n-, -(CH2)yC(O)-, -C(R9)=C(R10)-, -C(O)-, -N(R9)- and -C6H4-, where y is an integer chosen from 1 to 10 and R9 and R10 are each independently chosen from H and alkyl in Ci-C6.

[0113] Examples of linking agents are chosen from compounds of formula (1), formula (2) and formula (3), (1) H2N-(CH2VSSO3M2 (2) M^S-SyCHs^-S-SOyM2 (3). M1 and M2 are as defined herein, R6 and R7 are chosen independently from H and CrC8 alkyl (e.g., chosen independently from H and Ci-C6 alkyl or chosen independently from H and CrC4 alkyl). Alternatively, M1 and M2 are each chosen independently from H, Na+, and N(R')4+, e.g., from H and Na+, and R6 and R7 are identical, e.g., R6 and R7 are each H. An example of a linker of formula (1) is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, commercially available as Sumilink® 200 coupling agent, and an example of a linker of formula (2) is S-(3-aminopropyl)thiosulfuric acid, commercially available as Sumilink® 100 coupling agent (Sumitomo). An example of a bonding agent of formula (3) is commercially available as a Duralink™ HTS tire additive (Eastman Chemical Co.). Other bonding agents include cystamine and thiourea.

[0114] As an option, the uncured composite is a mixture product of at least one filler, an elastomer (or latex) and at least one bonding agent, for example, during a first mixing process phase with the filler and the elastomer (or latex), or in combination with a coagulum resulting from the mixing of a filler slurry and latex, or during the compounding of a composite (productive or non-productive) and / or other treatment of an uncured composite. Examples of composites and processes for forming such composites containing bonding agents are disclosed in US patents Nos. 9,365,497, 10,208,137, 10,343,455, 10,793,702, 10,889,685 and US publications Nos. 2018 / 0105654, 2019 / 0218350, 2019 / 0144634, 2019 / 0241723 and PCT application No. PCT / US21 / 62433 filed on December 8, 2021, the disclosures of which are cited by reference. For example, uncured composite is the product of known dry mixing processes, e.g., mixing of filler, elastomer and at least one bonding agent.As another example, the uncured composite is a product of mixing (in one or more mixing steps) at least one solid elastomer, wet filler, and bonding agent to form a mixture, and removing at least some of the liquid from the mixture by evaporation, or as described in PCT Application No. PCT / US21 / 62433, filed on December 8, 2021, the disclosure of which is cited by reference. As another example, the uncured composite is prepared by mixing a wet filler and a solid elastomer, as described in PCT Publication No. WO 2020 / 247663 A1, the disclosure of which is cited by reference, and further combined with at least one bonding agent as described in PCT Application No. PCT / US21 / 62433 filed on December 8, 2021, the disclosure of which is cited by reference.The amount of bonding agent added to the composite, coagulum or compound, or loaded into the mixer (or by any of the processes disclosed herein) may be 10% or less, for example, 6% or less, 5% or less, 4% or less, 3% or less or 2% or less, for example, an amount from 0.1% to 10%, from 0.1% to 8%, from 0.1% to 6%, from 0.1% to 5%, from 0.1% to 4%, from 0.1% to 3% or from 0.1% to 2%, or other amounts as disclosed in PCT Application No. PCT / US21 / 62433, filed on December 8, 2021, the disclosure of which is cited by reference.

[0115] The elastomeric composite can be stored in any form, for example, sheets, blocks, or small pieces such as chips, for example, balls of such small pieces such as a ball of chips. Small pieces of composite can be formed by means of a granulator, as disclosed in US Patent No. 7,341,141, the disclosure of which is cited by reference. The shape of the elastomeric composite can affect the amount of oxygen present in the container. For example, a ball of randomly arranged chips can have a porosity of at least 25%.

[0116] When mixing telastomer with the filler, some degradation of the rubber may occur. In some cases, elastomeric composites exhibiting Dispersed fillers such as carbon black, silica, silicon-treated carbon black, or any fillers disclosed herein, may benefit from the containers, packaging, and / or storage methods disclosed herein. The distribution and dispersion of the filler within the elastomeric network may be indicated by a "dispersion state" or macrodispersion. As an option, macrodispersion may be indicated by a "d90" particle size distribution, in which particle sizes are determined by measuring the percentage surface area contribution from particles > 2 pm. The surface area contribution from particles may be reported per image area, and a total image area (pm²) of an image may be determined from the number of pixels and the image resolution.An image can have width and height dimensions, each expressed in pixels, and the corresponding area can be expressed in (pixels)2. For an area, the resolution can be expressed in (pm / pixel)2. The imaging area is the product of: . (surface) * (resolution).

[0117] As an option, d90 is the equivalent surface diameter (pm) of the filler particles in the composite, where d90 does not exceed 100 pm, for example, does not exceed 90 pm, does not exceed 80 pm, does not exceed 70 pm, does not exceed 60 pm, does not exceed 50 pm or does not exceed 40 pm, does not exceed 30 pm, does not exceed 20 pm or does not exceed 10 pm.

[0118] As an option, the composite has a G'(10%) of at least 50 kPa, for example, of at least 100 kPa or of at least 200 kPa, for example, the G'(10%) ranges from 50 to 1500 kPa, from 100 to 1500 kPa, from 200 to 1500 kPa, from 100 to 1000 kPa or from 200 to 1000 kPa, in which the G'(10%) is a dynamic storage modulus measured at a strain amplitude of 10%. EXAMPLES

[0119] The following tests were used to obtain performance data on each of the vulcanizers: The tensile stress at 100% elongation (M100) and the tensile stress at 300% elongation (M300) were evaluated according to ASTM D412 (Test Procedure A, Die C) at 23 °C, 50% relative humidity, and a rate of 500 mm / min. Extensometers were used to measure the tensile strain. The ratio M300 / M100 is referred to as the tensile stress ratio (or modulus ratio). - The maximum tan θ was measured with an ARES-G2 or ARES 2K rheometer (manufacturer: TA Instruments) using a parallel plate geometry with a diameter of 8 mm in torsion mode. The vulcanized specimen was 8 mm in diameter and approximately 2 mm of thickness. The rheometer was used at a constant temperature of 60 °C and a constant frequency of 10 Hz. Strain sweeps were performed from a strain amplitude of 0.1–63%. Measurements were taken at ten points per decade, and the maximum measured tan θ (“tan θ max”) was reported, also referred to as “tan θ” unless otherwise specified. The Payne ratio of the compound was calculated from the ratio of the dynamic storage modulus G' at a strain of 0.1% to G' at a strain of 50%, namely G'(0.1%) / G'(50%). - Rheological properties were determined using a rubber process analyzer (RPA; D-RPA 3000, MonTech Rubber Testing Solutions). A 5 g sample was cut from rubber composites. The temperature was set at 100 °C, and a shear frequency of 1 Hz was used throughout the test procedure. The test program consisted of a static test for 5 minutes, followed by 10 shear cycles at 50% strain, then 30 minutes at 0.3% strain, and finally a strain sweep from 0.3% to 51.5% strain. The Payne ratio of the compound was calculated from the ratio of the dynamic storage modulus G' at 0.3% strain to G' at 51.5% strain, i.e., G'(0.3%) / G'(51.5%). Example 1

[0120] This example describes the results of storing different parts of the same elastomer composite under air, nitrogen and vacuum, where the elastomer composite was prepared by a liquid mixing process.

[0121] The composite was prepared by the liquid process of US Patent No. 8,586,651, Example 2, except as described herein. The elastomeric latex (diluted MVL Field Latex with sludge removed) had a dry rubber content of 28 wt%, and the filler slurry contained 13-14 wt% carbon black (Propel® E7 Carbon Black, "E7"; Cabot Corporation). Flow rates were adjusted to produce a final carbon black loading of 55 wt% at the desired production rate. The average carbon black loading level of the resulting composite was 55 wt%. The dehydrated composite was masticated, mixed with 2 pcc of antioxidant (6PPD) and dried in a continuous mixer (Farrell Unimix (FCM) continuous mixer, equipped with two #15 rotors; operating at 190-320 rpm, Farrel Corporation, Ansonia, CT) and masticated again, cooled and dried in a roller mixer.

[0122] The composite was formed into fries by processing a 90 mm strip through a granulator to form smaller pieces approximately 80 mm long by 8 mm wide by 8 mm thick. Strip-cutting methods with a granulator are disclosed in US Patent No. 7,341,142, the disclosure of which is cited by reference. The fries were then separated into a number of samples that were stored according to a set of conditions set out in Table 3.

[0123] After storage, all the elastomeric composites were compounded in a 300 mL CW Bradbender internal mixer equipped with cams according to the formulation shown in Table 1 and the protocol shown in Table 2. The BBTS accelerator was (N-tert-butyl-2-benzothiazole sulfenamide) from Akrochem, Akron, Ohio. The compounding conditions were: starting temperature = 40 °C; rotor speed = 60 rpm; fill factor = 60%. [Tables 1] Formulation (pc) For elastomeric composite Latex NR 100 CB E7 55 6PPD 2 For compounding Elastomeric composite 157 Zinc oxide 4 Stearic acid 2 6PPD 0.5 Accelerator BBTS 0.8 Sulfur 1.2 [Tables 2] Time(s) Description 0 Add the elastomer composite, start the timer 120 Add the zinc oxide, 6PPD, and stearic acid 240 Add the BBTS and sulfur 300 Empty - check the temperature and weight of the compound

[0124] The compounds were then rolled into sheets on a 2-roller operating at 50 °C at a speed of 10.5 m / min, followed by four passes (wound end to end) through the rolling mill with a gap between rolls of approximately 5 mm. The samples were cured in a press heated to 150 °C for 30 min.

[0125] Table 3 sets out the storage conditions for each composite (before compounding) and the properties of the composite and the resulting compounds (vulcanizates). "Time" in Table 3 refers to the number of days the sample was stored under the conditions indicated.

[0126] In Table 3, "Atm" indicates whether the sample was stored in air, under nitrogen ("N2"), or under vacuum ("Vacuum"). For samples stored under vacuum, the composites were placed in metallized bags (Marvelseal® 360 barrier film from Berry Global Inc., a biaxially oriented sealing layer (nylon / PE / aluminum foil / PE / LLDPE); total film thickness = 132 µm; oxygen transmission rate = 0.009 cm³ / (m²-day-atm) at 0% relative humidity (RH), 73°F). Within three hours of composite production, the bags were rinsed with nitrogen, evacuated to a pressure of 84.7 kPa, and sealed. For samples stored under nitrogen, within three hours of production, the composites were placed in metallized bags, evacuated, rinsed with nitrogen, and sealed at ambient pressure. The gas rinsing and evacuation steps were performed using an AmeriVacs AVN vacuum heat sealer with a shrink nozzle.

[0127] In Table 3, "Temp" refers to the storage temperature of the composite. "60 °C" refers to samples stored at 60 °C (50% relative humidity), achieved by placing the samples in an oven (including samples stored in a bag). After storage for the specified time at 60 °C, the samples are allowed to equilibrate at room temperature overnight before compounding. "20 °C" refers to samples stored in air-conditioned rooms with a temperature control of 20 ± 3 °C.

[0128] The properties of the reference composite were measured before sealing (Day = 0, i.e., no storage). The values ​​in Table 3 reported for samples stored under air conditioning are average values ​​obtained from six samples. The values ​​reported for samples stored at 60 °C are average values ​​obtained from four samples. All reported properties relate to vulcanizates, except where indicated that they relate to composites, indicated by "(C)". [Tables 3] Tem PS (days) At m Tem P Rapp ort Payne( C) G'0.3%, kP a(C) G'51.5%, kPa (C) tan ô m ax Ml 00 (MP a) M30 0(M Pa) M30 0 / M10 0 Rapp ort Payne G'0.1%, M Pa G'50%, M Pa 0 Air 20° C 2.9 999 341 0.13 6 3.0 19.1 6.3 3.2 4.5 1.4 60 Air 20° C 3.3 1107 337 0.13 7 3.1 18.6 6.0 3.4 5.3 1.6 90 Air 20° C 3.6 1234 345 0.14 2 3.1 18.7 6.0 3.4 5.3 1.6 60 N2 20° C 2.9 1046 363 0.12 6 2.9 18.8 6.5 2.9 4.3 1.5 90 N2 20° C 2.8 1029 369 0.12 8 2.7 17.7 6.4 2.9 4.0 1.4 60 vid e 20° C 2.9 1056 368 0.12 1 2.9 18.7 6.4 2.8 4.4 1.5 90 vid e 20° C 2.9 1050 361 0.12 4 2.9 18.6 6.4 2.8 4.0 1.4 2 At 60° C 3.1 1040 339 0.14 8 2.7 18.5 6.7 3.3 4.3 1.3 5 At 60° C 3.1 1046 337 0.15 2 2.9 18.3 6.3 3.5 4.7 1.3 7 At 60° C 3.3 1115 333 0.15 4 2.9 18.6 6.4 3.5 4.6 1.3 14 At 60° C 3,6 1144 318 0,16 3 2,9 18,5 6,4 3,7 4,6 1,2 21 At 60° C 3,9 1219 316 0,15 9 3,1 18,7 6,1 3,8 5,5 1,5 2 N2 60° C 2,8 1057 372 0,13 2 2,9 19,5 6,7 3,0 4,1 1,4 5 N2 60° C 2,7 1033 377 0,12 6 2,8 18,3 6,6 2,8 3,7 1,3 7 N2 60° C 2,8 1070 381 0,13 2,9 19,4 6,7 2,9 3,8 1,3 14 N2 60° C 2,8 1077 390 0,12 7 2,9 19,8 6,9 2,8 3,7 1,3 21 N2 60° C 2,9 1084 379 0,12 2 2,8 19,3 6,9 2,7 3,4 1,2 2 at e 60° C 2.8 1035 364 0.13 2 2.8 19.1 6.8 2.9 4.0 1.3 5 at e 60° C 2.7 1043 382 0.12 7 2.8 18.4 6.7 2.8 3.7 1.3 7 at e 60° C 2.7 1025 377 0.12 8 2.7 18.8 6.9 2.9 3.8 1.3 14 at e 60° C 2.7 1018 375 0.12 2 2.9 19.6 6.9 2.6 3.2 1.2 21 at e 60° C 2.8 1080 385 0.12 1 2.8 19.4 7.0 2.7 3.5 1.3

[0129] The data in Table 3 provide the properties of the stored composite and the resulting compound, namely the vulcanizate produced from the stored composite. Regarding the properties of the composite, the Payne ratio is advantageously reduced for samples stored under nitrogen and vacuum compared to samples stored in air over a 30-day period. Regarding the properties of the compound, it can be seen that under all temperature conditions, the samples packaged under nitrogen and vacuum show a maintenance or reduction of the maximum tan θ values ​​and the Payne ratio. Conversely, the maximum tan θ increases for all samples stored in air (with a standard oxygen content of 21%) over the 90-day period.This effect is pronounced during storage at 60 °C, as shown by the increase in maximum tan θ for samples stored in air compared to the corresponding reduction for samples stored under nitrogen or vacuum. The present composites and the corresponding compounds exhibit a highly unexpected improvement in hysteresis compared to samples stored in air (i.e., not stored in an oxygen barrier container). Example 2

[0130] This example describes the results of storing different parts of the same elastomer composite in air, under nitrogen and under vacuum, where the composite was prepared by dry mixing processes.

[0131] All samples were prepared with ASTM N234 grade carbon black, supplied under the name VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The elastomer used was a standard RSS3 grade natural rubber (Hokson Rubber, Malaysia). Technical descriptions of this natural rubber are widely available, such as in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA).

[0132] The composite mixture was prepared in one phase using a Banbury® BR-1600 mixer (“BR1600”; manufacturer: Farrell). The resulting composites were compounded in one phase in a 439 mL CW Brabender internal mixer. Table 4 shows the formulations for mixing and compounding. The wax beads were Akrowax™ 5031 wax beads from Akrochem, Akron, Ohio. [Tables 4] Formulation (pc) For NR 100 CB V7H 50 6PPD 2 elastomeric composite For compounding Elastomeric composite 152 Zinc oxide 3 Stearic acid 2 6PPD 0.5 Antioxidant DQ pellets 1.5 Wax beads 1.5 BBTS accelerator 1.4 Sulfur 1.2

[0133] The mixing protocol is shown in Table 5, where the mixing was carried out under the following conditions: temperature of the temperature control unit (TCU) = 50 °C, rotor speed = 80 rpm, filling factor = 60% and dynamic pressure = 2.8 bar. [Tables 5] Step Time or Temperature Step Description 0s Add NR 60s Add 2 / 3 of load 120s Sweep / Add the rest of the load 150s Sweep 140°C Add 6PPD Sweep / Scrape 160 °C Empty

[0134] The resulting composites were sheeted on a rolling mill operating at approximately 50 °C and 37 rpm, followed by six passes of the end roll with a gap between rolls of approximately 5 mm. The composite sheets were separated into several samples for storage either in air or under nitrogen. For samples stored in a nitrogen environment, the elastomeric composites were placed in a nitrogen-purged glove box (oxygen concentration less than 2%). All samples were stored in a climate-controlled atmosphere (20 °C).

[0135] The compounding protocols are presented in Table 6, where compounding was carried out under the following conditions: temperature TCU = 40 °C, rotor speed = 60 rpm, filling factor = 60%. [Tableauxô] Time (s) Description 0 Slowly add the composite (60 s for ingestion + 60 s for chewing) 120 Add zinc oxide, stearic acid, and 6PPD 240 Sweep / scrape - Add BBTS and sulfur (premixed) 300 Empty

[0136] The resulting compounds were rolled into sheets on a 2-roller operating at 50 °C and 37 rpm, followed by four passes (wound end to end) through the rolling mill with a gap between rolls of approximately 5 mm. The samples were cured in a press heated to 150 °C for 30 min.

[0137] The properties of the compound and the composite are presented in Table 7 where "Atm" is as defined in Example 1. The properties of the reference composite were measured before sealing (Day = 0, i.e., no storage). [Tables 7] Tem PS (J ours) At m Tem P Rapp ort Pa yne( C) G’0,3 %,k Pa (C) G’51,5 %, kPa (C) tan ô m ax Ml 00 (MP a) M30 0(M Pa) M30 0 / M10 0 Rapp ort Payne G’0,1 %, M Pa G’50 %, M Pa 0 Air 20° C 5,5 1597 287 0,20 5 3,2 17,2 5,4 5,2 7,6 1,5 30 Air 20° C 6,0 1636 272 0,21 7 3,3 17,1 5,3 5,7 8,2 1,5 90 Air 20° C 6,3 1719 276 0,22 5 3,0 15,8 5,2 5,9 7,9 1,4 180 Air 20° C 6,3 1701 270 0,22 8 3,3 16,8 5,2 6,4 10,6 1,7 30 N2 20° C 4,8 1510 316 0,18 2 3,2 17,6 5,6 4,3 5,6 1,3 90 N2 20° C 4,6 1519 331 0,19 2 3,0 16,8 5,6 4,8 6,2 1,3 180 N2 20° C 4,3 1458 345 0,18 7 3,2 17,8 5,6 4,5 6,9 1,5

[0138] From Table 7, it can be seen that the composites stored under nitrogen exhibited lower Payne ratio values ​​compared to the samples stored in air for the same duration. For the properties of the compound (vulcanized), the maximum tan θ values ​​for the samples stored in air increased over the 180 days. Conversely, the maximum tan θ values ​​for the samples stored under nitrogen were remarkably lower than those of the samples stored in air. The samples stored under nitrogen also exhibited a slightly higher tensile stress ratio (M300 / M100) and a lower Payne ratio compared to the samples stored in air (i.e., not stored in an oxygen barrier container). Example 3

[0139] This example describes the results of storing different parts of the same elastomeric composite under air or nitrogen where the composite was prepared by mixing a wet filler with a solid elastomer. The composite was stored in sheet form.

[0140] All samples were prepared with ASTM N234 grade carbon black, supplied as VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The elastomer used was RSS3 standard grade natural rubber (Sri Trang Agro-Industry Public Company Limited, Thailand). Wet carbon black was prepared by grinding dry carbon black granules with an 8" model Microjet pulverizer to generate flaky carbon black particles having a particle diameter 99.0% less than 10 microns. This flaky carbon black was then wet-granulated in a pin granulator. The black the resulting wet carbon (remoistened carbon black) had a moisture content of 57%.

[0141] The composites were prepared via a two-phase mixing process followed by two-phase compounding to generate the vulcanizers. The formulations are presented in Table 8; the carbon black loading is reported on a dry basis. [Tables 8] Formulation (pcc) For RSS3 100 CB Vulcan® 7H 50 6PPD 2 elastomeric composite Compounding 1 Elastomeric composite 152 Zinc oxide 3 Stearic acid rubber grade c 2 6PPD 0.5 Antioxidant DQ pellets 1.5 Wax beads 1.5 Compounding 2 BBTS accelerator powder 1.4 Sulfur 1.2 The first composite mixing phase was carried out in a Kobelco BB-72 tangential mixer equipped with 4WN rotors (66 L capacity), at a 66% fill factor. The mixing chamber, rotors, and piston were heated with a temperature control unit (TCU) set at 75 °C. The dynamic pressure was 15.5 MPa. After the first mixing phase, the composite was processed in a Kobelco TSR-125 twin-screw discharge extruder equipped with stationary knives (Kobelco Kobe Steel Group).

[0142] The mixing protocol for the first phase is shown in Table 9. The resulting batch times were 9.2–9.4 minutes. The first phase composite exhibited a probe temperature range of 123-131 °C and a moisture content of 4%. [Tables 9] Mixer RPM Description 45 Add rubber to mixer in 20 s 45 Masticate rubber to 110°C 60 Add charge in 20 s 80 Mix to 130°C 60 Add charge in 20 s 80 Mix to 130°C 60 Add charge in 20 s 80 Mix to 168°C 60 Add 6PPD in 20 s 80 Mix to 175°C and discharge batch

[0143] The mixing protocol for the second phase is shown in Table 10. The second phase of composite mixing was carried out on a Kobelco BB-16 tangential mixer, equipped with 6WI rotors (14-liter capacity), at a fill factor of 40% (Kobelco Kobe Steel Group). The mixing chamber and rotors were maintained at a constant temperature using a temperature control unit (TCU) set at 50 °C. Mixing was carried out with the piston raised to its upper position, so that it did not apply pressure to the contents of the mixer. The time between the first and second phases of composite mixing did not exceed 2 hours. After initial mastication, the second phase of composite mixing was carried out under PID (proportional-integral-differential) control, which allows for automated batch temperature control via a feedback loop.A thermocouple inserted through the hinged door of the mixer measures the batch temperature, which is transmitted to a PID controller. The controller output is used to control the speed of the mixer rotors. The second-phase composite mixing protocol is shown in Table 10. The second-phase composite had a probe temperature range of 133–140 °C and a moisture content of <1%. [Table 10] Mixer speed (rpm) Description 35 Add the composite to the mixer 35 Mix with the piston raised for 90 seconds 35-50 Masticating with piston raised for 390 s. Temperature of 1 ot automatically controlled via PID control, using a setpoint of 135 °C

[0144] After the second mixing phase, the composite was processed in a TSR-125 twin-screw discharge extruder equipped with a die (Kobelco Kobe Steel Group) to create sheets. After 27 days under ambient conditions, the composites were then stored in sheet form under the conditions set out in Table 13. Storage temperatures were 20 °C (air-conditioned) and the samples were stored in air or in a nitrogen-purged (“N2”) glove box (oxygen concentration less than 2%).

[0145] Two-phase compounding was carried out with the BR1600 mixer under the following conditions: temperature TCU = 50 °C (1st and 2nd phases); rotor speed = 80 rpm (1st phase) or 60 rpm (2nd phase); filling factor = 68% (1st phase) or 65% (2nd phase); dynamic pressure = 2.8 bar (1st and 2nd phases). The compounding protocols for the 1st and 2nd phases are presented in Tables 11 and 12, respectively. [Tableauxll] Time (s) Description Compounding phase 1 0 Add the composite 30 Add the "Compounding 1" formulation 90 Scrape / Sweep 150 Empty at 150 s, adjust the speed (rpm) until a temperature < 125 °C [Tables 12] Time (s) Description Compounding Phase 2 0 Add V2 of phase 1 composite / "compounding 2" formulation / residual phase 1 composite 30 Sweep 90 Empty, adjust the flow rate until the temperature is < 115 °C

[0146] After each compounding phase, the compounds were sheeted on a two-roll mill operating at 50 °C and approximately 37 rpm, followed by six passes of the end roll through the mill with a gap between the rolls of approximately 5 mm. The Phase 2 samples were cured in a heated press (150 °C, 2500 lbs) for a specified time (30 minutes). The properties of the vulcanized compounds are shown in Table 13. The properties of the reference composite were measured before sealing (Day = 0, i.e., no storage). [Tables 13] Time (days) Atm Temp tan ô max M100 ( MPa) M300 ( MPa) M300 / M100 P ayne ratio G'0.1% (MPa) G'50% (MPa) 0 Air 20 °C 0.176 2.9 16.6 5.8 4.3 5.3 1.3 90 Air 20 °C 0.186 2.8 14.7 5.3 4.3 6.2 1.5 90 N2 20 °C 0.166 2.8 15.5 5.6 3.8 5.2 1.4 180 N2 20% 0.151 2.9 16.1 5.5 3.5 5.8 1.7

[0147] From the data in Table 13, it can be seen that the maximum tan θ values ​​for the leaves stored in air at 20 °C are maintained or increase over the 180-day period. In contrast, the samples stored under nitrogen show considerably reduced maximum tan θ values ​​at the end of the 180-day storage period. Furthermore, the samples stored under nitrogen exhibit smaller reductions in tensile stress than the samples stored at 20 °C in air. Moreover, only the samples stored under nitrogen showed reduced Payne ratio values. Example 4

[0148] This example describes the results of storing different parts of the same elastomer composite in sheet form under air or vacuum where the composite was prepared by mixing a wet filler with a solid elastomer and a bonding agent, and an evaluation of the properties of the compound prepared from the composite.

[0149] All samples were prepared with ASTM grade N234 carbon black, supplied as VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The carbon black granules had a moisture content of 56% and were prepared by grinding with an 8" Microjet pulverizer to generate flaky carbon black particles with a particle diameter of less than 10 µm at 99.5%. This flaky carbon black was then moistened with the pin granulator to regenerate the moistened granules. The elastomer used was RSS3 standard grade natural rubber (Von Bundit Co. Ltd., Thailand). Technical descriptions of natural rubber are widely available, such as in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA).The linking agent used was sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, commercially available as the coupling agent Sumilink® 200 (“S200”; Sumitomo Chemical).

[0150] The composites were prepared by means of a two-phase mixing process followed by one-phase compounding. The formulations are presented in Table 8; the carbon black loading is reported on a dry basis. The formulations used are presented in Table 14. Carbon black loading was planned on a dry basis. [Tables 14] Formulations (pc) Formulation phase 1 RSS3 100 V7H wet 50 S200 2 6PPD 2 For compounding TMQ 1.5 zinc oxide 3 stearic acid 2 wax beads 1.5 6PPD 0.5 BBTS 1.4 Sulfur 1.2

[0151] The first phase of the two-phase mixing protocol is set out in Table 15. The time intervals denote the time of the step. The first phase of mixing was carried out on the BB-16 mixer equipped with 4WN rotors (capacity of 16.2 L) under the following conditions: temperature TCU = 90 °C, filling factor = 66%, dynamic pressure = 112 barg. [Tables 15] Time or t temp. rotor speed (rpm) Description 20 s 50 Introduce the rubber into the mixer 110 °C 60 Masticate the rubber up to 110 °C 20 s 60 Proceed with the 1st addition of filler (75%) 120 s or 1 30 °C 85 Mix until reaching either 120 seconds or 130 °C, depending on the value reached the first time 20 s 60 Add S200 then proceed with the 2nd addition of filler 20 s 60 Mix at 60 rpm for 20 seconds to allow the hydraulic system to reach pressure 155 °C 85 Mix until the 6PPD addition temperature (155 °C) 20 s 60 Add 6PPD 160 °C 85 Mix until the discharge temperature (160 °C) 30 s 50 Discharge after 30 s

[0152] The moisture content of the composite after the first mixing phase was 4.96% (mixing time = 7 min 20 s, probe temperature = 125 °C). After the first mixing phase, the composite was processed with a TSR-125 twin-screw discharge extruder equipped with stationary knives (Kobelco Kobe Steel Group).

[0153] The mixing protocol for the second phase is shown in Table 16, and the mixing was carried out on the BB-16 mixer equipped with 6WI rotors (capacity 14.4 L) under the following conditions: TCU temperature = 65 °C, fill factor = 35%, dynamic pressure = 112 barg. After initial mashing, the mixing was carried out under PID temperature control with the piston raised to its highest position, as described in Example 3. [Tables 16] Time or temp P- Rotor speed (rpm) Description 20 s 35 Add the composite to the mixer 90 s 35 Masticate with the piston raised for 90 s 35-54 Variable masticate under PID temperature control with the piston raised; batch temperature automatically controlled with a setpoint of 135 °C 30 Discharge unload the mixer and close the hinged door after 30 s

[0154] After the second mixing phase, the composite was processed in a TSR-125 twin-screw discharge extruder equipped with a die (Kobelco Kobe Steel Group) to create sheets. The resulting sheets were cooled under ambient air for 27 days.

[0155] The composites were then stored in sheet form in air or under vacuum for a period of 90 days at 20 °C. For the samples stored under vacuum, the composites were placed in metallized bags (Marvelseal® 360 barrier film) and subjected to gas rinsing and then vacuum sealing with an AmeriVacs AVN shrink-nozzle vacuum sealer.

[0156] After the storage period, vulcanizates were formed by compounding the stored composites with the phase 3 formulation of Table 14 in a 439 mL CW Brabender prep mixer equipped with cams according to the protocol shown in Table 17. The accelerator used was BBTS (N-tert-butyl-2-benzothiazole sulfenamide), from Akrochem, Akron, Ohio. The compounding conditions were: starting temperature = 40 °C; rotor speed = 60 rpm; fill factor = 60%. [Tables 17] Time(s) Description of compounding phase 1 0 Add the composite 120 Add the zinc oxide, stearic acid and 6PPD 240 Scrape / sweep - Add the BBTS and sulfur 300 Empty

[0157] After the compounding phase, the composites were sheeted on a two-roll mill operating at 50 °C and approximately 37 rpm, an operation followed by six passes with a gap between the rolls of approximately 5 mm. The final compounds were sheeted to a thickness of 2.4 mm on a two-roll mill operating at 60 °C. The final compounds were cured in a press heated to 150 °C for 30 minutes.

[0158] The properties of the vulcanizates prepared from three samples of each of the composite samples aged for 90 days are presented in Table 18. "Atm" refers to the atmosphere in which the sample was stored, either in air or under vacuum. [Table 18] Time (days) Atm tan ô max avg. Payne ratio G'@0.1% (MPa) G'@50% (MPa) M100 (MPa) M300 (MPa) M300 / M100 1 Air 0.157 3.88 5.61 1.45 3.3 18.8 5.73 1 Air 0.153 3.94 5.92 1.50 3.3 18.8 5.69 1 Air 0.152 3.82 5.73 1.50 3.0 17.6 5.82 90 Air 0.152 3.66 4.65 1.27 3.3 18.0 5.45 90 Air 0.145 3.58 4.61 1.29 3.1 17.7 5.71 90 Air 0.148 3.69 4.87 1.32 3.3 18.7 5.67 90 Empty 0.134 3.19 4.12 1.29 3.2 18.0 5.63 90 Empty 0.136 3.42 4.63 1.35 3.5 20.2 5.77 90 Empty 0.132 3.20 4.13 1.29 3.2 19.1 5.97

[0159] From the data in Table 5, it can be seen that the maximum tan θ values ​​for the leaves stored under vacuum at 20 °C decreased considerably after the 90-day storage period. Furthermore, the vacuum-stored leaves exhibited reduced Payne ratio values. Example 5

[0160] This example demonstrates the result of storing different parts of the same elastomer composite in packages having varying TTO values ​​ranging from 0.527 cm3 / m2 / 24 hours at 0% relative humidity and 73°F to 1160 cm3 / m2 / 24 hours at 0% relative humidity and 73°F.

[0161] Table 19 below lists the properties of the tested packages, including wall structure, TTO (at 0% relative humidity and 73°F), and wall thickness. Packages A through D are flexible, transparent bags measuring 12 in. (length) x 12 in. (width) (volume of 3,865 cm³), marketed by ILC Dover, Inc. The reported TTO values ​​were measured according to ASTM D3985 at 73°F, 0% relative humidity. [Tables 19] Packaging Wall Materials Wall Thickness (sqm) TTO (cm3 / m2 / 24 hours) A PE / EVOH / PE / LLDPE (sealant) 81 0.527 B LLDPE / Nylon / EVOH / Nylon / LLDPE (sealant) 76 2.33 C EVA / Nylon / EVA (sealant) 51 233 D LLDPE 152 1160

[0162] The tested composites were prepared according to the elastomer composite formulation in Table 1, Example 1. The formulation for the rubber composites was the same as that in Table 1, Example 1, without any compounding ingredients since no compounding was carried out for this example.

[0163] After 15 days of air storage, the composites (150 g, specific gravity of 1.112 g / cm³) were stored in the packagings and subjected to the conditions set out in Table 20. The comparison samples (“Comp”) were stored in air. The remaining samples were stored in one of bags A, B, C, or D, having respective TTO values ​​set out in Table 19. The samples were stored under a unique combination of packaging atmosphere (“Packing Atm”) and number of days stored in an oven at 60 °C (“Days”). Under the “Packing Atm” column, “Sealed” refers to composites that were sealed in the packaging without any modification of the atmosphere. “Vacuum / N₂” refers to composites that The samples were stored after the packaging (containing the composite) was vacuum-sealed to a pressure of 84.7 kPa, followed by nitrogen rinsing of the bags and sealing of the packaging. The gas evacuation and rinsing steps were performed using an AmeriVacs AVN vacuum heat sealer with a shrink nozzle. All samples were stored for 14 or 21 days in an oven at 60 °C to simulate long-term storage under ambient conditions.

[0164] Oxygen content is reported as a concentration (%) of the total gas in the headspace of the bag and was determined by two separate methods. For the transparent bags (bags A to D), the oxygen content in the headspace was measured non-invasively with an OpTech®-02, model P (“OpTech”) oxygen and headspace analyzer, which uses optical fluorescence to measure sensors placed inside the transparent packaging. Measurements were taken on day 0, then on day 14 and / or day 21 of storage at 60 °C after allowing the bags to reach room temperature. For all bags, the oxygen content in the headspace was also measured by applying a resealable septum to the outer surface of a bag and piercing the bag through the septum with a Dansensor® CheckPoint® 3S, 02-Premium semiconductor sensor headspace and oxygen analyzer (“CheckPoint”).Both types of oxygen analyzers are available from Ametek Mocon (Minnesota, USA). [Tables 20] Packaging TTO cm3 / m2 / 24 hours Atm packaging Day conc. in O2 (%) (Check Point) conc. in O2 (%) day 0 (Op Tech) conc. in O2 (%) day 14 (O pTech) conc. in O2 (%) day ur21 (O pTech) Comp SO Air 0 21 Comp so Air 14 21 Comp SO Air 21 21 A 0.527 Sealed 14 4 20.9 4.7 A 0.527 Sealed 21 3.8 19.3 7.2 3.9 A 0.527 Vacuum / N2 14 2.8 1.9 2.5 B 2.33 Sealed 14 3.0 20.5 3.0 B 2.33 Sealed 21 6.6 20.0 9.6 6.9 B 2.33 Vacuum / N2 14 3.6 1.4 3.6 C 233 Sealed 14 13.2 19.7 14.1 C 233 Sealed 21 13.2 20.8 12.0 12.5 c 233 Empty / N2 14 8.5 1.4 8.9 c 233 Empty / N2 21 13.7 0.3 1.0 14.1 D 1160 Sealed 14 20.2 19.7 20.5 D 1160 Sealed 21 20.2 19.4 20.0 19.5 D 1160 Empty / N2 14 20.8 2.3 22.0 D 1160 Empty / N2 21 20.8 2.2 20.0 19.7

[0165] In Table 20, all comparison samples (“Comp”) have a headspace oxygen concentration of 21% because they are stored in air. All TTO values ​​are reported at 0% RH and 73°F. All CheckPoint data points refer to measurements taken on the day indicated in the “Day” column. OpTech measurements were taken on the days indicated in their respective “OpTech” columns. Oxygen content is expressed as the measured oxygen concentration.

[0166] From the data in Table 20, the general trend shows that the lower the TTO value, the lower the oxygen content measured in the headspace, as indicated by both the CheckPoint and OpTech data.

[0167] The oxygen content in bags A and B (which have the lowest TTO and second lowest respectively) was reduced or maintained over the storage time whether they were air-sealed (“Sealed”) or under modified atmospheres (“Vacuum / N2”).

[0168] The oxygen content of bag C, which was air-sealed, also decreased over the storage time, but not to the extent of bags A and B. The oxygen content of bag B, stored under air (“Sealed”), did not decrease over time. When stored under a modified atmosphere, the oxygen concentration increased for both bags C and D over time, and the final oxygen concentration values ​​were considerably higher than those of bags A and B, regardless of the storage method. Example 6

[0169] This example demonstrates the viability of packaging with high barrier wall properties for storing composites containing hardening agents (green compounds).

[0170] The composites were prepared according to the elastomeric composite formulation in Table 1, Example 1. The rubber compounds (green compounds) were prepared according to the compound formulation in Table 1, Example 1 and the protocol in Table 2, Example 1. The green compounds were then sheeted on a two-roll mill at 50 °C at a speed of 10.5 m / min, an operation followed by four passages (wound end to end) through the rolling mill with a gap between cylinders of approximately 5 mm.

[0171] Different portions of the same elastomeric composite, namely, the green compound (sheet before curing), were stored at 30 °C under the conditions set forth in Table 21. In Table 21, "Atm" indicates whether the sample was stored in air or under vacuum ("vacuum"). "Day" denotes the number of days the sample was stored in the stated state after compounding and before curing in the press. For the vacuum-stored samples, the green compounds were placed in bags with the Marvelseal® 360 barrier film for three hours of compounding. The bags were then rinsed with nitrogen, evacuated to a pressure of 84.7 kPa, and sealed. The gas rinsing and vacuum sealing steps were performed using an AmeriVacs AVN shrink-nozzle vacuum heat sealer. The reference composites were measured before sealing (Day = 0, i.e., no storage).

[0172] After storage, the compounds were hardened in a heated press (150 °C) for 30 minutes. The properties of the vulcanizers are also shown in Table 21. [Tables 21] Time (days) Atm tan ô max avg M100 (MPa) M300 (MPa) M300 / M100 0 Air 0.136 3.11 18.97 6.1 0 Air 0.125 3.19 19.48 6.11 15 Air 0.139 2.86 17.83 6.23 15 Air 0.137 2.99 18.3 6.13 15 Vacuum 0.127 2.97 18.49 6.23 15 Vacuum 0.124 2.93 18.3 6.25 30 Air 0.141 2.95 17.96 6.09 30 Air 0.139 3.06 18.4 6.01 30 Vacuum 0.130 2.9 18.24 6.29 30 Vacuum 0.129 2.99 18.32 6.13 90 Air 0.155 2.95 17.82 6.04 90 Air 0.158 2.99 18.1 6.06 90 Vacuum 0.118 3.04 19.35 6.37 90 Empty 0.116 2.8 19.01 6.79

[0173] Regarding the properties of the compounds, it can be seen that under all temperature conditions, the green compounds stored under vacuum yielded rubber compounds that exhibited a maintenance or reduction of the maximum tan θ values. Furthermore, these rubber compounds also showed an increase in the tensile stress ratio (M300 / M100). Conversely, the maximum tan θ increased for all samples stored in air (with a standard oxygen content of 21%) over the 90-day period.

[0174] The terms "comprising," "having," "including," and "containing" are to be interpreted as open terms (i.e., meaning "including, but not limited to") unless otherwise stated. The enumeration of value ranges herein is solely for the purpose of serving as an abbreviated method of individual reference to each distinct value within the range, unless otherwise stated herein, and each distinct value is cited in the specification as if stated individually therein. All the methods described herein may be performed in any order unless otherwise stated herein or unless clearly expressed in a contradictory manner by the context.The use of any or all of the examples, or of exemplary language (e.g., "such as") provided herein, is solely for the purpose of further clarifying the invention and in no way limits the scope of the invention unless otherwise claimed. No language in the description shall be construed as indicating any unclaimed element as essential to the practice of the invention.

Claims

Demands

1. Packaged elastomeric composite, comprising: • a sealed package containing the composite in an atmosphere having a partial pressure of oxygen less than 10 kPa, wherein the composite is uncured and comprises at least one elastomer and at least one filler, wherein: • the package comprises at least one wall surrounding the composite, wherein at least one wall comprises at least one oxygen barrier layer such that the package has an oxygen transmission rate not exceeding 100 cm3 / (m2-day-atm) at 23°C and 0% relative humidity.

2. Elastomeric composite packaged according to claim 1, in which the atmosphere has a partial pressure of oxygen not exceeding 7 kPa.

3. Elastomeric composite packaged according to claim 1, in which the atmosphere has a partial pressure of oxygen not exceeding 5 kPa.

4. Elastomeric composite packaged according to any one of claims 1 to 3, wherein the atmosphere comprises at least 90% of at least one gas that is non-reactive with the elastomeric composite.

5. Elastomeric composite packaged according to claim 4, wherein at least one gas that is non-reactive with the elastomeric composite is selected from nitrogen, argon, helium, xenon and carbon dioxide.

6. Packaged elastomeric composite according to any one of claims 1 to 5, wherein at least one oxygen barrier layer comprises a material selected from polyamide, polyethylene, polyethylene terephthalate, polyethylene naphthalate, aluminium, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, and mixtures thereof and metallized layers thereof.

7. Elastomeric composite packaged according to any one of claims 1 to 5, wherein at least one oxygen barrier layer comprises a material selected from polyamide, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, metals, and mixtures thereof and metallized coatings thereof.

8. Elastomeric composite packaged according to any one of claims 1 to 5, wherein at least one oxygen barrier layer comprises a metallized layer or a metallic layer.

9. Elastomeric composite packaged according to any one of claims 1 to 5, wherein at least one wall does not contain a metallized layer or a metallic layer.

10. Elastomeric composite packaged according to any one of claims 1 to 5, wherein at least one oxygen barrier layer comprises a material selected from metals, metal alloys, carbon-based ceramic nanomaterials and melamine-based materials.

11. Elastomeric composite packaged according to any one of claims 1 to 10, wherein at least one wall is a monolayer wall which is the oxygen barrier layer.

12. Packed elastomeric composite according to any one of claims 1 to 10, wherein at least one wall comprises two or more layers, wherein at least one of the layers is the oxygen barrier layer.

13. Elastomeric composite packaged according to any one of claims 1 to 12, wherein at least one wall is flexible.

14. Elastomeric composite packaged according to any one of claims 1 to 12, wherein at least one wall is rigid.

15. Elastomeric composite packaged according to any one of claims 1 to 14, wherein the inside of the package has a volume of at least 10 L.

16. Elastomeric composite packaged according to any one of claims 1 to 14, wherein the inside of the package has a volume of at least 50 L.

17. Elastomeric composite packaged according to any one of claims 1 to 16, wherein the composite comprises a protective agent present in an amount of at least 0.5 pcc.

18. Elastomeric composite packaged according to any one of claims 1 to 16, wherein the composite comprises a protective agent present in an amount from 0.5 pcc to 10 pcc.

19. Elastomeric composite packaged according to any one of claims 1 to 16, wherein the composite comprises a protective agent present in an amount from 0.5 pcc to 3 pcc.

20. Elastomeric composite packaged according to any one of claims 1 to 16, wherein the composite is substantially free of protective agents.

21. Composite packaged according to claim 20, wherein the composite has a moisture content of 3% to 20% by weight relative to the total weight of the composite.

22. Elastomeric composite packaged according to any one of claims 1 to 21, wherein the packaging further contains at least one deoxygenating agent.

23. Elastomeric composite packaged according to claim 22, wherein at least one deoxygenating agent is contained in an oxygen-permeable sachet.

24. Elastomeric composite packaged according to claim 23, wherein the sachet is glued to an internal wall of the packaging.

25. Elastomeric composite packaged according to any one of claims 22 to 24, wherein at least one deoxygenating agent is selected from metallic powders, ascorbic acids and salts thereof, and catechol.

26. Elastomeric composite packaged according to any one of claims 1 to 25, wherein at least one filler is selected from carbon materials, carbon black, silica, bio-based fillers, clays, nanoclays, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, regenerated carbon or combinations thereof, and materials coated and chemically treated with the same.

27. ​​Packed elastomeric composite according to any one of claims 1 to 25, wherein at least one filler is selected from rice hull silica, lignin, nanocellulose and hydrothermal carbon.

28. Elastomeric composite packaged according to any one of claims 1 to 25, wherein at least one filler is selected from carbon black, silica, and silicon-treated carbon black.

29. 67 Elastomeric composite packaged according to any one of claims 1 to 28, wherein at least one 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 mixtures thereof.

30. Elastomeric composite packaged according to any one of claims 1 to 28, wherein at least one elastomer is selected from diene-based elastomers.

31. Elastomeric composite packaged according to any one of claims 1 to 28, wherein at least one elastomer is selected from natural rubber, polyisoprene rubber, butadiene rubber and mixtures thereof.

32. Elastomeric composite packaged according to any one of claims 1 to 28, wherein at least one elastomer comprises at least 30% natural rubber and at least one filler comprises at least 50% carbon black.

33. Elastomeric composite packaged according to any one of claims 1 to 32, wherein the composite further comprises hardeners.

34. Elastomeric composite packaged according to any one of claims 1 to 33, wherein the composite has a Payne ratio of at least 1.1, wherein the Payne ratio is G'(0.3%) / G'(51.5%), wherein G'(0.3%) is a dynamic storage modulus measured at a strain amplitude of 0.3% and G'(51.5%) is a dynamic storage modulus measured at a strain amplitude of 51.5%.

35. Elastomeric composite packaged according to any one of claims 1 to 34, wherein the composite has a macrodispersion d90 not exceeding 80 pm, in which d90 is the equivalent surface diameter (pm) of particles of the filler in the composite.

36. Elastomeric composite packaged according to any one of claims 1 to 35, wherein the composite is a heat-treated composite.

37. Elastomeric composite packaged according to any one of claims 1 to 36, wherein an amount of oxygen in the atmosphere of the packaging does not exceed 75 mmol / kg of elastomeric composite.

38. Elastomeric composite packaged according to any one of claims 1 to 37, wherein the composite has been packaged for a period of time of at least 5 days.

39. Elastomeric composite packaged according to any one of claims 1 to 37, wherein the composite has been packaged for a period of time of at least 14 days.

40. A method for storing an elastomeric composite, comprising: • sealing the elastomeric composite in a container and storing the composite in the sealed container for a period of time of at least 5 days, wherein: • the elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and • the container comprises at least one wall surrounding the composite, in which at least one wall comprises at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm3 / (m2-day-atm) at 23°C and 0% relative humidity.

41. A method according to claim 40, wherein prior to sealing, the method further comprises rinsing the inside of the container with at least one gas that is non-reactive with the composite and / or applying a vacuum inside the container.

42. A method according to claim 40 or 41, wherein the sealed container has an atmosphere comprising at least 90% of at least one gas that is non-reactive with the elastomeric composite.

43. A method according to claim 40 or 41, wherein the sealed container is under vacuum.

44. A method according to any one of claims 40 to 43, wherein the composite is stored in the sealed container for a period of time of at least 14 days.

45. A method according to any one of claims 40 to 44, wherein prior to sealing, the method further comprises heat treating the composite at a temperature of at least 40°C.

46. A method according to any one of claims 40 to 45, wherein at the time of sealing, the composite has a probe temperature of at least 40°C.

47. A method according to any one of claims 40 to 46, wherein the composite is prepared by combining at least one solid elastomer and a wet filler comprising a filler and a liquid, wherein the liquid is present in an amount of at least 15% by weight based on the total weight of the wet filler.

48. A method for preserving or improving at least one property of an elastomeric composite or of a compound formed from the composite, comprising: • storing the elastomeric composite in a sealed container for a period of time of at least 5 days, wherein: • the elastomeric composite is uncured and comprises at least one elastomer and at least one filler; and • the container comprises at least one wall surrounding the composite, in which at least one wall comprises at least one oxygen barrier layer such that the container has an oxygen transmission rate not exceeding 100 cm3 / (m2-day-atm) at 23°C and 0% relative humidity.

49. A method according to claim 48, wherein the elastomeric composite is stored in the sealed container for a period of time of at least 14 days.

50. A method according to claim 48 or 49, wherein the stored elastomeric composite or a compound formed from the stored elastomeric composite has a Payne ratio that is reduced by at least 10% compared to the Payne ratio of the composite before packaging sealing,

51.

52.

53.

54.

55. • in which the Payne ratio is G'(0.3%) / G'(51.5%), in which G'(0.3%) is a dynamic storage modulus measured at a strain amplitude of 0.3% and G'(51.5%) is a dynamic storage modulus measured at a strain amplitude of 51.5%. A process according to any one of claims 48 to 50, wherein the compound formed from the stored elastomeric composite has a maximum tan θ value that is reduced by at least 10% compared to the maximum tan θ value of the composite before the packaging was sealed. A packaged elastomeric composite according to any one of claims 1 to 39, wherein the composite is the product formed by incorporating at least one bonding agent during the mixing of at least one elastomer with at least one filler. A process according to any one of claims 40 to 51, wherein the composite is the product formed by incorporating at least one bonding agent during the mixing of at least one elastomer with at least one filler. A method according to any one of claims 40 to 51, wherein the composite further comprises at least one bonding agent. A method according to claim 53 or 54, wherein the at least one bonding agent comprises: • a first functional group is chosen from -NR*R2, -N(R')(R2)(R3)+A, -S-SO3M1, and structures represented by formula (I) and formula (II), in which A is chloride, bromide, iodide, hydroxyl, nitrate, or acetate, X = NH₄⁺, O₂, or S, Y = H₂, OR₄, NR₄R₅, -SnR₄, and n is an integer chosen from 1 to 6, and a second functional group is chosen from thiocarbonyl, nitrile oxide, nitrone, nitrile-imine, -S- SO3M2, -Sx-R6, -SH, -C(R6)=C(R7)-C(O)R8, -C(R6)=C(R7 )-CO2R8, -C(R6)=C(R7)-CO2M2, and • R'-R8 are each independently chosen from H and CrC8 alkyl; M1 and M2 are each independently chosen from H, Na+, K+, Li+, N(R')4+ in which each R' is independently chosen from H and Ci-C20 alkyl, and x is an integer chosen from 1 to 8.

56. A method according to claim 55, wherein the linker further comprises at least one spacer between the first and second functional groups, wherein the at least one spacer is selected from -(CH2)n-, -(CH2)yC(O)-, -C(R9)=C(R10)-, -C(O)-, -N(R9)-, and -C6H4-, wherein R9 and R10 are each independently selected from H and Ci-C6 alkyl and y is an integer selected from 1 to 10.

57. A method according to claim 53 or 54, wherein the linking agent is selected from thiourea, cystamine, and compounds of formula (1), formula (2), and formula (3), H2N-Ar-N(H)-C(O)-C(R^C(R7)-CO2M2 (1), HsN-CŒxU-SSOsM2 (2), and M1O3S-S-(CHàrS-SO3M2 (3), where n is an integer selected from 1 to 6, R6 and R7 are each independently selected from H and CrC8 alkyl, and M1 and M2 are each independently selected from H, Na+, K+, Li+, and N(R')4+, wherein each R' is independently selected from H and Ci zi 20 alkyl

58. V Method according to any one of claims 55 to 57, wherein M1 and M2 are each independently chosen from H, Na+ and N(R')4+ and R6 and R7 are independently chosen from H and CrC6 alkyl.

59. Method according to claim 57 or 58, wherein the bonding agent is selected from compounds of formula (1) and R6 and R7 are each H.

60. A process according to claim 53 or 54, wherein the linking agent is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate.