Stored elastomer composites

Abstract

An elastomeric composite is disclosed that is stored in a container or package. The composite is uncured and includes at least one elastomer and at least one filler. The package or container includes at least one wall surrounding the composite, the at least one wall including at least one oxygen barrier layer. The container or package having the oxygen barrier layer has a 100 cm oxygen barrier at 23° C. and 0% relative humidity. 3 (m 2 The oxygen transmission rate of the elastomer composite material is preferably less than 100 atm / day. Also disclosed are methods of storing the elastomer composite material in the packages or containers disclosed herein.

Description

[Technical Field]

[0001] Disclosed herein are elastomer composites stored or packaged in containers or packaging having oxygen barrier walls. [Background technology]

[0002] Numerous commercially useful products are formed from elastomer composites, in which reinforcing fillers are dispersed in various synthetic elastomers, natural rubber, or elastomer mixtures. Carbon black and silica are widely used, for example, to reinforce natural rubber or other elastomers. It is common to produce a masterbatch, which is a preliminary mixture of reinforcing fillers, elastomers, and various optional additives, such as extender oils. Such a masterbatch is then compounded with processing and curing additives, and curing produces numerous commercially useful products. Such products include, for example, pneumatic, non-pneumatic, or solid tires for vehicles, which include tread sections such as caps and bases, undertreads, inner liners, sidewalls, wire skims, and carcasses. Other products include, for example, engine mounts, bushings, conveyor belts, windshield wipers, rubber components for aerospace and marine equipment, vehicle track elements, seals, liners, gaskets, wheels, bumpers, and vibration damping systems.

[0003] Good dispersion of reinforcing fillers in rubber compounding is recognized as a factor in achieving mechanical strength and consistent performance of elastomer composites and rubber compounding. Rubber compounding is prepared from elastomer composites, which are uncured mixtures of fillers and elastomers with one or more additives of any choice. Elastomer composites, also known as masterbatches, can be compounded with additional additives and curing agents and then subjected to one or more vulcanization processes. For this reason, elastomer composites may be more susceptible to degradation than (cured) rubber compounding, which presents challenges if stored and / or shipped before vulcanization. Therefore, there is a need to prevent substantial degradation of elastomer composites when stored for extended periods. [Overview of the project] [Means for solving the problem]

[0004] One aspect is, A sealed package containing a composite material in an atmosphere having a partial pressure of oxygen of less than 21 kPa (e.g., less than 20 kPa, less than 15 kPa, less than 10 kPa, less than 7 kPa, or less than 5 kPa), wherein the composite material is uncured and comprises at least one elastomer and at least one filler, where, The packaging includes at least one wall surrounding the composite material, the at least one wall including at least one oxygen barrier layer, and so the packaging can withstand temperatures of 100 cm at 23°C and 0% relative humidity (RH). 3 / (m 2 It has an oxygen permeability of less than 1 / day atm. It is a packaged elastomer composite material containing [the specified ingredient].

[0005] Other embodiments include, The elastomer composite material is sealed in a container, and the composite material in the sealed container is stored for at least 5 days, where, The elastomer composite is uncured and contains at least one elastomer and at least one filler, and further, The container includes at least one wall surrounding the composite material, and that at least one wall includes at least one oxygen barrier layer, so that the container can withstand 100 cm at 23°C and 0% relative humidity. 3 / (m 2 It has an oxygen permeability of less than 1 / day atm. This is a method for storing elastomer composite materials containing [a specific substance].

[0006] Another embodiment is a method for maintaining or improving at least one property of an elastomer composite or a compound formed from such a composite, Store in a sealed container for at least 5 days, where The elastomer composite is uncured and contains at least one elastomer and at least one filler, and The container includes at least one wall surrounding the composite material, wherein the at least one wall includes at least one oxygen barrier layer, so that the container can withstand 100 cm at 23°C and 0% relative humidity. 3 / (m 2 It has an oxygen permeability of less than 1 / day atm. This method includes [something].

[0007] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein (e.g., a method for storing an elastomer composite or a method for maintaining or enhancing at least one property of an elastomer composite or a formulation formed from such composite) may further include one or more of the following aspects: the atmosphere in the package or container has an oxygen partial pressure of 7 kPa or less or 5 kPa or less; the atmosphere in the package or container contains at least 90% of at least one gas that is nonreactive with the elastomer composite; the at least one gas that is nonreactive with the elastomer composite is selected from nitrogen, argon, helium, xenon, and carbon dioxide; and the sealed package or container is under vacuum.

[0008] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: 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, metal, and mixtures thereof, and metallized layers thereof; at least one oxygen barrier layer comprises a metallized layer or metal layer; the at least one wall does not comprise a metallized layer or metal layer; the at least one oxygen barrier layer comprises metal, metal alloy, ceramics 、The packaging comprises a material selected from carbon-based nanomaterials and melamine-based materials; at least one of the walls is a single layer wall which is an oxygen barrier layer; the at least one wall comprises two or three or more layers, where at least one of the layers is an oxygen barrier layer; the at least one wall is flexible; the at least one wall is rigid; and the interior of the packaging has a volume of at least 10 L or at least 50 L.

[0009] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further comprise one or more of the following aspects: the composite contains a degradation inhibitor in an amount of at least 0.5 phr, for example, in the range of 0.5 phr to 10 phr, or in the range of 0.5 phr to 3 phr, or in any other range disclosed herein; the composite is substantially free of a degradation inhibitor; the composite has a moisture content in the range of 3% to 20% by mass relative to the total mass of the composite; the package further comprises at least one oxygen scavenger; the at least one oxygen scavenger is contained in an oxygen-permeable sachet; the sachet is attached to the inner wall of the package; the at least one oxygen scavenger is selected from metal powders, ascorbic acid and their salts, and catechol.

[0010] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: at least one filler selected from carbonaceous materials, carbon black, silica, bio-based fillers, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, recycled carbon, or combinations thereof, and coatings and chemically treated materials thereof; at least one filler selected from rice husk silica, lignin, nanocellulose, and hydrothermal carbon; at least one filler selected from carbon black, silica, and silica-treated carbon black.

[0011] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: at least one elastomer is natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomer, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, or polysulfide rubber. The elastomers are selected from polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers, and mixtures thereof; at least one elastomer is selected from diene elastomers; at least one elastomer is selected from natural rubber, polyisoprene rubber, butadiene rubber, and mixtures thereof; the composite comprises at least one filler containing at least 30% natural rubber and at least 50% carbon black; the composite further comprises a curing agent.

[0012] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: the composite having a Payne ratio of at least 1.1, where the Payne ratio is G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the dynamic storage modulus measured at a strain amplitude of 51.5%; the composite having macrodispersion d of 80 μm or less 90 It has, and here d 90 This is the area-equivalent diameter (μm) of the filler particles in the composite material.

[0013] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: the composite is a heat-treated composite; the amount of oxygen in the package or container atmosphere is 75 mmol / kg elastomer composite or less; the composite is packaged, stored, or cured for at least 5 days or at least 14 days or any other period disclosed herein.

[0014] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: the inside of the package or container is flushed with at least one gas that is nonreactive with the composite and / or vacuumed before sealing the package or container; the composite is heat-treated at a temperature of at least 40°C before sealing the package or container; the composite has a probe temperature of at least 40°C when sealing the package or container containing the composite; the composite is prepared by mixing at least a solid elastomer and a wetting filler comprising a filler and a liquid, wherein the liquid is present in an amount of at least 15% by mass based on the total mass of the wetting filler.

[0015] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further include one or more of the following aspects: the stored elastomer composite or formulation formed from the stored elastomer composite has a Paine ratio that is reduced by at least 10% with respect to the Paine ratio of the composite before the package is sealed, where the Paine ratio is G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the dynamic storage modulus measured at a strain amplitude of 51.5%; the formulation formed from the stored elastomer composite has a maximum tanδ value that is reduced by at least 10% with respect to the maximum tanδ value of the composite before the package is sealed.

[0016] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the packaged elastomer composite or method disclosed herein may further comprise one or more of the following aspects: the composite is a product formed by mixing at least one crosslinking agent while mixing at least one elastomer with at least one filler; the composite is a product formed by mixing at least one crosslinking agent while mixing at least one elastomer with at least one filler; the composite further comprises at least one crosslinking agent. [Modes for carrying out the invention]

[0017] Elastomers (e.g., diene elastomers) are known to degrade in the presence of air / oxygen. Degradation can occur in the form of polymer chain severance and / or crosslinking, which can affect rubber properties. Elastomer composites can be cured in the presence of crosslinking agents, such as sulfur, resulting in a vulcanized product that is cured (relative to the composite) and has greater stability with respect to degradation. While degradation of the vulcanized product can still occur, it may have a smaller impact on certain performance properties compared to the degradation of the uncured composite. However, there may be a need to store uncured elastomer composites for extended periods (e.g., 3, 6, or 9 months, or 1 or 2 years). Furthermore, high temperatures often present in warehouses or during transportation (trucks, shipping containers) can accelerate the rate of degradation. To reduce this rate, composites can be stored in refrigerators or under air conditioning. Such storage solutions, however, require excessive energy consumption and cooling equipment.

[0018] It has not been previously recognized that high oxygen barrier materials can provide an atmosphere with a low oxygen content for a sufficient period of time so that the rubber properties of uncured composites containing rubber and fillers, and formulations formed from such composites, are effectively maintained, or, in certain cases, surprisingly, improved. Therefore, storing such elastomers and composites in a low oxygen atmosphere is not typical in the industry. The improvement may be in the rubber properties, which can be increased by at least 5%, or at least 10%, where the improvement can be an increase in a numerical value (e.g., tensile stress ratio) or a decrease in a numerical value (e.g., hysteresis, Payne effect, and / or Payne ratio, indicated by the maximum tanδ).

[0019] Disclosed herein are packaged elastomer composites (or stored or cured elastomer composites), methods for storing and / or packaging such composites, and methods for maintaining and / or enhancing (improving) at least one rubber property of composites or rubber compounds formed from such stored or packaged composites. The rubber properties mentioned herein can be rubber properties of the composite itself or of a rubber compound formed from the composite, wherein the rubber compound is obtained by vulcanizing the elastomer composite (vulcanizate), that is, curing the composite in the presence of a curing agent (vulcanizing agent) such as sulfur, peroxide, or the like.

[0020] Disclosed herein is a packaged elastomer composite, a sealed package that accommodates the composite in an atmosphere having an oxygen partial pressure of 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, the at least one wall comprises at least one oxygen barrier layer, whereby the package has 100 cm at 23° C. and 0% relative humidity 3 / (m 2 ·day·atm) or less oxygen permeability, .

[0021] Accordingly, in one embodiment, a container or packaging for containing or housing a sealed composite material or the composite material is provided, wherein the container or packaging includes at least one wall surrounding the composite material, and the at least one wall includes at least one oxygen barrier layer, thereby maintaining a low oxygen content in the container or packaging over a long period of time. The wall may include a single layer which is the oxygen barrier layer, or it may include multiple layers (two or more layers), at least one of which is the oxygen barrier layer. The oxygen barrier layer substantially reduces the rate of oxygen transport from the outside of the container to the inside of the container. By limiting the amount of oxygen exposed to the composite material through the container or packaging having an oxygen barrier wall (including at least one oxygen barrier layer), degradation of the composite material can be substantially prevented.

[0022] The composite materials disclosed herein are stored and / or packaged and / or housed in one or more containers or packaging that surround and contain the elastomer composite and can be of any shape or size insofar as they provide desired oxygen barrier performance. The container may be a packaging (e.g., a box, crate, bag) or any chamber, such as a glove box or room of any volume, in which the amount of oxygen inside can be maintained at a desired level. In one embodiment, the container or packaging is 100 cm³ at standard temperature and pressure. 3 / (m 2 It has an oxygen permeability (OTR) of 100 cm² or less (atm). The oxygen permeability of containers and packaging can be determined from the oxygen barrier properties of the walls constituting the oxygen barrier layer (oxygen barrier wall). Oxygen permeability can be determined according to ASTM D3985, which can be done under conditions such as 73°F and 0% relative humidity at sea level. In other embodiments, oxygen permeability can be measured or reported at 50% relative humidity or 65% relative humidity. Optionally, at least one wall is 100 cm² at 23°C (73°F) and 0% relative humidity (RH). 3 / (m2 Below 23°C (atm), for example at 23°C (0% relative humidity), the values ​​are 50 or less, 10 or less, 5 or less, 1 or less, 0.5 or less, 0.1 or less, 0.05 or less, 0.01 or less, 0.005 or less, and 0.001 cm. 3 / (m 2 It can have an oxygen permeability of less than (atm / day).

[0023] The walls of a container or packaging can include one or more parts that form the container when sealed. For example, a typical box can include four side wall parts in addition to the top and bottom wall parts. It is understood that the number of wall parts can vary, for example, a single, cylindrical side wall part sealed by the top and bottom wall parts, or a continuous wall configured to fold along a recess to form the container, or a continuous wall further joined with one or more additional wall parts. Any number of side wall parts can be used (e.g., hexagonal boxes or containers, wedge-shaped boxes or containers). Bags and pouches typically include two or more flexible wall parts, which are joined to one or more side wall parts (and optionally a bottom wall part) via, for example, abutting ends, so that at least two unclosed ends form an opening that can be sealed during packaging (e.g., sealed to be airtight).

[0024] As a more specific example, a flexible packaging can include two identical flexible wall sections having the same dimensions in length and width, each having four ends and forming a square or rectangular wall section. These two flexible wall sections can be joined together by sealing three abutting ends, while the fourth end remains unsealed, providing an opening for inserting an elastomer composite into the packaging. Typically, all wall sections of the container (side wall sections, top and / or bottom wall sections) are made of the same material; the oxygen barrier properties of the walls (and packaging) can then be determined from the oxygen permeability of any of the wall sections. Modifications can be made; for example, the bottom wall section may include one or more structural support layers to provide further strength, and the top or side wall sections may be configured to facilitate the release of adhesive for sealing (heat sealing) the container and / or a sealable layer (e.g., heat-sealable) or packaging. As a result, these sections may have different oxygen barrier properties. Therefore, the oxygen permeability of the packaging material can be the area average across the entire surface of the container.

[0025] Regarding the seal, airtightness refers to an airtight seal, which gives the packaging O2 barrier properties, thereby reducing the oxygen permeability from the outside to the inside of the packaging to 100 cm³ at 23°C and 0% relative humidity. 3 / (m 2 (atm per day) or less, or other quantities disclosed herein. An airtight seal can be formed, for example, by heat-sealing two sealable layers together, for example, by heat-sealing the edges of the side walls together. An airtightly sealed (e.g., end-sealed) package can have the same or substantially the same oxygen permeability as an oxygen barrier wall.

[0026] A container or packaging having two or more walls can be two or three or more containers, for example, a first container surrounding a second container that surrounds and contains an elastomer composite. Each container contains walls that can be single-layer or multi-layer. For example, the first container may have walls with first oxygen barrier properties, and the second container may have walls with second oxygen barrier properties. In a specific example, one container (one wall) may include a flexible membrane (e.g., a liner) that surrounds the shape of the material to be packaged and is optionally conformal, resulting in a lined or wrapped or shrink-wrapped material. The second container (or second wall) may include a less flexible or rigid material that surrounds the lined material, protecting it from breakage and / or deformation during storage (which may include transport). In any case. Even if there are multiple walls or multiple containers, each container can have oxygen barrier properties, thereby the elastomer composite material can have desired oxygen barrier properties, for example, 100 cm³ at 23°C and 0% relative humidity. 3 / (m 2 The oxygen permeability of the composite material is less than or equal to 100 (cm³) or other values ​​disclosed herein. For example, the composite material can be housed inside two walls, each having oxygen barrier properties, for example, one wall being a liner enclosing the elastomer composite material, and a second wall being a container housing the enclosed composite material. The oxygen permeability of each wall (of each container) is 100 (cm³). 3 / m 2 The temperature does not have to be lower than (100cm²), however, a container that is combined and includes two walls (e.g., liner and packaging) must be (100cm²). 3 / m 2 A desired oxygen permeability of less than or equal to (atm / day) can be achieved. For two or more containers (or two or more walls), the overall oxygen permeability (OTR) can be determined by the following formula.

number

[0027] Optionally, one or more containers without oxygen barrier properties may be used to store the elastomer composite in addition to the container with an oxygen barrier wall. For example, if the composite is in the form of frit or granules, this additional container may be a flexible mesh or bag to support or maintain the shape of the composite. Alternatively, the additional container may be a box made of wood, paper, or corrugated cardboard (or other non-barrier material) with no or poor oxygen barrier properties, or a sheet or grid, or a fibrous material such as cloth. This additional container may be placed outside or inside (or both) the oxygen barrier container (i.e., the container with an oxygen barrier wall) to provide additional structural support and / or to facilitate transport and / or handling.

[0028] The containers or packaging disclosed herein may have any desired volume or size. The interior of the container may have a volume (internal volume) of at least 1 L, at least 10 L, at least 20 L, or at least 50 L. The container may be the size of a sealed room or transport container, for example, in the range of 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. In the case of two or more containers, one of which is housed inside another, the volume is the volume of the larger oxygen barrier container. For example, a transport container may have a volume up to 20,000 L or up to 40,000 L, and a crate may have a volume up to 1,500 L or up to 2,000 L.

[0029] In other embodiments, the oxygen barrier properties of at least one wall can be selected to limit the amount of oxygen exposed to the elastomer composite over a specific period of time, thereby preventing substantial degradation of the composite. For example, by knowing the mass of the elastomer composite present in the packaging or container, the maximum amount of oxygen relative to the mass of the composite can be calculated. As one option, the container or packaging includes at least one wall containing at least one oxygen barrier layer, thereby the amount of oxygen in the packaging being 75 mmol / kg elastomer composite or less, for example, 60 mmol / kg elastomer composite or less, 50 mmol / kg elastomer composite or less, 40 mmol / kg elastomer composite or less, 30 mmol / kg elastomer composite or less, 20 mmol / kg elastomer composite or less, 15 mmol / kg elastomer composite or less, 10 mmol / kg elastomer composite or less, 6 mmol / kg elastomer composite or less, 5 mmol / kg elastomer composite or less, 4 mmol / kg elastomer composite or less, 3 mmol / kg elastomer composite or less, 2 mmol / kg elastomer composite or less, or 1 mmol / kg elastomer composite or less. The amount of oxygen present in a sealed container or package can be measured at the time the package is sealed or thereafter using an oxygen sensor (many types of oxygen sensors are commercially available). For example, the headspace of a container can be measured by a sensor having a needle that punctures the package through a resealable partition bonded to the outside of the package or incorporated into the wall, or by an adhesive sensor that can be inserted into and attached to the package before sealing. Illustrative oxygen sensors include CheckPoint® or OpTech® optical oxygen sensors, commercially available from Ametek Mocon (Minnesota, USA). From the respective volumes of the container and package, as well as the mass of the composite material, the amount of oxygen in the container (e.g., in millimoles) can be determined per unit mass of the composite material (e.g., kg). One option is that the volume of the package is at least 1 L, or at least 10 L, or any other volume disclosed herein.As one option, the disclosed amount of oxygen per unit of composite material in the container or packaging is maintained for 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, for any period of at least 5 days or longer (e.g., up to 1 year), the amount of oxygen present in the container is minimized to the disclosed level, for example, 20 mmol / kg composite material or less.

[0030] The number of moles of oxygen in a closed container can be calculated according to equation (1).

number

[0031] In containers for storing composite materials, V air The volume can be determined by subtracting the volume of the composite material from the volume of the container, and the volume of the composite material can be calculated as the mass of the composite material / the specific gravity of the composite material. From the result of equation (1), and by knowing the mass of the composite material, the oxygen content per unit mass of the composite material (millimoles / kg composite material) can be determined. In the specific case where the container is a flexible bag, the container can be conformed to the shape of the composite material by storing the container under vacuum or partially. In this state, 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 material.

[0032] As one option, oxygen content can be expressed as the partial pressure of oxygen. The partial pressure disclosed here represents the value measured under ambient conditions, e.g., at sea level at 20°C. Under ambient conditions, the partial pressure of oxygen is calculated from atmospheric pressure (101.3 kPa at sea level) multiplied by the percentage of oxygen in the atmosphere (21%).

[0033] One option is that, at the time of sealing, the initial atmosphere present in the container or packaging has a low oxygen content (for example, immediately before or when the packaging is airtightly sealed). For example, the atmosphere in the container can be changed to reduce the oxygen content inside the packaging (i.e., the atmosphere in the container is a modified atmosphere). Another option is that the inside of the packaging has oxygen partial pressures of less than 21kPa, less than 20kPa, less than 19kPa, less than 18kPa, less than 17kPa, less than 16kPa, less than 15kPa, less than 12kPa, less than 10kPa, less than 9kPa, less than 8kPa, less than 7kPa, less than 6kPa, less than 5kPa, less than 4kPa, less than 3kPa, less than 2kPa, and less than 1kPa, which is described as a modified atmosphere. As one option, a modified atmosphere (e.g., a low oxygen partial pressure) can be achieved by creating a vacuum inside or within the packaging, thereby resulting in an atmosphere in the container having an absolute pressure of 90 kPa or less, e.g., 80 kPa or less, 70 kPa or less, 60 kPa or less, 50 kPa or less, 40 kPa or less, 30 kPa or less, 20 kPa or less, 10 kPa or less, or 5 kPa or less. As another option, the atmosphere in the container can be modified by flashing with an unreactive gas (e.g., unreactive with the composite material). Examples of unreactive atmospheres include inert gases such as nitrogen, argon, helium, and xenon. Another unreactive gas is carbon dioxide. This atmosphere can be modified in one or more flashing steps (e.g., two or three or four or more flashing steps). As yet another option, the atmosphere can be modified in one or more combinations of vacuum and flashing steps to achieve the low oxygen content values ​​disclosed herein.

[0034] Alternatively, a low oxygen content in the atmosphere inside a package or container can be determined from the difference in oxygen partial pressure between the outside and inside of the container or package, where the outside atmosphere is greater than the inside atmosphere. For example, the difference in oxygen partial pressure between the outside and inside of the container or package can be at least 1 kPa, e.g., 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] Alternatively, a low oxygen content inside the packaging (inside the container) can be expressed by the amount of (molecular) oxygen in the packaging, e.g., the number of moles of oxygen per unit mass of the elastomer composite (e.g., millimoles) (e.g., 75 mmol / kg elastomer composite or less, as discussed here), the volume of oxygen (or the volume of oxygen per kg of composite), or the concentration of oxygen present in the atmosphere inside the container, e.g., less than 7%, less than 5%, less than 3%, less than 2%, or less than 1%. The oxygen concentration can be measured with an oxygen sensor, as discussed here.

[0036] As one option, the oxygen content of the container and packaging when sealed can be altered by sealing at least one type of oxygen scavenger inside the container. The oxygen scavenger removes (captures, removes) oxygen from the atmosphere of the closed container. The oxygen scavenger can remove oxygen by reaction (e.g., by oxidation) or by trapping oxygen. As another alternative, the atmosphere inside the container or packaging can be altered with a vacuum and / or a non-reactive gas, and the elastomer composite is further packaged with at least one oxygen scavenger. The oxygen content achieved by the use of the oxygen scavenger depends on the amount of scavenger used; the achieved oxygen content can be any of the values ​​disclosed herein, e.g., below 21 kPa, or any other level disclosed herein. The oxygen scavenger can be packaged together with the composite, for example, contained in or sealed in a sachet. This sachet must be oxygen-permeable and can be placed adjacent to the composite or attached to the inner wall (inside) of the container or packaging. Examples of oxygen scavengers include metals, e.g., metal powder or iron filings, ascorbic acid and its salts, any of the degradation inhibitors disclosed herein (e.g., antioxidants), catechol, and other oxygen scavengers known in the art. Degradation inhibitors can be mixed with elastomers during the mixing of elastomers with fillers, as is known in the art. For example, composites can contain the degradation inhibitors described herein. Another example is that at least one wall of a packaging can contain a material capable of removing oxygen. Examples of oxygen scavengers, oxygen barriers, and oxygen-depleting packaging, including packaging walls containing oxygen-depleting materials, can be found in Ahmed et al., Food Control, Volume 82, pp. 163-178 (2017), and their disclosure is incorporated herein by reference. As one alternative, the only oxygen scavenger present is a degradation inhibitor dispersed in a composite, as described herein.

[0037] At least one wall (oxygen barrier wall) may include one or more layers, such as one or more sheet laminates, films, liners, panels, etc. The wall may be a single-layer wall containing a material that provides suitable oxygen barrier properties (oxygen barrier material), or a multilayer wall (two or more layers) in which at least one of the layers contains the oxygen barrier material, i.e., that layer is the oxygen barrier layer. The layers of the wall may be films, panels, or laminates. Multilayer walls may be formed by extrusion or co-extrusion, extrusion coating, lamination (e.g., adhesive lamination), use of adhesives, or deposition of one layer onto other layers, use of bonding layers, or metallization.

[0038] Oxygen barrier walls (or layers) can contain many materials, the most common of which are polymers and / or metals. Polymeric oxygen barrier materials 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, copolymers of acrylonitrile and methyl acrylate (e.g., Barex® resin, which is a copolymer of acrylonitrile and methyl acrylate grafted with nitrile rubber), cycloolefin copolymers (COC), and mixtures thereof. Multilayer walls can contain one or more oxygen barrier layers. One or more barrier layers can be biaxially oriented, for example, by stretching polymer chains laterally to align with the plane of the layer or wall. Biaxial orientation allows the film to be stretched to orient its chains, which can provide enhanced strength, toughness, and pressure resistance (improved tensile properties).

[0039] Other oxygen barrier materials include those containing metals, such as metal layers. Metallized layers (indicated by the prefix "m", e.g., mPET) can be formed by a process known as metallization or metallization. In metallization, a metal can be deposited on a substrate by many methods, where the substrate can be a polymer material with desired flexibility or rigidity. For example, metallization can involve the evaporation of a metal, such as aluminum, followed by its deposition on a substrate film (e.g., vacuum deposition, chemical vapor deposition), resulting in the deposition of a thin metal layer on the substrate film. Methods for depositing the metal layer include sputtering and electroplating. Alternatively, a thin metal layer can be formed and then bonded to one or more polymer layers. Metals that can be used as metal layers or metallized layers include aluminum, tin, nickel, iron, silver, and their alloys, such as aluminum-zinc alloys, silver-zinc-aluminum alloys, and copper-zinc alloys. Other materials that can be deposited on polymer films include, in addition to metals, ceramics (e.g., gold oxides, e.g., silicon dioxide (SiO₂)). x Examples include carbon-based materials (e.g., silica, aluminum oxide, zinc oxide, magnesium oxide, titanium oxide, kaolinite, glass, and clay), carbon-based materials (e.g., carbon nanomaterials (e.g., carbon nanotubes and graphene materials, e.g., graphene, graphene oxide, reduced graphene oxide)), and melamine-based coating materials. Materials, such as metals, ceramics, and carbon-based coatings, can also be deposited as particles having submicron dimensions, e.g., in the range of 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 an alternative, at least one wall does not contain a metallized or metallic layer.

[0040] Metal containers that can be joined / welded to form an airtight seal can also provide oxygen barrier properties, such as stainless steel, tin, and aluminum. Containers containing metal can also contain other materials, such as glass, ceramics, and plastics, for example, glove boxes or rooms or other chambers. Rigid containers can be formed from thermoplastic elastomers and thermoplastic vulcanized materials. Thermoplastic elastomers (TPEs) contain one or more polymers; an elastomer (giving elasticity) and a second polymer (giving strength). Examples of TPEs include styrene block copolymers, e.g., styrene-butadiene-styrene block copolymers and ethylene acrylic copolymers. Thermoplastic vulcanized materials (TPVs) are a class of thermoplastic elastomers prepared by vulcanization or crosslinking, possessing the melt-processability of thermoplastics combined with the properties of crosslinked rubber, resulting in materials that can have high resistance to compression and thermal deformation. Examples of TPVs include Santoprene® thermoplastic vulcanized material (ExxonMobil) and vulcanized ethylene propylene diene (EPDM) rubber in a thermoplastic matrix of polypropylene (PP). Rigid containers can be sealed with adhesive materials, gaskets, O-rings, or similar sealing materials (e.g., nitrile rubber, butyl rubber, etc.).

[0041] An oxygen barrier wall or layer may optionally include an oxygen-depleting material embedded within the layer itself. Such an oxygen-depleting barrier layer is typically sandwiched between a structural layer and / or a protective layer that can function as a sealing layer. Alternatively, the film may be oxygen-depleting, i.e., an oxygen scavenger is embedded within the oxygen barrier material, or the film may be made of an oxygen-depleting material.

[0042] Suitable oxygen barrier properties of at least one wall can be achieved by one or more factors, such as the type of wall or layer material or the arrangement of layers (in multilayer walls). In multilayer walls, a typical layered arrangement includes a sealing layer as the innermost layer (e.g., polyethylenes, e.g., polypropylene, LDPE, LLDPE, or ethylene vinyl acetate (EVA)), followed by an oxygen barrier layer (e.g., a metal layer, polyamide) and a structural layer as the outer layer (e.g., PET, polyethylene).

[0043] The wall and layer thicknesses can also be selected to provide oxygen barrier properties (and other properties) of at least one wall, while taking into account the overall package mass to reduce transportation costs. For rigid packaging, the wall thickness can be at least 10 μm and no more than 10 cm, e.g., no more than 5 cm. For flexible packaging, the wall thickness can be in the range of 10 μm to 250 μm, e.g., 10 μm to 200 μm, 10 μm to 150 μm, 10 μm to 100 μm, or 10 μm to 50 μm. For example, PVdC coatings, EVOH-based films, polyamide films (e.g., nylon), and metallized polymer films can have thicknesses in the range of 10 μm to 30 μm, e.g., 15 μm to 30 μm. The oxygen barrier wall can have a thickness in the range of 5 μm to 50 μm, 5 μm to 40 μm, 5 μm to 40 μm, 5 μm to 30 μm, or 5 μm to 20 μm. The rigid packaging can have a thickness of at least 250 μm, for example, at least 500 μm.

[0044] The single-layer wall can be provided in the form of a flexible membrane, such as a liner or shrink wrap, or a rigid membrane (e.g., a metal container, a ceramic container). Examples of flexible membranes include PVdC shrink / stretch membranes as liners having a thickness of at least 30 μm, for example, in the range of 30 μm to 100 μm, 30 μm to 75 μm, or 30 μm to 50 μm.

[0045] In multilayer walls, any number of layers, such as 2, 3, 4, 5, 6, or 7 layers, can be used, up to 10 or 12 or more layers (e.g., up to 20 or even more). These layers can provide many properties, such as structural properties, odor and / or moisture barrier properties, oxygen barrier properties, sealable layers (e.g., heat-sealable layers), and combinations thereof, selected to give the desired flexibility or rigidity, transparency, and oxygen barrier level. Regardless of the number of layers, the resulting wall will have the desired oxygen barrier properties.

[0046] Regarding other properties of oxygen barrier properties, one or more layers can provide strength and / or rigidity and / or structural support, for example, to prevent deformation or fracture of the oxygen barrier wall (e.g., resistance to perforation). Some materials can provide two or more functions. Examples of such materials include the following: • Polyesters, such as polyethylene terephthalate and polycarbonate Polyethylenes (PE), such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), very low-density polyethylene (ULDPE), or linear low-density polyethylene (LLDPE), and mixtures thereof. • Polypropylene • Polyvinyl chloride (PVC) • Polylactic acid (PLA) • Ethylene-(meth)acrylic acid copolymer (e.g., Surlyn® resin from DuPont) • Acid copolymer resins (e.g., NUCREL® resin from Dow, which is a ternary copolymer of ethylene, methacrylic acid, and acrylate), and, • those mixtures

[0047] For any of the above, the corresponding metal or metallized layer can also be used by bonding, vacuum vapor deposition (CVD), sputtering, electroplating, or any other method of bonding a thin metal film to the plastic.

[0048] One or more layers of a multilayer structure can be a sealing layer or a sealable layer (sealant). A sealable layer allows panels (e.g., one or more top, side, and bottom panels) to be bonded to each other along their edges. One option is for the sealable layer to be a heat-sealable layer, which deforms or melts the polymer with the application of heat to enable adhesion. Alternatively, the sealable layer can be a laminate that bonds the layers together. In a multilayer wall, the sealable layer is often located on one or both of the outer edges of the multilayer wall; for example, the sealable layer can be the innermost layer (forming the inner wall) or the outermost layer (forming the outer wall). Examples of sealable layers include: • Polyesters, such as PET and metallized layers (e.g., mPET) • The polyethylenes disclosed above, such as low-density polyethylene (LDPE), chain-type low-density polyethylene (LLDPE), and HDPE, and the metallized layer, such as mVLDPE. • Polypropylene • Ethylene-acrylic acid copolymer (e.g., NUCREL® resin) • Ethylene-(meth)acrylic acid copolymer (e.g., Surlyn® resin) • Ethyl vinyl acetate (EVA), and, • those mixtures

[0049] Alternatively, an adhesive may be coated or laminated onto the layers to improve interlayer adhesion (e.g., adhesive-coated oxygen barrier layer and / or structural layer).

[0050] A sealable layer can bond or otherwise adhere one or more adjacent sealable layers to form an airtight seal, which provides barrier properties similar to those of a barrier wall. Alternatively, the sealable layer can be a layer that has good adhesion to and supports the adhesive. Certain sealable layers can also function as structural layers, such as polyesters, polyethylenes (e.g., LDPE, LLDPE, HDPE), polypropylene, ethylene-(meth)acrylic acid copolymers, EVA, and others known in the art.

[0051] One or more layers in a multilayer wall can be a moisture barrier, such as LDPE, that prevents water from entering or leaving (by elastomer composites). Other types of layers can be used to prevent the entry of other chemical vapors and / or light and / or other undesirable elements (e.g., polyamide and EVOH). Processability, hue / transparency, and odor barrier properties are also other factors in selecting layers.

[0052] For example, the following layer arrangements can be considered for multi-layer walls (the direction from left to right is from the inside to the outside of the container; "|" indicates the interface between layers). (i) Seal layer | O2 barrier | Seal layer (ii) Structural layer | O2 barrier | Seal layer (iii) Seal layer | O2 barrier | Structural layer (iv) First O2 barrier | structural layer | second O2 barrier | sealing layer (v) Structural and / or sealing layer | First O2 barrier | Second O2 barrier | Structural and / or sealing layer (vi) Structural and / or sealing layer | O2 barrier | Moisture barrier (vii) Structural and / or sealing layer | O2 barrier | Moisture barrier | Structural and / or sealing layer (viii) Structure and / or sealing layer | O2 barrier + moisture barrier

[0053] While arrangements of three or four layers are shown, one or more additional layers may be provided to complement any of the above arrangements. For example, an adhesive layer or laminate may be added between the oxygen barrier and the structural and / or sealing layers. Any number of layers of oxygen barrier walls are known in the art, e.g., single layer, two layers, three layers, four layers, five layers, six layers, seven layers, or more, e.g., ten layers and even twenty-layer walls (or more).

[0054] A multilayer wall may include two or more O2 barrier layers (e.g., a first and second O2 barrier layer, or even a third or fourth oxygen barrier layer or more). When there are two or more O2 barrier layers, the materials forming each O2 barrier layer may be the same or different. For example, each O2 barrier layer may be (or may include) polyamide (PA), poly(ethylene vinyl alcohol) (EVOH), poly(vinylidene chloride) (PVdC), polyvinyl alcohol (PVOH), methyl acrylate, or a metallized layer, such as mPET, mPA, mPE and mixtures thereof, or a metal layer (e.g., an aluminum layer); the structural layer may be HDPE, LDPE, VLDPE, ULDPE, LLDPE, polypropylene, PVC, PET, and mixtures thereof; and the sealing layer may be LDPE, LLDPE, HDPE, polypropylene, and EVA.

[0055] Selectively, any or all of these layers, or the oxygen barrier layer, may be biaxially stretched ("Bo").

[0056] Specific examples include the following: PA|PE|Aluminum foil|PE|LLDPE PE|EVOH|PE LLDPE | Nylon | EVOH | Nylon | LLDPE EVA|PA|EVA EVA | PA | mPET EVA | PA | mPP | LLDPE BoPP|LDPE|mBoPP|SURLYN In the above, "BoPP" represents biaxially oriented polypropylene, "m" represents a metallized layer, and "SURLYN" represents Surlyn® resin. One or more additional layers may be provided to complement any of the above arrangements.

[0057] A desired partial pressure of oxygen in a sealed container can be achieved in various ways. Methods for removing oxygen from a sealed container (or a container to be sealed) are known in the art. One option is to evacuate the inside of the container or packaging (or the contents or the inside of the container), flush it with a non-reactive gas (e.g., an inert gas), expose it to an oxygen absorber, and subject it to a combination thereof. For example, a container or packaging can be vacuum sealed with a device configured to evacuate the contents and then seal the packaging. Vacuum sealing machines (vacuum sealers) or vacuum heat sealing machines (vacuum heat sealers) are known in the art of packaging, such as flexible packaging. One example of a vacuum sealer has two surface members that can be opened and closed to clamp a substantially flat packaging opening. These surface members may include one bar that is raised and lowered relative to a base, and the open end of the packaging is inserted between the bar and the base. Alternatively, two bars may be used, for example, an upper bar rotatably attached to a lower bar. In either option, one or both bars may include heating and / or compression elements to achieve a seal. Between the two surface members are a vacuum pump and one or more nozzles optionally connected to an inert gas source. After the package is filled with the elastomer composite, the unsealed end of the package can be inserted between the two bars of the vacuum sheeter, while at least one retractable nozzle is inserted into the opening of the package. By clamping or engaging the two bars, the opening of the package can be effectively sealed and given a tight fit around at least one nozzle. Vacuum can be applied and optionally repeated with a flush with an inert gas. After vacuum is applied, the nozzle can be retracted and removed from the opening of the package. Immediately thereafter, heat is applied through the heating and / or pressurizing elements to seal the package. For the heating element, the heat can flex the sealing layer of the package wall and / or the adhesive coated on the sealing layer.Alternatively, the packaging can be housed in a chamber that can be placed under a vacuum and / or inert gas atmosphere, in which the chamber has bars that clamp and seal the open end of the packaging. An example of such a vacuum heat sealer is the retractable nozzle vacuum sealer with gas purging sold by AmeriVacs (San Diego, California). Instead of heating and pressurizing, a welding process can be used. For example, a CO2 laser can be used to heat and melt polymer layers to melt them.

[0058] As another example (for example, typically applied to more rigid containers, but also applicable to flexible containers), a container or packaging may include one or more holes or outlets that allow gas flow between the inside of the packaging and a vacuum pump. This hole may extend through the wall of the packaging and may be attached to the outside of the wall of the packaging (the surface of the outer wall) to seal a hose or tube extending to the vacuum pump. A collar (e.g., a substantially circular collar) may be included. This hole may further include a valve, for example a one-way valve, through which air or other gas can be drawn out from the inside of the container by the operation of the vacuum pump. As one option, this valve may be a two-way valve for filling the bag with nitrogen after the gas inside has been removed. Once the desired level of vacuum or the desired partial pressure of oxygen is achieved, the pump is stopped and the valve is activated to restrict air or oxygen from entering the container. Optionally, the collar can be fitted with a cap or other similar enclosure or closure to further prevent oxygen from entering the packaging, for example, at an oxygen permeability greater than that of the wall. This cap may be made of an oxygen barrier material and may be bonded to the collar with an adhesive material (e.g., glue). Alternatively, the valve area may be covered with adhesive when there is no cap.

[0059] Methods for storing or curing elastomer composites are also disclosed herein. Storing in sealed containers or packaging may occur in warehouses and may involve shipping / transportation processes. The method may involve storing the elastomer composite in a sealed container disclosed herein, for example, a container or packaging comprising at least one wall surrounding the composite, wherein the at least one wall comprises at least one oxygen barrier layer, thereby allowing the container to withstand temperatures of 100 cm at 23°C and 0% relative humidity. 3 (m 2 The packaging has an oxygen permeability of 75 mmol / kg or less (atm / day) and / or the amount of oxygen inside the packaging is 75 mmol / kg or less for the elastomer composite, or other ranges disclosed herein. As disclosed herein, at least one wall is an oxygen (O2) barrier wall comprising at least one layer which is an oxygen barrier. The method disclosed herein can result in an elastomer composite that maintains or even enhances at least one rubber property. Thus, also disclosed herein is a method for maintaining or enhancing at least one rubber property of an elastomer composite or a compound formed from such composite, comprising storing the composite in a sealed container for at least 5 days, or at least 14 days, or other periods disclosed herein. For example, this storage can be carried out in a low-oxygen atmosphere in one or more sealed containers having an oxygen barrier wall.

[0060] Disclosed herein is a method for storing elastomer composites, comprising the following steps: The elastomer composite material is sealed in a container, and the composite material is stored in the sealed container for at least 5 days, where, This elastomer composite is uncured and contains at least one elastomer and at least one filler, and This container includes at least one wall surrounding its composite material, At least one wall includes at least one oxygen barrier layer, thereby the container can withstand 100 cm at 23°C and 0% relative humidity. 3 (m 2 It has an oxygen permeability of less than 1 / 2 atm.

[0061] Disclosed herein is a method for maintaining or enhancing at least one property of an elastomer composite or a compound formed from such a composite, comprising the following steps: The elastomer composite material is stored in a sealed container for at least 5 days, where, This elastomer composite is uncured and contains at least one elastomer and at least one filler, and This container includes at least one wall surrounding its composite material, Here, at least one wall includes at least one oxygen barrier layer, thereby the container can withstand 100 cm at 23°C and 0% relative humidity. 3 (m 2 It has an oxygen permeability of less than 1 / 2 atm.

[0062] Before sealing (and storing), this method may include subjecting the composite material inside the container or packaging to at least one step of altering the atmosphere inside the container to achieve an atmosphere with a low oxygen content. One option is to alter the atmosphere inside the container by flashing it with at least one gas that is non-reactive with the composite material (a non-reactive gas), e.g., a gas containing 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, e.g., nitrogen, argon, helium, xenon, or other non-reactive gases, e.g., carbon dioxide, or mixtures of these gases. Flushing involves replacing at least a portion of the air present in the packaging with at least one non-reactive gas (e.g., nitrogen, argon, etc.), thereby the atmosphere containing at least 90% non-reactive gas, e.g., at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, and at least 99% non-reactive gas. In other words, the atmosphere contains at least 90% (or other amounts disclosed herein) of at least one gas that is non-reactive with the elastomer composite.

[0063] As an alternative, the atmosphere can be altered by removing a substantial amount of oxygen from the container, for example by creating a vacuum inside the container (or by applying a vacuum inside the container) by any of the methods disclosed herein or known in the art. The inside of the container can be left at any desired level of vacuum disclosed herein, in which case the vacuumed container can have an absolute pressure of 90 kPa or less, for example, 80 kPa or less, 70 kPa or less, 60 kPa or less, 50 kPa or less, 40 kPa or less, 30 kPa or less, 20 kPa or less, 10 kPa or less, 5 kPa or less, or 1 kPa or less. In addition to, or as an alternative to, gas flushing and / or vacuuming, a sachet containing an oxygen scavenger can be placed inside the container, in which case, over time, the scavenger will remove oxygen from the inside, thereby reducing the oxygen content inside the container.

[0064] As one option, the atmosphere can be altered by subjecting the composite material inside the container (the inside of the container housing the composite material) to at least one of the following steps: flushing the inside of the container with at least one gas that is non-reactive with the composite material, and applying a vacuum to the inside of the container. The alteration of the atmosphere may include one or a combination of these steps. For example, after the composite material has been placed inside the container, the inside of the container may be flushed with a non-reactive gas, and then or beforehand, a vacuum may be applied to the inside of the container, in which case this flushing / vacuum procedure with an inert gas can be repeated as needed, for example, one, two, three, four, or even five or more times, consisting of the procedure of flushing the inside of the container (the composite material inside the container) with a non-reactive gas, followed by the application of a vacuum to the inside of the container, or one, two, three, four, or even five or more times, consisting of the procedure of applying a vacuum to the inside of the container, followed by the flushing of the inside of the container with a non-reactive gas. One option is that the final step after one or more sequences is a step of sealing the container under vacuum, for example, a vacuum-packed container or package (regardless of the sequences applied before it). Alternatively, the final step after one or more sequences is a flushing of the inside of the container with a non-reactive gas, resulting in a sealed composite inside the container under an atmosphere containing at least 90% of the elastomer composite and at least one gas that is non-reactive with the composite. Another option is a single or more step of applying a vacuum inside the container (without flushing with a non-reactive gas) followed by a step of sealing the container. Alternatively, a single or more step with at least one non-reactive gas (without applying a vacuum) may be performed, followed by a step of sealing the container (without applying a vacuum).

[0065] Elastomer composites in sealed containers or packaging can be stored for at least 5 days, or for any other period disclosed herein. The storage period can be determined from the time of sealing. As one option, elastomer composites can 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 2 years or more, and potentially indefinitely. Other options include the storage of elastomer composites over periods ranging from 5 days to 2 years, 5 days to 1 year, 5 days to 6 months, 5 days to 3 months, 2 weeks (14 days) to 2 years, 2 weeks (14 days) to 1 year, 2 weeks (14 days) to 9 months, 2 weeks (14 days) to 6 months, 2 weeks (14 days) to 3 months, 21 days to 1 year, 21 days to 9 months, 21 days to 6 months, 21 days to 3 months, 1 month to 1 year, 1 month to 9 months, 1 month to 6 months, 1 month to 3 months, and other periods in between.

[0066] One option is for the composite material to be stored under low oxygen content (modified atmosphere) immediately after mixing or compounding (within 15 minutes after the composite material is discharged from the mixer or compounding machine), or within 1 hour, 2 hours, 3 hours, 6 hours, 1 day, 1 week, or 1 month (30 days), provided that the degradation of the composite material is not substantial. For example, the composite material may be stored in air or refrigerated before packaging or long-term storage or transport. Alternatively, the composite material may be transported in air to a facility where it can be moved to packaging or other conditions that provide storage under low oxygen content. Another option is for the composite material to be sealed in a container in air, where a high oxygen barrier wall prevents substantial entry of oxygen into the container. Sealing in the air can be done within 1 hour, 2 hours, 3 hours, 6 hours, 1 day, 1 week, or 1 month (30 days) after discharge from the mixer or compounder.

[0067] The composite material can be stored in packaging or containers at any temperature in the range of 20°C to 200°C. Alternatively, the packaged composite material can be stored under ambient conditions (at temperatures in the range of 20°C to 40°C, or 20°C to 30°C) in either a climate-controlled atmosphere or an unclimate-controlled area (e.g., a warehouse, a truck).

[0068] As one option, the composite material can be stored in a container at a high temperature, for example, at least 40°C, for example, 40°C to 200°C, 40°C to 180°C, 40°C to 150°C, 40°C to 120°C, 40°C to 100°C, 40°C to 90°C, 40°C to 75°C, 50°C to 200°C, 50°C to 180°C, 50°C to 150°C, 50°C to 120°C, 50°C to 100°C, 50°C to 90°C, 50°C to 75°C, 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 for at least 5 days. In certain embodiments, the composite material may be stored at high temperatures for, for example, at least 7 days, at least 2 weeks (14 days), at least 3 weeks (21 days), or at least 1 month, 6 months or less, or 1 year or less. As one option, storage at high temperatures may be carried out for 1 month or less, 2 weeks or less, or 1 week or less, for example, 5 days to 1 month.

[0069] As one option, before storage, the composite material may be heated, for example, in 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 may be carried out for a period of time of at least 15 minutes, at least 30 minutes, at least 1 hour, at least 2 hours, at least 3 hours, at least 6 hours, at least 12 hours, at least 18 hours, at least 1 day, or at least 2 days, and no more than 5 days. The heat treatment may be carried out 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 other high temperatures disclosed herein. The upper limit of the temperature may be determined by the composition of the composite material and / or the container used. For example, depending on whether the composite material contains a specific synthetic rubber (or a mixture containing synthetic rubber) or a majority of natural rubber, the composite material may be heated to a temperature of 200°C or less, 180°C or less, 160°C or less, or 150°C or less (e.g., 40°C to 160°C).

[0070] Heating or heat treatment can be carried out in a chamber (e.g., an oven, glove box) having a substantially oxygen-free atmosphere, or in a container or packaging having an oxygen barrier wall. The composite material can be heat-treated in an oven or glove box or other chamber and then transferred to a container or packaging for sealing and storage, and the composite material can be cooled to ambient temperature (e.g., 20–40°C, or 20–30°C) before being transferred to the container or packaging, at which point the composite material has a high temperature as defined by the probe temperature disclosed herein. Alternatively, the composite material can be heat-treated in packaging having an oxygen barrier wall and then cooled in the packaging. Depending on the temperature of the composite material, heat-stabilized vacuum packaging may be used.

[0071] Therefore, prior to storage, the method includes a step of forming a heat-treated elastomer composite, which includes heating an uncured elastomer composite in an oxygen barrier container or packaging disclosed herein at a temperature of at least 40°C for a period of 5 days or less, wherein the elastomer 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 of less than 17 kPa. (ii) The inside of the container has an oxygen content of 10 mmol / kg or less of elastomer composite material. (iii) The inside of the container has an oxygen concentration of less than 7%, less than 5%, less than 3%, less than 2%, or less than 1%.

[0072] Alternatively, the composite material may be discharged from the mixer and sealed under a modified atmosphere, for example, an atmosphere having an oxygen partial pressure of less than 21 kPa (or other ranges disclosed herein), an atmosphere containing at least 90% unreactive gas, for example, a nitrogen atmosphere, or an atmosphere having an oxygen-to-elastomer ratio of 75 mmol / kg of elastomer composite material, or under vacuum (for example, with an absolute pressure of 90 kPa or less inside the container). The time between discharge from the mixer and sealing under the modified atmosphere may be immediately (e.g., within 5 minutes, 10 minutes, or 15 minutes), or within 30 days, for example, within 2 weeks, 1 week, 1 day, 12 hours, 6 hours, 3 hours, 2 hours, 1 hour, or 30 minutes. This time is determined in relation to minimizing the amount of degradation of the composite material.

[0073] Alternatively, the composite material can be discharged from the mixer under a modified atmosphere (e.g., an inert gas atmosphere, e.g., a nitrogen atmosphere) and maintained or stored under the modified atmosphere (e.g., discharged, transported, and sealed in packaging, with all processes performed under the modified atmosphere). The composite material discharged from the mixer (either discharged into or transferred to the modified atmosphere) may have a probe temperature of 200°C or less (e.g., immediately after discharge from the mixer), depending on the mixing conditions and / or whether the composite material is cooled.

[0074] The probe temperature of a composite material is typically the temperature of the composite mass and can be measured, for example, by inserting a thermocouple or other temperature measuring device into the composite material. One option is that when sealed in a container or packaging, the composite material may have a probe temperature in the range of 20°C to 200°C, e.g., 20°C to 180°C, 20°C to 100°C, 40°C to 200°C, or 40°C to 100°C. Typically, upon discharge, the composite material may have a probe temperature in the range of 100°C to 180°C. Alternatively, the discharged composite material may be subjected to cooling and may have a temperature in the range of 20°C to 60°C, e.g., 20°C to 50°C, 20°C to 50°C, or 20°C to 60°C. In other embodiments, the composite material has a probe temperature in the range of 30°C to 100°C, for example, 40°C to 100°C, 50°C to 100°C, 60°C to 100°C, 30°C to 90°C, 40°C to 90°C, 50°C to 90°C, 60°C to 90°C, 30°C to 60°C, 40°C to 60°C, or 30°C to 50°C, or 30°C to 40°C.

[0075] An elastomer composite can be considered an uncured (e.g., unvulcanized or pre-vulcanized) mixture containing fillers and elastomers, along with one or more additives of any choice, the additives of which will be discussed in further detail here. Packaged, this composite can be considered a mixture or a masterbatch. This composite can, as one option, be an intermediate product subjected to a subsequent curing or vulcanization process to obtain a rubber compound or rubber article.

[0076] Elastomer composites contain fillers dispersed within an elastomer. These composites can be prepared in many ways, for example, by mixing at least one elastomer with at least one filler in a mixer, such as a meshing or tangential mixer (e.g., a Banbury or Brabender mixer), an extruder, a roll mill, a continuous compounder, or other rubber mixing apparatus. The fillers and / or elastomers can be mixed in a dry or wet state. A dry mixing process involves mixing a solid elastomer with a filler in a dry state (not wetted or dispersed in a liquid). The mixing process may involve, or include, providing a continuous flow under pressure of a first fluid (slurry) containing at least one filler, and a continuous flow of at least a second fluid containing the elastomer latex, and mixing the flows of the first and second fluids to distribute the filler into the elastomer latex. The mixed latex and filler slurry solidify to form a wet crumb, which is then dehydrated to form a composite material. This is also known as the “wet mixing” process and is described in many publications, e.g., U.S. Patents No. 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, which are incorporated herein by reference. The mixer may be a continuous mixer or any other type of mixer.

[0077] Alternatively, PCT Publication WO2020 / 247663 describes a mixing process involving a solid elastomer and a wetting filler containing a filler and a liquid, which is incorporated herein by reference. Under the conditions outlined in PCT Publication WO2020 / 247663, this mixing yields a composite material containing a filler dispersed in the elastomer, where the liquid content is sufficiently small to allow compounding operations and optional further post-processing steps, such as extrusion, calendering, milling, granulation, baling, compounding, and sheeting. Such compounding and post-processing steps can be performed on the elastomer composite regardless of the mixing method performed.

[0078] Furthermore, the composite materials can be prepared by continuous mixing, as described in PCT Publications WO2018 / 219630, WO2018 / 219631, WO2020 / 001823, and WO2020 / 247663, and their disclosures are incorporated herein by reference.

[0079] In addition to fillers and elastomers, the composite material may include degradation inhibitors, coupling agents, processing aids (to facilitate rubber mixing and processing, e.g., various oils and plasticizers, waxes), activators (to activate the vulcanization process, e.g., zinc oxide and fatty acids), accelerators (to accelerate the vulcanization process, e.g., sulfenamides and thiazoles), vulcanizing agents (or curing agents, to crosslink the rubber, e.g., sulfur, peroxides), and other rubber additives, for example, but not limited to, at least one additive selected from vulcanization retarders, crosslinking aids, peptizers, tack enhancers, tackifiers, resins, flame retardants, colorants, and foaming agents. As one option, the composite material may not contain a vulcanizing agent. For example, the composite material may further include at least one additive selected from degradation inhibitors, coupling agents, processing aids, activators, accelerators, vulcanization retarders, crosslinking aids, peptizers, adhesion promoters (e.g., the use of cobalt salts to promote adhesion of steel cords to rubber elastomers, e.g., as described in U.S. Patent No. 5,221,559 and U.S. Patent Application Publication No. 2020 / 0361242, which are incorporated herein by reference), resins (e.g., tackifiers, traction resins), flame retardants, colorants, foaming agents, and heat-reducing additives (HBU). As another option, the rubber chemical may include processing aids and activators. As yet another option, one or more rubber chemicals may be selected from zinc oxide, fatty acids, zinc salts of fatty acids, waxes, vulcanization accelerators, resins, and process oils. Examples of resins include one or more C5 resins, C5-C9 resins, C9 resins, rosin resins, terpene resins, aromatically modified terpene resins, dicyclopentadiene resins, alkylphenol resins, and resins disclosed in U.S. Patent Nos. 10,738,178, 10,745,545 and U.S. Patent Application Publication No. 2015 / 0283854 (these disclosures are incorporated herein by reference).

[0080] For example, after the composite is initially formed by dry mixing, wet mixing, solid elastomer / wet filler mixing, or other mixing processes, the composite can be optionally compounded with one or more additional components, such as degradation inhibitors, zinc oxide, fat residues, zinc salts of fatty acids, waxes, vulcanization accelerators, resins, coupling agents, and process oils. As one option, the composite may include degradation inhibitors added during the initial mixing process, in which fillers (if any) are mixed and dispersed in the elastomer before compounding. Since degradation inhibitors can react with oxygen to prevent rubber degradation, they can also be considered a type of oxygen scavenger. A degradation inhibitor (e.g., an antioxidant) may be present in the composition in amounts ranging from 0.5% to 5% by mass, 1% to 5% by mass, 0% to 3% by mass, 0.5% to 3% by mass, 1% to 3% by mass, 0% to 2% by mass, 0.5% to 2% by mass, or 1% to 2% by mass, based on the mass of the composite material. In other words, a degradation inhibitor (e.g., an antioxidant) may be present in the composite material (either after the initial mixing or after the formulation) in amounts ranging from 0.5 phr to 10 phr, 0.5 phr to 5 phr, 0.5 phr to 3 phr, 0.5 phr to 2 phr, 1 phr to 10 phr, 1 phr to 5 phr, 1 phr to 3 phr, or 1 phr to 2 phr.

[0081] As one option, the composite material may include a vulcanizing agent (or a curing or hardening agent for crosslinking the rubber, e.g., sulfur, peroxide) in addition to any other additives disclosed herein, e.g., a “green compound”. With or without a vulcanizing (hardening) agent, a composite material packaged according to the parameters and methods disclosed herein is considered uncured until subjected to a vulcanization process.

[0082] As one option, the storage or method of the composite material in the oxygen barrier container disclosed herein can enable the composite material to be substantially free of any degradation inhibitor or antioxidant. Oxidation or reaction with oxygen is one factor in the degradation of elastomer composite materials. Removal of oxygen can make the addition of degradation inhibitors or antioxidants unnecessary. As one option, a composite material substantially free of any degradation inhibitor may contain a degradation inhibitor in an amount of 1% by mass or less of the composite material, for example, 0.5% by mass or less, 0.3% by mass or less, 0.2% by mass or less, 0.1% by mass or less, for example, 0.1% to 1% by mass, 0.2% to 1% by mass, 0.1% to 0.5% by mass, 0.2% to 0.5% by mass, 0.1% to 0.3% by mass, or 0% to 0.1% by mass. In other words, the composite material contains a degradation inhibitor in amounts ranging from 0 to 0.5 phr, 0.1 to 0.5 phr, 0.2 to 0.5 phr, 0 to 0.3 phr, 0.1 to 0.3 phr, 0 to 0.2 phr, or 0 to 0.1 phr. In formulations that are substantially free of degradation inhibitors (e.g., substantially free of antioxidants), the formulation may optionally contain one or more other additives, such as zinc oxide, fatty acids, zinc salts of fatty acids, waxes, vulcanization accelerators, resins, coupling agents, process oils, and / or vulcanizing agents.

[0083] One option is for the uncured composite to consist essentially of fillers dispersed in an elastomer, or for the uncured composite to consist essentially of fillers and degradation inhibitors dispersed in an elastomer. Another option is for the uncured composite to consist essentially of fillers and crosslinking agents dispersed in an elastomer, or for the uncured composite to consist essentially of fillers, degradation inhibitors, and crosslinking agents dispersed in an elastomer.

[0084] In certain embodiments, composite materials may have excess moisture, for example, composite materials made in accordance with PCT Publication WO2020 / 247663. For example, composite materials may have a moisture content in the range of 3% to 20%, for example, 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%. In the absence of degradation inhibitors, such composite materials are susceptible to mold formation. Containers and packaging with oxygen barrier walls can enable the storage of such composite materials containing excess moisture (even if substantially no degradation inhibitors are included) because the low oxygen content inside the packaging can reduce the degree of mold formation (if any).

[0085] When packaging or storing an elastomer composite in a container containing an oxygen barrier wall as disclosed herein, the composite can 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 (e.g., 5 days to 2 years, or 5 days to 1 year, or any other period disclosed herein), and such composite can be referred to as a cured or stored composite.

[0086] The resulting stored or cured composites and / or rubber compounding made from stored or cured composites may exhibit similar properties (maintaining 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 stored or cured under ambient conditions (e.g., ambient oxygen partial pressure, ambient absolute pressure, etc., e.g., composites stored in air). Furthermore, corresponding compounding made from such stored composites may obtain equivalent or even enhanced properties compared to compounding made from the composite at the time of sealing and / or compared to compounding made from composites stored or cured under ambient conditions (e.g., stored in air). At the time of sealing, a sample of the composite may be subjected to various measurement techniques or compounded to form other rubber compounding whose properties are to be measured or acquired. Such measured properties of the composite at the time of packaging serve as a control sample (rubber compounding formed from the control sample composite serves as a control rubber compound). After storage or curing over a certain period, for example, the period disclosed herein, the properties of a sample of the cured or stored composite material and the subsequent compound formed therefrom can be measured or obtained.

[0087] In certain cases, such rubber properties are maintained, for example, with a decrease in properties of less than 10%, less than 5%, less than 3%, less than 2%, or less than 1% of the values ​​when packaged or sealed. In other cases, cured or stored composites and corresponding formulations made from cured or stored composites exhibit enhanced values. The improvement can be observed by an enhancement of at least 5%, or at least 10%, of rubber properties compared to the properties when sealed or packaged, and / or compared to composites stored or cured under ambient conditions (and corresponding formulations made from such composites). Such improvements can be a decrease in a beneficial value (e.g., the Paine effect or Paine ratio of the composite or the corresponding rubber formulation, or the hysteresis of the rubber formulation indicated by the maximum tanδ), or an increase in a beneficial property, such as tensile strength, tensile stress, or the modulus ratio of the corresponding formulation.

[0088] For example, the rheological properties of composites (and formulations formed from such composites) can be enhanced for storage of the composites in the high oxygen barrier containers disclosed herein. One such property is the Payne effect of the composite (unvulcanized), which can be expressed by the Payne ratio or Payne difference. The Payne ratio is defined by G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the 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 over different periods, insofar as the measurements are taken before vulcanization. In some examples, after at least 5 days (at least 14 days) from the sealing or storage of the packaging or container at a temperature of, for example, at least 25°C, at least 30°C, at least 40°C, at least 50°C, or at least 60°C, the elastomer composite has a Pane ratio defined by G'(0.3%) / G'(51.5%) that is reduced by at least 10% (e.g., at least 15%, or at least 20%) compared to the Pane ratio of the composite on day 0 from the sealing of the packaging. As one option, the composite has a Pane ratio of 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 Pane ratio in the range of 1-15, 1-12, 1.5-15, 1.5-12, 2-15, or 2-12.

[0089] For example, the properties of a cured compound (formed from such cured or stored composites) can be favorably enhanced, such as by rubber compound properties, e.g., rheological properties, e.g., a decrease in the Payne ratio as defined above (by at least 10%), or a decrease in the hysteresis of the rubber compound indicated by the maximum tanδ (by at least 10%), or by mechanical properties, e.g., an increase of at least 10% in the modulus ratio or tensile stress ratio (where the modulus ratio or tensile stress ratio 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 material may be packaged after the filler has been mixed and dispersed in the elastomer, or after a further mixing step in which the composite material is compounded with one or more additives (e.g., degradation inhibitors, coupling agents, processing aids, activators, vulcanization accelerators, vulcanizing agents, as discussed in more detail herein), while the composite material is still uncured. The composite material may be packaged with minimal degradation immediately after discharge from the mixer or after a period of time at the temperatures disclosed herein.

[0091] When packaging composites with high internal or probe temperatures, the packaging or container can be selected to withstand such high-temperature filling processes. Shrinkage or other deformation may occur when cooling the composite, especially if the inside of the packaging is under reduced pressure, for example, under vacuum. High-temperature filled packaging is typically flexible and configured to deform upon cooling. Thermally stabilized vacuum methods can also be used. Alternatively, the packaging can be very rigid, e.g., a plastic with a high Tg, or one with thick walls (e.g., walls thicker than 250 μm), or a metal container.

[0092] The fillers and elastomers forming the composite material may be any fillers and elastomers known in the art. Examples of elastomers include natural rubber (NR), functionalized natural rubber, synthetic elastomers, e.g., styrene-butadiene rubber (SBR, e.g., solution SBR (SSBR), emulsion SBR (ESBR), or oil-extracted SSBR (OESSBR)), functionalized styrene-butadiene rubber, polybutadiene rubber (BR), functionalized polybutadiene rubber, polyisoprene rubber (IR), ethylene propylene rubber (EPDM), isobutylene elastomers (e.g., butyl rubber), halogenated butyl rubber, polychloroprene rubber, nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers, and mixtures thereof. Other synthetic polymers that can be used in this method include hydrogenated SBR and thermoplastic block copolymers (e.g., recyclable ones). Examples of synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene, and isoprene. Other synthetic elastomers include those synthesized by metallocene chemistry, in which case 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, such as monomers containing modern carbon as defined by ASTM D6866, for example, polymers made from bio-derived styrene monomers disclosed in U.S. Patent No. 9,868,853 (which is incorporated herein by reference), or polymers made from bio-derived monomers, such as butadiene, isoprene, ethylene, propylene, farnesene, and their comonomers, can also be used.

[0093] As one option, the composite may include at least one elastomer that degrades upon exposure to oxygen, such as diene elastomers, including natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, and mixtures thereof. As another option, the composite may further include other elastomers that are substantially unaffected by oxygen, as known in the art. As yet another option, the at least one elastomer may include natural rubber (e.g., at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% natural rubber) and further include at least one synthetic elastomer. As yet another option, the at least one elastomer may include natural rubber and further include at least one further elastomer, such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, or any synthetic rubber known in the art or disclosed herein.

[0094] Any filler known in the field of elastomer composites can be used. The filler can be particulate, fibrous, or plate-like. For example, particulate fillers are made of separated solids. Such fillers often have aspect ratios (e.g., length to diameter) of 3:1 or less, 2:1 or less, or 1.5:1 or less. Fibrous fillers can have aspect ratios of 2:1 or more, 3:1 or more, 4:1 or more, or higher.

[0095] Fillers include carbonaceous materials, carbon black, silica, bio-based fillers such as nanocellulose and lignin, clay, nanoclay, metal oxides, metal carbonates, and fillers from recycled materials such as pyrolysis carbon, recycled carbon, and recycled carbon black (e.g., ASTM). The materials may include at least one material selected from those defined in D8178-10 (rCB), graphene, graphene oxide, reduced graphene oxide (e.g., reduced graphene oxide disclosed in PCT Publication WO2019 / 070514, or densely packed reduced graphene oxide granules disclosed in U.S. Patent Application Publication 62 / 857,296 filed June 5, 2019 and PCT Publication WO2020 / 247681 (these disclosures are included herein by reference)), carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures (CNS), carbon nanotube fragments, crushed multi-walled carbon nanotubes (such as those disclosed in PCT Application PCT / US2021 / 27814, the disclosures are included herein by reference), or combinations thereof, or corresponding coated or chemically treated materials thereof (e.g., chemically treated carbon black).

[0096] Other suitable fillers include carbonaceous nanostructures (CNS, single-walled CNS), multiple carbon nanotubes (CNTs) crosslinked in a polymer structure by branching, e.g., dentrimer-like, interlocked, entangled, and / or having common walls. CNS fillers are described in U.S. Patent No. 9,447,259 and PCT Publication WO2021 / 247153, and are incorporated herein by reference to their disclosures. Mixtures of fillers may also be used, e.g., silica and carbon black, silica and silicon-treated carbon black, and mixtures of carbon black and silicon-treated carbon black. Fillers may be chemically treated (e.g., chemically treated carbon black, chemically treated silica, silicon-treated carbon black) and / or chemically modified. Fillers may be or contain carbon black having bound organic groups. Fillers may have one or more coatings on the filler (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 restrictions on the type of filler (e.g., silica, carbon black, or other fillers).

[0097] The fillers may include fibrous fillers, such as natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nano-sized carbon filaments), such as short-chain fibers disclosed in PCT Publication WO2021 / 153643 (which are incorporated herein by reference). Other fibrous fillers include poly(p-phenylene terephthalamide) pulp, commercially available as Kevlar® pulp (DuPont).

[0098] Examples of bio-derived or bio-based materials (derived from biosources), recycled materials, or other fillers considered renewable or sustainable include hydrothermal carbon (HTC, in which case the filler includes lignin treated by hydrothermal carbonization as described in U.S. Patent Nos. 10,035,957 and 10,428,218, which are incorporated herein by reference), rice husk silica, carbon from methane pyrolysis, modified polysaccharide particles, siliceous soil, crumb rubber, and functionalized crumb rubber. Examples of modified polysaccharides include those described in U.S. Patent Application Publication Nos. 2020 / 0181370 and 2020 / 0190270, which are incorporated herein by reference. For example, the polysaccharide can be selected from polyalpha-1,3-glucan; polyalpha-1,3-1,6-glucan; water-insoluble alpha-(1,3-glucan) polymers having 90% or more alpha-1,3-glycosidic bonds, less than 1% by mass of alpha-1,3,6-glycosidic branching points, and a number-average degree of polymerization in the range of 55 to 10,000; dextran; compositions containing polyalpha-1,3-glucan ester compounds; and water-insoluble cellulose having a mass-average degree of polymerization (DPw) of about 10 to about 1000 and a cellulose II crystalline structure. As one option, at least one filler can be selected from rice husk silica, lignin, nanocellulose, and hydrothermal carbon.

[0099] There are no limitations on the types of fillers that can be used (e.g., silica, carbon black, or other fillers disclosed herein), including bio-based (derived from biosources) and recycled materials (e.g., recycled carbon). Examples of coating fillers are those described in U.S. Patent No. 10,519,298, which are incorporated herein by reference. Examples of chemically treated fillers include those with at least one organic group bonded to them (e.g., by a diazonium reaction) (e.g., carbon black), such as those described in U.S. Patents 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, and 5,922,118, which are incorporated herein by reference.

[0100] The filler may include silicon-treated carbon black, silicon-containing species such as silicon oxides or carbides, which are distributed as an intrinsic portion of the carbon black through at least a portion of the carbon black aggregates. Silicon-treated carbon black is not a coated or otherwise modified carbon black aggregate, but actually represents two-phase aggregate particles. One phase is carbon, which still exists as graphitic crystals and / or amorphous carbon, while the second phase is silica and possibly other silicon-containing species. Thus, the silicon-containing species phase of silicon-treated carbon black is an intrinsic portion of the aggregate and is distributed through at least a portion of the aggregate. Ecoblack® silicon-treated carbon black is available from Cabot Corporation. The manufacture and properties of these silicon-treated carbon blacks are described in U.S. Patent No. 6,028,137, which is incorporated herein by reference. Silicon-treated carbon black may include silicon-containing regions primarily on the surface of carbon black aggregates, but which may still be parts of carbon black, and / or silicon-treated carbon black may include silicon-containing regions distributed throughout the carbon black aggregates. Silicon-treated carbon black may be oxidized.

[0101] At least one filler (e.g., carbon black, silica, silicon-treated carbon black, or any other filler disclosed herein or a combination thereof) can be dispersed in at least one elastomer in filling amounts ranging from 20 phr to 250 phr, e.g., 20 phr to 240 phr, 20 phr to 230 phr, 20 phr to 220 phr, e.g., 20 phr to 180 phr, 20 phr to 150 phr, 20 phr to 120 phr, 20 phr to 100 phr, 20 phr to 80 phr, 20 phr to 60 phr, 30 phr to 100 phr, 30 phr to 80 phr, 30 phr to 60 phr, 40 phr to 100 phr, 40 phr to 80 phr, and 40 phr to 60 phr. Certain carbon-based nanomaterials, such as graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, fragments of carbon nanostructures, and fragmented multi-walled carbon nanotubes, can be dispersed in at least one elastomer in a packing amount of at least 0.1 phr, either alone or together with one or more non-carbon-based nanomaterials, such as carbon black, silica, silicon-treated carbon black, and other fillers and combinations disclosed herein. Carbon-based nanomaterials can be dispersed in at least one elastomer in packing amounts ranging from 0.1 phr to 50 phr, 0.5 phr to 50 phr, 0.5 phr to 40 phr, 0.5 phr to 30 phr, 0.5 phr to 20 phr, 0.5 phr to 10 phr, 0.5 phr to 5 phr, 0.5 phr to 3 phr, 0.5 phr to 2 phr, 0.5 phr to 1 phr, 1 phr to 20 phr, 1 phr to 10 phr, 1 phr to 5 phr, 1 phr to 3 phr, or 1 phr to 2 phr. Other ranges can be envisioned, such as those disclosed in PCT Publication WO2020 / 247663, PCT Publication WO2019 / 070514, and PCT Application PCT / US2021 / 27814.

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

[0103] If the filler contains 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 if the filler is substantially all carbon black, the uncured composite can be a product formed by mixing at least one crosslinking agent. For example, the composite can be prepared by mixing at least a filler, an elastomer (or elastomer latex), and at least one crosslinking agent, or the composite may further contain at least one crosslinking agent. Composites prepared in the presence of specific crosslinking agents, such as those disclosed in PCT application PCT / US21 / 62433 filed on December 8, 2021 (the disclosure thereof is incorporated herein by reference), can exhibit reduced degradation over long periods, for example, at a temperature of at least 20°C, for more than 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, and even for at least 6 months (at least 180 days), 1 year (12 months) or less, or even 2 years or less. Such reduced degradation may be at least a partial adduct with the benefits obtained by the storage / packaging method disclosed herein. As one option, the composite further comprises at least one crosslinking agent, for example, an uncured composite or masterbatch comprising fillers and elastomers is prepared according to any method known in the art and then subjected to one or more compounding or processing steps with at least one crosslinking agent and optionally at least one additive (e.g., a degradation inhibitor or other additive disclosed herein) before forming a crosslinked product.

[0104] As one option, the crosslinking agent is selected from compounds having at least one functional group, where, The first functional group is -NR 1 R 2 , -N(R 1)(R 2 )(R 3 ) + A - ,- S-SO3M 1 , selected from the structures represented by equations (I) and (II), [ka] In the formula, A - The compounds are chloride, bromide, iodide, hydroxyl, nitrate, or acetate, where X=NH, O, or S, Y=H, OR 4 , NR 4 R 5 , -S n R 4 And n is an integer selected from 1 to 6, and, The second functional group is thiocarbonyl, nitrile oxide, nitrone, nitrile imine, -S-SO3M 2 , -S x R 6 -SH, -C(R 6 )=C(R 7 )--C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 Selected from, and,

[0105] R 1 ~R 8 Each is independently selected from H and C1-C8 alkyl groups, and M 1 and M 2 These are H and Na, respectively, independently. + , K + Li + , N(R')4 + Selected from, where each R' is independently H and C1~C 20 It is selected from alkyl groups, and x is an integer selected from 1 to 8.

[0106] While not wishing to be bound by any theory, it is believed that while the mixing process with a wet filler can promote dispersion of the filler, the crosslinking agent can interact with the filler and / or the elastomer to generate stronger interactions between the filler and the elastomer. In one option, the crosslinking agent can have at least two functional groups, wherein the first and second functional groups are capable of interacting with the elastomer and / or filler. This interaction may include adsorption or chemical bonding, for example, ionic interactions, dipole-dipole interactions, hydrogen bonding, covalent bonding, and the like. In the present composite material, the crosslinking agent may be present in the same form as it remains when filled into the mixer, or in a different form, for example, when it interacts with the filler and / or elastomer via chemical bonding.

[0107] A crosslinking agent having at least two functional groups may comprise two, three, four, or five or more functional groups. In any of these embodiments, the crosslinking agent is - NR 1 R 2 , -N(R 1 )(R 2 )(R 3 ) + A - , - S-SO3M 1 , and may be selected from the structures represented by formula (I) and formula (II).

Chemical Formula

[0108] The crosslinking agent may further comprise a second functional group, which is selected from thiocarbonyl, nitrile oxide, nitrone, nitrile imine, -S-SO3M 2 , - S x -R 6 , -SH, - C(R 6 )=C(R 7 )-C(O)R 8 , - C(R 6 )=C(R 7 )-CO2R 8 , - C(R 6 )=C(R 7 )- CO2M 2 can be selected from. In certain embodiments, the second functional group is selected from -S-SO3M 2 and -CR 6 =CR 7 -CO2M 2 can be selected from. When the functional groups are - CO2M 1 and - S-SO3M 1 - S-SO3M 2 and - CR 6 =CR 7 - CO2M 2 , they can be selected from acids or salts thereof, for example, M 1 and M 2 are each independently selected from H, Na + , K + , Li + and N(R')4 + (for example, ammonium salts, in which case each R' is independently selected from H and C1~C 20 alkyl, for example, C1~C 12 alkyl or C1~C6 alkyl or C1~C4 alkyl, for example, monoalkyl, dialkyl, trialkyl, or tetraalkyl ammonium salts). When the crosslinking agent comprises two or three or more M 1 or two or three or more M2 groups, each M 1 or M2 These are independently H and Na + , K + Li + , and N(R')4 + You can choose from these.

[0109] In the manner described herein, R 1 ~R 8 Each is independently selected from H and C1-C8 alkyl groups, and M 1 and M 2 These are H and Na, respectively, independently. + , K + Li + , N(R')4 + It is selected from and x is an integer selected from 1 to 8.

[0110] As one option, the first functional group can interact with carbon black. Carbon black may have one or more surface functional groups, for example, oxygen-containing groups, such as carboxylic acids (and their salts), hydroxyls (e.g., phenols), esters or lactones, ketones, aldehydes, anhydrides, and benzoquinones. As another option, the second functional group can interact with a solid elastomer. The solid elastomer can be a natural elastomer, a synthetic elastomer, or a mixture thereof. For example, the solid elastomer 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 one option, the solid elastomer can be selected from natural rubber, styrene-butadiene rubber, and polybutadiene rubber. The solid elastomer may have olefin groups and / or be functionalized with several groups.

[0111] One option is that the first functional group is -NR 1 R 2 (For example, -NH2) and -S-SO3M 1 It can be selected from, and the second functional group is -S-SO3M 2 and -CR 3 =CR 4 -CO2M 2 You can choose from these.

[0112] A crosslinking agent may contain three or more functional groups. For such a crosslinking agent, each additional functional group, such as a third, fourth, etc., can be selected from the first and second functional groups disclosed herein. As one option, two or more types of crosslinking agents can be used to prepare a composite material.

[0113] The crosslinking agent may further include at least one spacer between the first and second functional groups. For example, one or more spacers may be bonded to each other and ultimately to the first and second functional groups. One option is that the first spacer is -(CH2) n -,- (CH2) y C(O)-, - C(R 9 )=C(R 10 ) -,- C(O)-,,- N(R 9 ) -, and - C6H4 - are selected, where y is an integer selected from 1 to 10, and R 9 and R 10 Each of these is independently selected from H and C1-C6 alkyl groups.

[0114] Exemplary crosslinking agents are selected from the compounds of formulas (1), (2), and (3). [ka] In the formula, M 1 and M 2 This is defined here, R 6 and R7 is independently selected from H and C1-C8 alkyl groups (for example, independently selected from H and C1-C6 alkyl groups, or independently selected from H and C1-C4 alkyl groups). One option is M 1 and M 2 H, Na + , and N(R')4 + For example, H and Na + Each is independently selected from, and R 6 And R7 are the same, for example R 6 and R 7 Each of these is H. An example of a crosslinking agent of formula (1) is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, which is commercially available as Sumilink® 200 crosslinking agent, and an example of a crosslinking agent of formula (2) is S-(3-aminopropyl)thiosulfate, which is commercially available as Sumilink® 100 crosslinking agent (Sumitomo). An example of a crosslinking agent of formula (3) is commercially available as Duralink® HTS tire additive (Eastman Chemical Co.). Other crosslinking agents include cystamine and thiourea.

[0115] As one option, the uncured composite is a product obtained by mixing at least a filler, an elastomer (or latex), and at least one crosslinking agent during a first-step mixing method, for example, in combination with a filler and an elastomer (or latex), or with a solid resulting from a mixture of a filler slurry and a latex, or during the formulation of the composite (productive or unproductive) and / or further processing of the uncured composite. Examples of composites and methods for forming such composites containing crosslinking agents are disclosed in U.S. Patent Nos. 9,365,497, 10,208,137, 10,343,455, 10,793,702, and 10,889,658, and U.S. Patent Publication Nos. 2018 / 0105654, 2019 / 0218350, 2019 / 0144634, and 2019 / 0241723, and PCT Application PCT / US21 / 62433 filed on 8 December 2021, which are incorporated herein by reference. For example, an uncured composite is the product of a known dry mixing process, e.g., mixing a filler, an elastomer, and at least one crosslinking agent. Other examples include uncured composites being products obtained by mixing at least a solid elastomer, a wetting filler, and a crosslinking agent (in one or more mixing steps) to form a mixture, and then removing at least a portion of the liquid from that mixture by evaporation, or as described in PCT application PCT / US21 / 62433 filed on 8 December 2021. Other examples include uncured composites being prepared by mixing a wetting filler and a solid elastomer as described in PCT application publication WO2020 / 247663 (the disclosure thereof is incorporated herein by reference), and then further mixing with at least one crosslinking agent as described in the PCT application filed on 8 December 2021 (the disclosure thereof is incorporated herein by reference).The amount of crosslinking agent added to the composite, solidified, or compound, or filled into the mixer (or any of the methods disclosed herein), may be 10 phr or less, for example, in the range of 6 phr or less, 5 phr or less, 4 phr or less, 3 phr or less, or 2 phr or less, for example, in the range of 0.1 phr to 10 phr, 0.1 phr to 8 phr, 0.1 phr to 6 phr, 0.1 phr to 5 phr, 0.1 phr to 4 phr, 0.1 phr to 3 phr, or 0.1 phr to 2 phr, or other amounts disclosed in PCT application PCT / US21 / 62433 filed on 8 December 2021, which is incorporated herein by reference.

[0116] Elastomer composites can be stored in any of the following forms, e.g., sheets, blocks, or smaller fragments, e.g., frit, e.g., bales of such smaller fragments, e.g., bales of frit. Small fragments of the composite can be formed by using a granulator, as disclosed in U.S. Patent No. 7,341,142, which is incorporated herein by reference. The form of the elastomer composite may affect the amount of oxygen present in the container. For example, a bale of randomly arranged frit may have a porosity of at least 25%.

[0117] When elastomers are mixed with fillers, some degradation of the rubber may occur. In certain cases, elastomer composites having dispersed fillers, such as carbon black, silica, silicon-treated carbon black, or any of the fillers disclosed herein, can benefit from the containers, packaging and / or storage methods disclosed herein. The distribution and dispersion of fillers in an elastomer network can be represented by “dispersion state” or “dispersion state” or macrodispersion. As one option, macrodispersion is “d 90This can be shown by the particle size distribution, where the particle size is determined by measuring the percentage area contribution from particles larger than 2 μm. The area contribution by particles can be reported for the imaging range, and the total imaging range of the image (μm) 2 The area can be determined from the number of pixels and the image resolution. An image can have width and height dimensions, each reported in the number of pixels, and the corresponding area is (in pixels). 2 It can be reported as follows: Regarding the area, the resolution is (μm / pixel) 2 It can be reported as follows. The imaging area is the product of the following: (Area) × (Resolution)

[0118] One option is d 90 is the area-equivalent diameter (μm) of the filler particles in the composite material, where d 90 This refers to particles smaller than 100 μm, for example, 90 μm or smaller, 80 μm or smaller, 70 μm or smaller, 60 μm or smaller, 50 μm or smaller, or 40 μm or smaller, 30 μm or smaller, 20 μm or smaller, or 10 μm or smaller.

[0119] One option is that the composite material has a G'(10%) of at least 50 kPa, for example, at least 100 kPa, or at least 200 kPa, where G'(10%) is in the range of 50–1,500 kPa, 100–1,500 kPa, 200–1,500 kPa, 100–1,000 kPa, or 200–1,000 kPa, where G'(10%) is the dynamic storage modulus measured at a 10% strain amplitude. [Examples]

[0120] The following tests were used to obtain performance data for each vulcanized product. The tensile stress at 100% elongation (M100) and 300% elongation (M300) were evaluated according to ASTM D412 at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. An extensometer was used to measure the tensile strain. The M300 / M100 ratio is expressed as the tensile stress ratio (or modulus ratio). • Maximum tanδ was measured in torsional mode using an ARES-G2 or ARES 2K rheometer (manufacturer: TA Instruments) with an 8 mm diameter parallel plate shape. The vulcanized specimens were 8 mm in diameter and approximately 2 mm thick. The rheometer was operated at a constant temperature of 60°C and a constant frequency of 10 Hz. Strain sweeps were performed with strain amplitudes from 0.1 to 63%. Measurements were taken at 10 points per set, and the maximum measured tanδ ("maximum tanδ") was reported and expressed as "tanδ" unless otherwise specified. The Payne ratio of the compound was calculated from the ratio of the dynamic storage modulus at 0.1% strain to that at 50% strain, i.e., G'(0.1%) / G'(50%). • Rheological properties were measured using a rubber process analyzer (RPA; D-RPA 3000, MonTech Rubber Testing Solutions). A sample (5g) was cut from a rubber composite. The temperature was set to 100°C, and a shear frequency of 1 Hz was used throughout the test. The test program consisted of 5 minutes of rest, followed by 10 cycles of shear at 50% strain, then 30 minutes at 0.3% strain, and finally a strain sweep from 0.3% to 51.5% strain. The Paine ratio of the composite was calculated from the ratio of the dynamic modulus G' at 0.3% strain to G' at 51.5%, i.e., G'(0.1%) / G'(50%). Example 1

[0121] This example illustrates 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.

[0122] The composite was prepared by the liquid process of Example 2 of U.S. Patent No. 8,586,651, except as shown below. The elastomer latex (diluted and depreciated MVL field latex) had a dry rubber content of 28% by mass, and the filler slurry contained 13–14% by mass of carbon black (Propel® E7 carbon black, “E7”; Cabot Corporation). The flow rate was adjusted to obtain a final carbon black filler of 55 phr at the desired production rate. The average carbon black filler level of the resulting composite was 55 phr. The dehydrated composite was kneaded, mixed with 2 phr of antioxidant (6 PPD), dried in a continuous mixer (Farrel Unimix Continuous Mixer (FCM) (Farrel Corporation, Ansonia, Connecticut) equipped with two #15 rotors and operated at 190-320 rpm), kneaded further, cooled, and dried on an open mill.

[0123] The composite material was formed into frit by processing 90 mm flakes through a granulator to form smaller fragments having dimensions of approximately 80 mm in length, 8 mm in width, and 8 mm in thickness. The method for cutting the flakes in the granulator is disclosed in U.S. Patent No. 7,341,142, which is incorporated herein by reference. The frit was then divided into many samples to be stored under a series of conditions listed in Table 3.

[0124] After storage, all elastomer composites were compounded in a 300 mL CWBrabender closed mixer equipped with cam blades, according to the formulations shown in Table 1 and the experimental design shown in Table 2. The vulcanization accelerator BBTS was N-tert-butyl-2-benzothiazole from Akrochem (Akron, Ohio). The compounding conditions were a starting temperature of 40°C, a rotor speed of 60 rpm, and a filling density of 60%. [Table 1] [Table 2]

[0125] The mixture was then sheeted in a two-roll mill operating at 50°C and a speed of 10.5 m / min, and subsequently passed through the mill four times (rolled with the edge facing upwards) at a nip interval of approximately 5 mm. These samples were heat-pressed at 150°C for 30 minutes.

[0126] Table 3 outlines the storage conditions for each composite material (before compounding) and the properties of the composite material and the resulting compound (vulcanized product). The "Time" in Table 3 indicates the number of days the sample was stored under the specified conditions.

[0127] In Table 3, "Atm" indicates whether the sample was stored in air, nitrogen ("N2"), or vacuum ("vac"). In the example of storage in vacuum, the composite material was stored in a metallized bag (Marvelseal® 360 barrier film from Berry Global, Inc., biaxially oriented nylon / PE / aluminum foil / PE / LLDPE (sealant layer); total film thickness = 132 μm; oxygen permeability at 0% RH, 73°F = 0.009 cm²). 3 / (m 2 The samples were placed in a 20°C (atm) environment. Within 3 hours of the composite material's manufacture, the bag was flushed with nitrogen, degassed to a pressure of 84.7 kPa, and then sealed. Samples stored under nitrogen, within 3 hours of manufacture, the composite material was placed in a metallized bag, degassed, flushed with nitrogen, and then sealed at ambient pressure within 3 hours of manufacture. The gas flushing and degassing process was performed using an AmeriVacs AVN retractable nozzle vacuum heat sealer.

[0128] In Table 3, "Temperature" represents the storage temperature of the composite material. "60°" indicates that the material was stored at 60°C (50% relative humidity), which was achieved by placing the sample in an oven (including samples stored in bags). After being stored at 60°C for the indicated time, the sample was allowed to equilibrate at room temperature overnight before compounding. "20°C" represents the sample stored in an air-conditioned room with a temperature control of 20°C ± 3°C.

[0129] The properties of the control composite were measured before sealing (days = 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 are for vulcanized products, unless otherwise indicated for composites indicated in "(C)". [Table 3]

[0130] The data in Table 3 provide the properties of the stored composites and the resulting formulations, i.e., the vulcanized products produced from the stored composites. Regarding the properties of the composites, the Payne ratio is favorably reduced for nitrogen and vacuum-stored samples compared to samples stored in air for more than 90 days. Regarding the properties of the formulations, it can be seen that under all temperature conditions, nitrogen and vacuum-packed samples maintain or decrease in maximum tanδ values ​​and Payne ratio. In contrast, maximum tanδ increases, second only to all samples stored in air (with a standard oxygen content of 21%) for more than 90 days. This effect is particularly pronounced when stored at 60°C, as evidenced by the increase in maximum tanδ for air-stored samples compared to the corresponding decrease for nitrogen or vacuum-stored samples. The composites and corresponding formulations of the present invention provide a highly unexpected improvement in hysteresis compared to their samples stored in air (i.e., not stored in oxygen barrier containers). Example 2

[0131] This example illustrates the results of storing different parts of the same elastomer composite under air, nitrogen, and vacuum, where the composite was prepared by a dry mixing process.

[0132] All samples were prepared with ASTM grade N234 carbon black, supplied as VULCAN® 7H carbon black ("V7H"; Cabot Corporation). The elastomer used was standard grade RSS3 natural rubber (Hokson Rubber, Malaysia). A technical description of this natural rubber is widely available, for example, in Rubber World Magazine's Blue Book, published by Lippincott and Peto, Inc. (Akron, Ohio, USA).

[0133] The composite was mixed in one step using a BR-1600 Banbury® mixer ("BR1600"; manufacturer: Farrel). The resulting composite was compounded in one step using a 439 mL CWBrabender closed mixer. Table 4 shows the formulations for mixing and compounding. The wax beads were Akrowax® 5031 wax beads from Akrochem (Akron, Ohio). [Table 4]

[0134] The mixing protocol is shown in Table 5, and the mixing was performed under the following conditions: Temperature control unit (TCU) temperature = 50°C; rotor speed = 80 rpm; filling density = 60%; and ram pressure = 2.8 bar. [Table 5]

[0135] The resulting composite material was sheeted on a roll mill operated at 50°C and approximately 37 rpm, and then passed through end rolls six times with a nip interval of approximately 5 mm. This composite sheet was divided into many samples for storage in either air or under nitrogen. For samples stored in a nitrogen atmosphere, the elastomer composite was placed in a nitrogen-purged glove box (oxygen concentration less than 2%). All samples were stored in an air-conditioned atmosphere (20°C).

[0136] The compounding protocol is shown in Table 6, and the compounding was carried out under the following conditions: TCU temperature = 40°C, rotor speed = 60 rpm; filling rate = 60%. [Table 6]

[0137] The resulting mixture was sheeted on a two-roll mill operated at 50°C and approximately 37 rpm, and then passed through four times (rolled edge-up) with a nip spacing of approximately 5 mm. These samples were cured in a heat press at 150°C for 30 minutes.

[0138] The properties of the compounding agents and composites are shown in Table 7, with "Atm" as defined in Example 1. The properties of the control composite were measured before sealing (Day=0, i.e., no storage). [Table 7]

[0139] From the data in Table 7, it can be seen that composites stored under nitrogen exhibited lower Payne ratio values ​​compared to samples stored in air for the same length of time. Regarding the properties of the compound (vulcanized material), the maximum tanδ value of samples stored in air increased over 180 days. In contrast, the maximum tanδ for samples stored under nitrogen was significantly lower compared to the value for samples stored in air. Samples stored under nitrogen also had a slightly higher tensile stress ratio (M300 / M100) and a lower Payne ratio compared to samples stored in air (i.e., not stored in an oxygen barrier container). Example 3

[0140] This example illustrates the consequences of storing different parts of the same elastomer composite under air or nitrogen, where the composite was prepared by mixing a wet filler with a solid elastomer. The composite was stored as a sheet.

[0141] All samples were prepared using ASTM grade N234, supplied as VULCAN® 7H carbon black ("V7H", Cabot Corporation). The elastomer used was standard grade RSS3 natural rubber (Sri Trang Agro-Industry Public Company Limited, Thailand). Wet carbon black was prepared by running dry carbon black pellets through an 8-inch MicroJet mill to produce cottony carbon black particles with a particle size of less than 10 microns for 99.0%. This cottony carbon black was then wet-pelletized in a pin pelletizer. The resulting wet carbon black (re-wetted carbon black) had a moisture content of 57%.

[0142] The composite material was prepared by a two-stage mixing process followed by a two-stage compounding process to produce the vulcanized product. The compounding is shown in Table 8, and the carbon black filler amounts are reported on a dry basis. [Table 8]

[0143] The first stage of composite mixing was carried out in a Kobelco BB-72 tangential mixer (66L capacity) equipped with a 4WN rotor at a 66% fill rate. The mixing chamber, rotor, and ram were heated in a TCU set to 75°C. The ram pressure was 5.5 MPa. After the first stage of mixing, the composite was processed in a Kobelco TSR-125 twin-screw discharge extruder (Kobelco Kobe Steel Group) equipped with a stationary knife.

[0144] The first-stage mixing protocol is shown in Table 9. The resulting batch time was 9.2–9.4 minutes. The first-stage composite material had a probe temperature range of 123–131°C and a moisture content of 4%. [Table 9]

[0145] The second stage mixing protocol is shown in Table 10. The second stage of composite mixing was performed in a Kobelco BB-16 tangential mixer (14L capacity) with a 6WI rotor at a 40% fill rate (Kobelco Kobe Steel Group). The mixing chamber and rotor were maintained at a constant temperature using a TCU set to 50°C. This mixing was carried out with the ram raised to its highest position, so the ram did not apply any pressure to the contents of the mixer. The delay between the first and second stages of composite mixing was less than 2 hours. After the initial mixing, the second stage of composite mixing was performed under PID control (proportional-integral-derivative), which allowed for automated control of the batch temperature via a feedback loop. The batch temperature was measured by a thermocouple inserted through the mixer's drop door and transmitted to the PID controller. The output of the controller was used to control the speed of the mixer rotor. The second stage of composite mixing protocol is shown in Table 10. The second-stage composite material had a probe temperature range of 133–140°C and a moisture content of <1%. [Table 10]

[0146] After the second stage of mixing, the composite material was processed in a TSR-125 twin-screw discharge extruder (Kobelco Kobe Steel Group) equipped with roller dies to produce sheets. After 27 days under ambient conditions, the composite material was then stored as sheets under the conditions outlined in Table 13. The storage temperature was 20°C (air-conditioned), and the samples were stored in air or in a nitrogen-purged glove box ("N2") (oxygen concentration less than 2%).

[0147] The two-stage compounding was carried out on a BR1600 mixer under the following conditions: TCU temperature = 50°C (first and second stages); rotor speed = 80 rpm (first stage) or 60 rpm (second stage); fill density = 68% (first stage) or 65% (second stage); ram pressure = 2.8 bar (first and second stages). The compounding protocols for the first and second stages are shown in Tables 11 and 12, respectively. [Table 11] [Table 12]

[0148] After each compounding stage, the compound was sheeted on a two-roll mill operated at 50°C and approximately 37 rpm, followed by six end roll passes on a roll mill with a nip spacing of approximately 5 mm. The Stage 2 sample was cured for a set period (30 minutes) in a heated press (150°C, 2500 lbs). The properties of the vulcanized material are shown in Table 13. The properties of the control composite were measured before sealing (days = 0, i.e., no storage). [Table 13]

[0149] From the data in Table 13, it can be seen that the maximum tanδ for sheets stored in air at 20°C was maintained or increased over the course of 180 days. In contrast, samples stored under nitrogen had a significantly decreased maximum tanδ after a 180-day storage period. Furthermore, samples stored under nitrogen showed a smaller decrease in tensile stress than samples stored in air at 20°C. Moreover, only samples stored under nitrogen showed a decreased Payne ratio value. Example 4

[0150] This example illustrates the results of storing different parts of the same elastomer composite as sheets under air or vacuum, where the composite was prepared by mixing a wet filler with a solid elastomer and a crosslinking agent, and also describes the evaluation of the properties of formulations prepared from this composite.

[0151] All samples were prepared using ASTM grade N234 carbon black, supplied as VULCAN® 7H carbon black ("V7H", Cabot Corporation). Wet carbon black pellets, with a 56% moisture content, were prepared by kneading in an 8-inch MicroJet mill to produce cottony carbon black particles with a 99.5% particle size of less than 10 μm. These cottony carbon black particles were then wetted in a pin pelletizer to regenerate wetted pellets. The elastomer used was standard grade RSS3 natural rubber (Von Bundit Co. Ltd., Thailand). Technical descriptions of this natural rubber are widely available, for example, in Rubber World Magazine's Blue Book, published by Lippincott and Peto, Inc. (Akron, Ohio, USA). The crosslinking agent used is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, which is available under the trademark name Sumilink® 200 coupling agent ("S200", Sumitomo Chemical).

[0152] The composite material was prepared by a two-stage mixing process followed by a single-stage compounding process. The compounding formulations are shown in Table 8, and the carbon black filler amounts are reported on a dry basis. The compounding formulations used are shown in Table 14. The carbon black filler amounts were set on a dry basis. [Table 14]

[0153] The first stage of the two-stage mixing protocol is outlined in Table 15. The time intervals represent the time of the process. The first stage mixing was performed in a BB-16 mixer (16.2L capacity) equipped with a 4WN rotor under the following conditions: TCU temperature = 90°C; fill density = 66%; ram pressure = 112 bar G. [Table 15]

[0154] The moisture content of the composite material after the first stage of mixing was 4.96% (mixing time = 7 minutes 20 seconds, probe temperature = 125°C). After the first stage of mixing, the composite material was processed using a TSR-125 twin-screw extruder (Kobelco Kobe Steel Group) equipped with a stationary knife.

[0155] The protocol for the second stage of mixing is shown in Table 16, and the mixing was carried out in a BB-16 mixer (14.4L capacity) with a 6WI rotor under the following conditions: TCU temperature = 65°C, filling rate = 35%, ram pressure = 112 bar G. After the initial kneading, the mixing was carried out under PID temperature control with the ram raised to its highest position, as described in Example 3. [Table 16]

[0156] Following the second stage of mixing, the composite material was processed in a TSR-125 twin-screw discharge extruder (Kobelco Kobe Steel Group) equipped with roller dies to produce sheets. The resulting sheets were cooled under ambient air for 27 days.

[0157] The composite material was then stored as a sheet in air or vacuum at 20°C for 90 days. For samples stored under vacuum, the composite material was placed in a metallized bag (Marvelseal® 360 barrier film) and subjected to gas flushing, followed by exhaust in an AmeriVacs AVN retractable nozzle vacuum heat sealer.

[0158] After the storage period, the vulcanizate is formed by compounding the stored composite material according to the formulation of step 3 in Table 14 in a 439 mL C.W. Brabender prep mixer equipped with a CAM blade following the protocol shown in Table 17. The vulcanization accelerator BBTS was (N-tert-butyl-benzothiazole sulfenamide) obtained from Akrochem (Akron, Ohio). The compounding conditions were: starting temperature = 40°C, rotor speed = 60 rpm, fill factor = 60%.

Table 17

[0159] After the compounding process, the composite material was formed into a sheet on a two-roll mill operated at 50°C and approximately 37 rpm, then passed through six times with a nip gap of approximately 5 mm. The final compound was formed into a sheet having a thickness of 2.4 mm on a two-roll mill operated at 60°C. The final compound was cured in a heat press at 150°C for 30 minutes.

[0160] Properties of vulcanizates prepared from composite samples each aged for 90 days are shown in Table 18. "Atm" represents the atmosphere in which the samples were stored, either air or vacuum.

Table 18

[0161] From the data in Table 5, it can be seen that the maximum tanδ value for sheets stored at 20°C in vacuum decreases significantly after a 90-day storage period. Furthermore, sheets stored under vacuum exhibited reduced Payne effect ratio values. Example 5

[0162] This example illustrates 0.527 cm at 0% relative humidity and 73°F 3 / m 2 / 24 hours to 1160 cm at 0% relative humidity and 73°F3 / m 2 This shows the results of storing different parts of the same elastomer composite material in packaging with OTR values ​​that vary over a range of up to 24 hours.

[0163] Table 19 below lists the characteristics of the tested packaging, including wall structure, OTR (at 0% relative humidity and 73°F), and wall thickness. Packaging A-D are flexible, transparent bags with dimensions of 12 inches (L) x 12 inches (W) (3,865 cm²). 3 It has the volume of [volume] and was purchased from ILC Dover, Inc. The reported OTR value was measured at 73°F, 0%RH according to ASTM D3985. [Table 19]

[0164] The tested composites were prepared according to the elastomer composite formulation in Example 1 of Table 1. The rubber composite formulation was the same as Example 1 of Table 1, except that no compounding operations were performed in this example, and therefore none of the compounding components were present.

[0165] After 15 days of storage in air, the composite material (150 g, specific gravity 1.112 g / cc) was stored in packaging and subjected to the conditions outlined in Table 20. A comparative sample ("Comp.") was stored in air. The remaining samples were stored in one of bags A, B, C, or D, each having the respective OTR values ​​listed in Table 19. These samples were stored under a unique combination of packaging atmosphere ("Packaging Atm") and the number of days ("Days") stored in a 60° oven. "Seal" under the "Packaging Atm" column indicates that the composite material was sealed in packaging without any changes in atmosphere. "Vac / N2" indicates that the composite material was stored after the packaging (containing the composite material) was degassed to a pressure of 84.7 kPa, followed by the bag being flushed with nitrogen, and then the packaging being sealed. The degassing and flushing processes were performed using an AmeriVacs AVN retractable nozzle vacuum sealer. All samples were stored in an oven at 60°C for 14 or 21 days to simulate long-term storage under ambient conditions.

[0166] Oxygen content was reported as the total gas concentration (%) in the space inside the bag and was measured by two separate methods. For transparent bags (bags A-D), the oxygen content in the space was measured without insertion using an OpTech®-O2, Model P oxygen headspace analyzer ("OpTech"), which uses optical fluorescence to measure a sensor placed inside the transparent packaging. Measurements were taken at day 0, followed by measurements on day 14 and / or day 21 of storage at 60°C, after the bags had reached room temperature. For all bags, oxygen content in the headspace was also measured by applying a resealable partition to the outer surface of the bag and piercing the bag through the partition with a Dansensor® CheckPoint® 3S, O2-Premium, solid-state sensor oxygen headspace analyzer ("CheckPoint"). Both types of oxygen analyzers are available from Ametek Mocon (Minnesota, USA). [Table 20]

[0167] In Table 21, all comparative samples ("Comp") have an oxygen headspace concentration of 21% as a result of being stored in air. All OTR values ​​are reported at 0% RH and 73°F. The time point for all checkpoint data represents the measurement performed on the day indicated in the "Days" column. OpTech measurements were performed on the day indicated in the respective "OpTech" column. Oxygen content is expressed as the measured oxygen concentration.

[0168] As shown by both the CheckPoint and PoTech data in Table 20, the overall trend indicates that the lower the OTR value, the lower the measured oxygen content in headspace.

[0169] The oxygen content in bags A and B (which have the lowest and second lowest OTRs, respectively) was reduced or maintained over the storage period, regardless of whether they were sealed in air ("Seal") or under a controlled atmosphere ("Vac / N2").

[0170] The oxygen content of bag C, sealed in air, also decreased over the storage period, but not as much as that of bags A and B. The oxygen content of bag D, stored in air ("Sealed"), did not decrease over time. When stored in a controlled atmosphere, the oxygen concentration increased over time for both bags C and D, and the final oxygen concentration values ​​were significantly higher than the final oxygen concentration values ​​of bags A and B, regardless of the storage method. Example 6

[0171] This example demonstrates the feasibility of packaging with high barrier wall properties for storing composite materials (green formulations) containing a curing agent.

[0172] The composite material was prepared according to the elastomer composite formulation of Example 1 in Table 1. The rubber compound (green compound) was prepared according to the compound formulation formula of Example 1 in Table 1 and the protocol of Example 1 in Table 2. The green compound was then sheeted in a two-roll mill operated at 50°C at a speed of 10.5 m / min, followed by passing through a mill with a nip spacing of approximately 5 mm four times (rolled with the edge facing upwards).

[0173] Different portions of the same elastomer composite, i.e., the green formulation (uncured sheet), were stored at 30°C under the conditions outlined in Table 21. In Table 21, "Atm" indicates whether the sample was stored in air or under vacuum ("vac"). "Days" indicates the number of days the sample was stored under the indicated conditions after the compounding operation and before curing in press. For samples stored under vacuum, the green formulation was placed in bags with Marvelseal® 360 barrier film within 3 hours of compounding. These bags were flushed with nitrogen, degassed to a pressure of 84.7 kPa, and sealed. The gas flushing and degassing processes were performed using an AmeriVacs AVN retractable nozzle vacuum heat sealer. A control composite was measured before sealing (Days = 0, i.e., no storage).

[0174] After storage, the mixture was cured in a heat press (150°C) for 30 minutes. The properties of the vulcanized product are also shown in Table 21. [Table 21]

[0175] Regarding the properties of the formulations, it can be understood that under all temperature conditions, the green formulations stored under vacuum resulted in rubber formulations that maintained or decreased in maximum tanδ value. Furthermore, these rubber formulations also showed an increase in tensile stress ratio (M300 / M100). In contrast, maximum tanδ increased for all samples stored in air (standard oxygen content of 21%) for 90 days.

[0176] Unless otherwise stated or clearly contradicted by context, the use of the terms "a", "an" and "the" is to be understood to encompass both the singular and the plural. The terms "comprising", "having", "including", and "containing" are to be understood as open-ended terms (that is, meaning "including, but not limited to") unless stated otherwise. Unless otherwise stated, the recitation of a range of values herein is merely intended to serve as a shorthand method of referring individually to each individual value falling within the range, and each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise stated or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the present invention and does not impose a limitation on the scope of the present invention unless otherwise stated. No language in the specification shall be construed as indicating that any non-claimed element is essential to the practice of the present invention. The present invention includes the following embodiments. (1) Packaged elastomer composite material, The present invention comprises a sealed package containing the composite material in an atmosphere having a partial pressure of oxygen less than 10 kPa, wherein the composite material is uncured and contains at least one elastomer and at least one filler, Before The packaging includes at least one wall surrounding the composite material, wherein the at least one wall has at least one oxygen barrier layer, thereby the packaging is protected at 100 cm at 23°C and 0% relative humidity. 3 / (m 2 It has an oxygen permeability of less than 1 / 2 atm. Packaged elastomer composite material. (2) The packaged elastomer composite material according to (1), wherein the atmosphere has a partial pressure of oxygen of 7 kPa or less. (3) The packaged elastomer composite material according to (1), wherein the atmosphere has a partial pressure of oxygen of 5 kPa or less. (4) The packaged elastomer composite according to any one of (1) to (3), wherein the atmosphere comprises at least 90% of at least one gas that is nonreactive with the elastomer composite. (5) The packaged elastomer composite according to (4), wherein the at least one gas that is nonreactive with the elastomer composite is selected from nitrogen, argon, helium, xenon, and carbon dioxide. (6) The packaged elastomer composite according to any one of (1) to (5), wherein the 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, mixtures thereof, and metallized layers thereof. (7) The packaged elastomer composite according to any one of (1) to (5), wherein the at least one oxygen barrier layer comprises a material selected from polyamide, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, metals, mixtures thereof, and metallized layers thereof. (8) The packaged elastomer composite material according to any one of (1) to (5), wherein the at least one oxygen barrier layer comprises a metallized layer or a metal layer. (9) The packaged elastomer composite material according to any one of (1) to (5), wherein at least one wall does not contain a metallized layer or a metal layer. (10) The packaged elastomer composite according to any one of (1) to (5), wherein the at least one oxygen barrier layer comprises a material selected from metals, metal alloys, ceramics, carbon-based nanomaterials, and melamine-based materials. (11) The packaged elastomer composite material according to any one of (1) to (10), wherein the at least one wall is a single layer wall which is the oxygen barrier layer. (12) The packaged elastomer composite material according to any one of (1) to (10), wherein the at least one wall comprises two or three or more layers, and at least one of the layers is the oxygen barrier layer. (13) The packaged elastomer composite material according to any one of (1) to (12), wherein at least one wall is flexible. (14) The packaged elastomer composite material according to any one of (1) to (12), wherein at least one wall is rigid. (15) The packaged elastomer composite material according to any one of (1) to (14), wherein the inside of the package has a volume of at least 10 L. (16) The packaged elastomer composite material according to any one of (1) to (14), wherein the inside of the package has a volume of at least 50 L. (17) The packaged elastomer composite material according to any one of (1) to (16), wherein the composite material contains a degradation inhibitor present in an amount of at least 0.5 phr. (18) The packaged elastomer composite material according to any one of (1) to (16), wherein the composite material contains a degradation inhibitor present in an amount in the range of 0.5 phr to 10 phr. (19) The packaged elastomer composite material according to any one of (1) to (16), wherein the composite material contains a degradation inhibitor present in an amount in the range of 0.5 phr to 3 phr. (20) The packaged elastomer composite material according to any one of (1) to (16), wherein the composite material substantially does not contain a degradation inhibitor. (21) The packaged elastomer composite material according to (20), wherein the composite material has a moisture content in the range of 3% to 20% by mass relative to the total mass of the composite material. (22) The packaged elastomer composite according to any one of (1) to (21), wherein the package further comprises at least one oxygen scavenger. (23) The packaged elastomer composite according to (22), wherein at least one of the oxygen scavengers is contained in an oxygen-permeable pouch. (24) The packaged elastomer composite material according to (23), wherein the small bag is attached to the inner wall of the packaging body. (25) The packaged elastomer composite according to any one of (22) to (24), wherein the at least one oxygen scavenger is selected from metal powders, ascorbic acid and salts thereof, and catechol. (26) A packaged elastomer composite according to any one of (1) to (25), wherein the at least one filler is selected from carbonaceous materials, carbon black, silica, bio-based fillers, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, recycled carbon, or combinations thereof, as well as coatings and chemically treated materials thereof. (27) The packaged elastomer composite material according to any one of (1) to (25), wherein at least one filler is selected from rice husk silica, lignin, nanocellulose, and hydrocarbon. (28) The packaged elastomer composite according to any one of (1) to (25), wherein the at least one filler is selected from carbon black, silica, and silicon-treated carbon black. (29) A packaged elastomer composite according to any one of (1) to (28), wherein the 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 elastomer, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, silicone elastomer, and mixtures thereof. (30) The packaged elastomer composite material according to any one of (1) to (28), wherein at least one elastomer is selected from diene elastomers. (31) The packaged elastomer composite according to any one of (1) to (28), wherein at least one elastomer is selected from natural rubber, polyisoprene rubber, butadiene rubber and mixtures thereof. (32) The packaged elastomer composite according to any one of (1) to (28), wherein the at least one elastomer comprises at least 30% natural rubber and the at least one filler comprises at least 50% carbon black. (33) The packaged elastomer composite material according to any one of (1) to (32), wherein the composite material further comprises a curing agent. (34) The packaged elastomer composite according to any one of (1) to (33), wherein the composite has a Payne ratio of at least 1.1, the Payne ratio being G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the dynamic storage modulus measured at a strain amplitude of 51.5%. (35) The composite material has a macrodispersion of 80 μm or less 90 It has, d 90 The packaged elastomer composite material according to any one of (1) to (34), wherein is the area-equivalent diameter (μm) of the filler particles in the composite material. (36) A packaged elastomer composite according to any one of (1) to (35), wherein the composite material is a heat-treated composite material. (37) The packaged elastomer composite material according to any one of (1) to (36), wherein the amount of oxygen in the packaging atmosphere is 75 mmol / kg elastomer composite material or less. (38) The packaged elastomer composite according to any one of (1) to (37), wherein the composite material is packaged for at least 5 days. (39) The packaged elastomer composite according to any one of (1) to (37), wherein the composite material is packaged for at least 14 days. (40) A method for storing an elastomer composite, comprising sealing the elastomer composite in a container and storing the composite in the sealed container for at least 5 days, The elastomer composite material is uncured and comprises at least one elastomer and at least one filler, The container includes at least one wall surrounding the composite material, The at least one wall includes at least one oxygen barrier layer, thereby the container can withstand 100 cm at 23°C and 0% relative humidity. 3 / (m 2 It has an oxygen permeability of less than 1 / 2 atm. method. (41) The method according to (40), further comprising, before sealing, flashing the inside of the container with at least one gas that is nonreactive with the composite material and / or creating a vacuum inside the container. (42) The method according to (40) or (41), wherein the sealed container has an atmosphere containing at least 90% of at least one gas that is nonreactive with the elastomer composite. (43) The method according to (40) or (41), wherein the sealed container is under vacuum. (44) The method according to any one of (40) to (43), wherein the composite material is stored in the sealed container for at least 14 days. (45) The method according to any one of (40) to (44), further comprising heat-treating the composite material at a temperature of 40°C or higher before sealing. (46) The method according to any one of (40) to (45), wherein the composite material has a probe temperature of 40°C or higher when sealed. (47) The method according to any one of (40) to (46), wherein the composite material is prepared by mixing at least a solid elastomer with a filler and a wetting filler containing a liquid, the liquid being present in an amount of at least 15% by mass based on the total mass of the wetting filler. (48) A method for maintaining or improving at least one property of an elastomer composite or a compound formed from the composite, This includes storing the elastomer composite material in a sealed container for at least 5 days. The elastomer composite material is uncured and comprises at least one elastomer and at least one filler, The container includes at least one wall surrounding the composite material, The at least one wall includes at least one oxygen barrier layer, thereby the container can withstand 100 cm at 23°C and 0% relative humidity. 3 / (m 2 It has an oxygen permeability of less than 1 / 2 atm. method. (49) The method according to (48), wherein the elastomer composite is stored in the sealed container for at least 14 days. (50) The stored elastomer composite or the compound formed from the stored elastomer composite has a payne ratio that is at least 10% lower than the payne ratio of the composite before the package was sealed. The Payne ratio is G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the dynamic storage modulus measured at a strain amplitude of 51.5%. The method described in (48) or (49). (51) The method according to any one of (48) to (50), wherein the compound formed from the stored elastomer composite has a maximum tanδ value that is at least 10% lower than the maximum tanδ value of the composite before the package was sealed. (52) The packaged elastomer composite according to any one of (1) to (39), wherein the composite is a product formed by mixing at least one crosslinking agent while mixing at least one elastomer with at least one filler. (53) The method according to any one of (40) to (51), wherein the composite material is a product formed by mixing at least one crosslinking agent while mixing at least one elastomer with at least one filler. (54) The method according to any one of (40) to (51), wherein the composite material further comprises at least one crosslinking agent. (55) The at least one crosslinking agent is The first functional group is -NR 1 R 2 , -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO 3 M 1 , as well as selected from the structures represented by formulas (I) and (II),

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Claims

1. Packaged elastomer composite material, The present invention comprises a sealed package containing the composite material in an atmosphere having a partial pressure of oxygen less than 10 kPa, wherein the composite material is uncured and contains at least one elastomer and at least one filler, The packaging includes at least one wall surrounding the composite material, wherein the at least one wall has at least one oxygen barrier layer, thereby the packaging can withstand temperatures of 100 cm at 23°C and 0% relative humidity. ３ / (m ２ It has an oxygen permeability of less than 1 / 2 atm, The atmosphere comprises at least 90% of at least one gas that is nonreactive with the elastomer composite material. The above-mentioned at least one elastomer contains at least 30% natural rubber, Packaged elastomer composite material.

2. Packaged elastomer composite material, The present invention comprises a sealed package containing the composite material in an atmosphere having an oxygen partial pressure of less than 10 kPa, wherein the composite material is uncured and contains at least one elastomer and at least one filler, the at least one filler being selected from rice husk silica, lignin, nanocellulose, and hydrocarbon, The packaging includes at least one wall surrounding the composite material, wherein the at least one wall has at least one oxygen barrier layer, thereby the packaging can withstand temperatures of 100 cm at 23°C and 0% relative humidity. ３ / (m ２ It has an oxygen permeability of less than 1 / 2 atm, The atmosphere comprises at least 90% of at least one gas that is nonreactive with the elastomer composite material. Packaged elastomer composite material.

3. The packaged elastomer composite according to claim 1 or 2, wherein the at least one gas that is nonreactive with the elastomer composite is selected from nitrogen, argon, helium, xenon, and carbon dioxide.

4. The packaged elastomer composite according to claim 1 or 2, wherein the at least one oxygen barrier layer is a layer comprising a material selected from polyamide, polyethylene, polyethylene terephthalate, polyethylene naphthalate, aluminum, poly(ethylene vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile, and mixtures thereof, or a metallized layer in which a metal is deposited thereon.

5. The packaged elastomer composite material according to claim 1 or 2, wherein the at least one oxygen barrier layer includes a metallized layer or a metal layer in which metal is deposited on a substrate.

6. The packaged elastomer composite according to claim 1 or 2, wherein the at least one oxygen barrier layer comprises a material selected from metals, metal alloys, ceramics, carbon-based nanomaterials, and melamine-based materials.

7. The packaged elastomer composite material according to claim 1 or 2, wherein the at least one wall is a single layer wall which is the oxygen barrier layer.

8. The packaged elastomer composite material according to claim 1 or 2, wherein the at least one wall comprises two or three or more layers, and at least one of the layers is the oxygen barrier layer.

9. The packaged elastomer composite material according to claim 1 or 2, wherein the inside of the package has a volume of at least 10 L.

10. The packaged elastomer composite material according to claim 1 or 2, wherein the composite material contains a degradation inhibitor present in an amount of at least 0.5 phr.

11. The packaged elastomer composite material according to claim 1, wherein the at least one filler is selected from carbon black, silica, bio-based fillers, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, recycled carbon, or combinations thereof, as well as coatings and silicon-treated materials thereof.

12. The packaged elastomer composite material according to claim 1, wherein the at least one filler is selected from carbonaceous materials and their coatings and silicon-treated materials.

13. The packaged elastomer composite material according to claim 1, wherein at least one filler is selected from rice husk silica, lignin, nanocellulose, and hydrocarbon.

14. The packaged elastomer composite according to claim 2, wherein the 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 elastomer, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomer, fluoroelastomer, perfluoroelastomer, silicone elastomer, and mixtures thereof.

15. The packaged elastomer composite material according to claim 2, wherein the at least one elastomer comprises at least 30% natural rubber.

16. The packaged elastomer composite material according to claim 1, wherein the at least one filler contains at least 50% carbon black.

17. The packaged elastomer composite material according to claim 1 or 2, wherein the composite material further comprises a curing agent.

18. The packaged elastomer composite according to claim 1 or 2, wherein the composite material has a Payne ratio of at least 1.1, the Payne ratio being G'(0.3%) / G'(51.5%), where G'(0.3%) is the dynamic storage modulus measured at a strain amplitude of 0.3%, and G'(51.5%) is the dynamic storage modulus measured at a strain amplitude of 51.5%.

19. The composite material has a macrodispersion of d of 80 μm or less ９０ It has, d ９０ The packaged elastomer composite material according to claim 1 or 2, wherein is the area-equivalent diameter (μm) of the filler particles in the composite material.

20. A method for storing an elastomer composite material according to claim 1 or 2, comprising sealing the elastomer composite material in a container and storing the composite material for at least 5 days in the sealed container having an atmosphere containing at least 90% of at least one gas that is nonreactive with the elastomer composite material, The elastomer composite material is uncured and comprises at least one elastomer and at least one filler, The container includes at least one wall surrounding the composite material, The at least one wall includes at least one oxygen barrier layer, thereby the container can withstand 100 cm at 23°C and 0% relative humidity. ３ / (m ２ It has an oxygen permeability of less than (atm / day), method.

21. A method for maintaining or increasing at least one of the Paine effect, hysteresis, tensile strength, tensile stress, or modulus ratio of the elastomer composite material or a compound formed from the composite material according to claim 1 or 2, The method includes storing the elastomer composite material in a sealed container having an atmosphere containing at least 90% of at least one gas that is nonreactive with the elastomer composite material for at least 5 days. The elastomer composite material is uncured and comprises at least one elastomer and at least one filler, The container includes at least one wall surrounding the composite material, Said at least one wall comprises at least one oxygen barrier layer, whereby said container has 100 cm at 23°C and 0% relative humidity ３ / (m ２ ·day·atm) or less oxygen permeability, method.

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