TR2024000621T2 - Stored elastomer composite products. - Google Patents

Abstract

Described herein are elastomer composite products stored in a container or package. The composite product is uncured and contains at least one elastomer and at least one filler. The package or container includes at least one wall surrounding the composite product, wherein the at least one wall includes at least one oxygen barrier layer. Containers or packages with this oxygen barrier wall have a maximum oxygen permeation rate of 100 cm3/(m2·day·atm) at 23°C and 0% relative humidity. Also disclosed are methods for storing elastomer composite products in the packages or containers disclosed herein.

Description

DESCRIPTION STORED ELASTOMER COMPOSITE PRODUCTS FIELD OF THE INVENTION Stored or stored in container(s) or package(s) having an oxygen barrier wall. Packaged elastomer composite products are described.

KNOWN ISSUES Various products of commercial importance, various synthetic elastomers, natural rubber or elastomer elastomeric material in which the reinforcing filler is dispersed in any of the mixtures It is created from combinations. For example, carbon black and silica, natural rubber and other elastomers It is widely used for reinforcement. Commonly, a master-batch material, that is, various optional additives such as reinforcing filler, elastomer and filling oil. A premix of the ingredients is prepared. These master-batch materials are then processed and mixed with curing additives and, after curing, various products of commercial importance is used to create . These products include, for example, cover and base, impact layer, inner lining, side wall, Pneumatics and pneumatics for vehicles, including tread band including wire-covering, carcass and others Non-filled or solid tires are included. Other products, such as engine mounting bushings, conveyor belts, windshield wipers, rubber components for space and marine equipment, vehicle pallets components, insulation, linings, seals, wheels, bumpers, anti-vibration systems and similar are included.

A good dispersion of the reinforcing filler in rubber compounds provides mechanical strength. and a factor in achieving consistent elastomer composite product and rubber compound performance. It is understood that it is. Rubber compounds, optionally with one or more additives elastomer composite, which is an uncured mixture of filler(s) and elastomer(s) together with It is prepared from its products. An elastomer composite product, also known as master-batch material can be combined with additional additives and curing agents and then one or more It can be subjected to vulcanization process. Therefore, elastomer composite products are made of rubber may be more susceptible to degradation compared to (cured) compounds, resulting in This poses a problem when stored and/or transported first. parallel to this As a result, elastomer composite products are significantly degraded when stored for long periods of time. There is a need to prevent deterioration.

One aspect is a packaged elastomer composite product containing: partial pressure of oxygen less than 21 kPa (e.g., less than 20 kPa, less than 15 kPa in an atmosphere (low, less than 10 kPa, less than 7 kPa, or less than 5 kPa) an insulated (sealed) package containing the composite product, wherein the composite product is uncured and comprising at least one elastomer and at least one filler, wherein: The package includes at least one wall surrounding the composite product, wherein the at least one wall is The package has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity (RH). It contains at least one oxygen barrier layer, such that the

Another aspect is a device for storing an elastomer composite product, comprising: The procedure is: isolating the elastomer composite product in a container and storage in an insulated container for a period of at least 5 days where: The elastomer composite product is uncured and has at least one elastomer and at least one contains filler; And The container includes at least one wall surrounding the composite product, wherein the at least one wall is It has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. As such, it contains at least one oxygen barrier layer.

Another aspect is that an elastomer composite product or composite product In order to protect or improve at least one property of a created compound, the following are It is a method that includes: elastomer composite product in an insulated container for a period of at least 5 days. storage during the period, where: The elastomer composite product is uncured and has at least one elastomer and at least one contains filler; And The container includes at least one wall surrounding the composite product, wherein the at least one wall is It has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. As such, it contains at least one oxygen barrier layer.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, packaged elastomer composite product or methods (e.g., an elastomer storage of a composite product or the storage of an elastomer composite product or composite aimed at protecting or improving at least one property of a compound formed from the product procedures) may also include any one or more of the following arrangements: package or the partial oxygen pressure of the atmosphere in the container is not more than 7 kPa or not more than 5 kPa; package or the atmosphere in the container is at least 90% non-reactive with the elastomer composite product. contains at least one gas; at least one gaseous nitrogen that does not react with the elastomer composite product, selected from argon, helium, xenon and carbon dioxide; insulated package or container It is vacuum.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following arrangements: at least one oxygen barrier layer polyamide, polyethylene, polyethylene terephthalate, polyethylene naphthalate, aluminum, poly(ethylene) vinyl alcohol), poly(vinylidene chloride), polyacrylonitrile and mixtures thereof and their metals It contains a material selected from layers; At least one oxygen barrier layer is polyamide, poly(ethylene Vinyl alcohol), poly(Vinilidene chloride), polyacrylonitrile, metals and their It contains a material selected from mixtures and their metallic layers; at least one the oxygen barrier layer includes a metallic layer or a metal layer; at least one wall does not contain a metallic layer or a metal layer; metals with at least one oxygen barrier layer, metal alloys, ceramics, carbon-based nanomaterials and melamine-based materials contains a selected material; A monolayer with at least one wall oxygen barrier layer is the wall; At least one wall includes two or more layers, wherein at least one of the layers It is the oxygen barrier layer; at least one wall is flexible; at least one wall is rigid; inside of the package its volume is at least 10 L or at least 50 L.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may contain any one or more of the following arrangements: composite product at least 0.5 phr amount, such as 0.5 phr to 10 phr or 0.5 phr to 3 phr An amount varying between or within other ranges described herein. contains inhibitors; the composite product contains virtually no antifouling; composite product moisture content varies between 3% and 20% by weight, based on the total weight of the composite product; The package further includes at least one oxygen scavenger; at least one oxygen-scavenging, permeable to oxygen It is located in a plastic bag; The bag is adhered to an inner wall of the packaging; at least one oxygen The scavenger is selected from metal powders, ascorbic acids and their salts and catechol.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may contain any one or more embodiments: at least one filler carbonaceous materials, carbon black, silica, bio-based fillers, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, recycled carbon or combinations thereof, and It is selected from coated and chemically treated materials; at least one filler selected from rice husk silica, lignin, nanocellulose and hydrothermal carbon; at least one filling The material is selected from carbon black, silica and silicone treated carbon black.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following embodiments: 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 elastomers, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers and their It is chosen from the mixtures; at least one elastomer is selected from diene-based elastomers; at least one elastomer natural rubber, polyisoprene rubber, butadiene rubber and mixtures thereof is chosen; composite product with at least one elastomer containing at least 30% natural rubber and at least 50% contains at least one filler containing carbon black; composite product plus curing agents Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following arrangements: Payne ratio of the composite product is at least 1.1, where the Payne ratio is G'(0.3%)/G'(51.5%), where G'(0.3%) is 0.3% strain is the dynamic storage modulus measured at 51.5% strain amplitude and G'(51.5%) is is the measured dynamic storage modulus; d90 macro-distribution of the composite product is at most is 80 µm, where d90 is the area-equivalent area of the filler particles in the composite product. is the diameter (um).

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may involve any one or more of the following arrangements: the composite product undergoes a heat treatment It is a well-seasoned composite product; The amount of oxygen in the atmosphere of the package or container is maximum It is a 75 mmol/kg elastomer composite product; composite product at least 5 days or at least 14 days or packaged or stored during other time periods described herein, or has been aged.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following arrangements: from sealing the package or container is first flushed with at least one gas that does not react with the package or cabin composite and/or vacuumed; Before insulating the package or cabinet, the composite product is thermally heated to at least 40°C. is subjected to processing; when insulating the package or cabinet containing the composite product the probe temperature of the composite product is at least 40°C; The composite product consists of at least one solid elastomer and one Prepared by combining a wet filler containing filler and a liquid, where the liquid is at least 15% by weight based on the total weight of the wet filler. available.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following arrangements: stored elastomer composite product or a compound formed from a stored elastomer composite product, A Payne ratio reduced by at least 10% compared to the Payne ratio of the composite product before closure. where the Payne ratio is G'(0.3%)/G'(51.5%), where G'(0.3%) is 0.3% strain is the dynamic storage modulus measured at 51.5% strain amplitude and G'(51.5%) is is the measured dynamic storage modulus, formed from the stored elastomer composite product compound according to the maximum tan value of the composite product before closing the package. It has a maximum tan value that is reduced by at least 10%.

Referring, as appropriate, to any aspect or method or arrangement disclosed herein, The packaged elastomer composite product methods described herein are also described below. may include any one or more of the following arrangements: composite product, at least one When mixing the elastomer with at least one filler, at least one coupling agent It is the product formed by adding; composite product, at least one filler of at least one elastomer It is the product formed by adding at least one binding agent while mixing with; The composite product also contains at least one binder.

DETAILED DESCRIPTION Elastomers (e.g., diene-based elastomers) have been shown to degrade in the presence of air/oxygen. is known. Degradation, breaking of polymer chains which can affect rubber properties and/or cross-linking. Elastomer composite products, crosslinking can be cured in the presence of curing agents such as sulfur to provide (relative to the composite) and a vulcanization product with higher stability in terms of degradation obtained; vulcanization products may also deteriorate, but uncured composite products may have less impact on certain performance characteristics than degradation.

However, uncured elastomer composite products are expected to last longer periods (e.g., 3, 6, 9 months). or 1 or 2 years) may need to be stored (and/or transported). Additionally, in warehouses or high temperatures often present during transportation (trucks, shipping containers) may increase the rate of degradation. To reduce this rate, composite products should be stored in the refrigerator or It can be stored in air-conditioned environments. However, these types of storage solutions are extremely energy costly. and requires a lot of cooling equipment.

Uncured materials containing high oxygen barrier materials, rubber and fillers rubber of composite products and compounds formed from such composite products features will be effectively preserved and, in some cases, even surprisingly has a low oxygen content for a sufficient period of time so that it can be improved It was not known before that it could provide an atmosphere. Therefore, this type of industry Storage of elastomers or composite products in a low-oxygen environment is typical It is not an application. Improvement of rubber properties by at least 5% or at least 10% may result in the development of a decrease in value (e.g., indicated by the maximum tan u, Payne Effect and/or Payne Ratio hysteresis) may occur.

Here you can find packaged elastomer composite products (or stored or aged elastomer composite products) and the storage and/or storage of such composite products methods for packaging and packaging of such stored or packaged composite products or protection of at least one rubber property of the rubber compound formed from them and/or Methods for its development (improvement) are explained. The rubber mentioned here properties of the composite product itself or a rubber formed from the composite product. may have properties of the compound, where rubber compound, elastomer composite product by vulcanization (vulcanization product), that is, the composite product is free of sulfur, peroxides, etc. It is obtained by curing in the presence of curing agents (curers) such as.

Described herein is a packaged elastomer composite product containing: the composite product in an atmosphere with a partial oxygen pressure of less than 10 kPa. An insulated sealed package containing the composite product uncured and containing at least one It contains elastomer and at least one filler, wherein: The package includes at least one wall surrounding the composite product, wherein the at least one wall is The package has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. It contains at least one oxygen barrier layer, such that the

Correspondingly, in one aspect, a container or package containing or containing the composite product An insulated composite product is provided in which the container or package contains the composite product. It includes at least one surrounding wall, and at least one wall is used to protect the container or package for a specified period of time. It contains at least one oxygen barrier layer to maintain low oxygen content throughout.

A wall may include a single layer that is an oxygen barrier layer or at least one layer that is an oxygen barrier layer. It may contain more than one layer (two or more layers) with a barrier layer. an oxygen The barrier layer regulates the rate of oxygen transfer from outside the cabin (outside) to inside the cabin (inside). reduces significantly. Container(s) or package(s) with an oxygen barrier wall (at least one oxygen barrier layer) to which the composite product is exposed. By limiting the amount, deterioration of the composite product can be stopped to a large extent.

The composite products described herein are the materials that surround and protect the elastomer composite product. stored and/or packaged and/or preserved in one or more containers or packages and any shape or form as long as they provide the desired oxygen barrier properties. may be in size. The container contains a package (e.g., box, crate, bag) or the desired amount of A glove box, room, etc. of any volume in which (molecular) oxygen can be maintained. It can be any chamber, including In one direction, the container or package is at standard temperature and pressure. has too much. Container or package oxygen permeation rate depends on the oxygen flow of the wall containing the oxygen barrier layer (oxygen barrier wall). can be determined from the barrier properties. Oxygen permeation rates, 23°C (73°F) at sea level and 0% relative humidity.

In some alternatives, the oxygen permeation rate is higher at 50% relative humidity or 65% relative humidity. can be determined or reported. Optionally, at least one wall is 23°C (73°F) and 0% at relative humidity (RH) not more than 100 cm3/(m2-day-atm), e.g. at 23°C (0% relative humidity) The wall of the container or package may contain one or more sections that form the container when sealed. For example, a typical box contains four side wall sections in addition to top and bottom wall sections.

Understandably, the number of wall sections can vary, for example, upper and lower wall sections. single, cylindrical side wall sections bonded with insulation or recesses to form the container made to be folded along its length or also with one or more wall sections It may be a continuous wall joined together. Any number of side wall sections can be used (hexagonal-shaped boxes or containers, wedge-shaped boxes or containers, etc.) A bag or sachet typically one or more wall sections, such as at least two unbonded edges, an opening that can be insulated (e.g., hermetically sealed) One or more side wall sections (and optionally a bottom wall section) two or more parts joined together by mating edges to form It contains a very flexible wall section.

As a more specific example, a flexible package will form a square or rectangular wall section. In the figure, two identical elastics with similar length and width dimensions, each with four sides may contain a wall section. Two flexible wall sections, three of the mating edges insulated together is glued, the fourth side is a hole for insertion of the elastomeric composite product into the package. It is not glued to provide clarity. Typically, a cabinet consists of all wall sections (side wall section, upper and/or lower wall section) are made of the same materials; your wall (and your package) oxygen barrier properties, in this case, any wall section does not allow oxygen to pass through. can be determined from the speed. Variations may occur, for example, a lower wall section may provide additional strength A top or side wall may contain one or more layers of structural support to provide The compartment may be made to facilitate opening the cabinet and/or a package may be insulated. Insulated sealable layers (e.g., heat sealable) to seal (hermetically seal) can be closed) or adhesives can be created. As a result, these compartments receive different oxygen May have barrier properties. In this case, the oxygen permeation rate of the package is can be an area-weighted average across the surface.

Referring to the adhesives, insulated adhesive is the rate of oxygen transfer from the outside to the inside of the package. At 23°C and 0% relative humidity, maximum 100 cm3/(m2-day-atm) or other airtight adhesives that provide 02 barrier properties at states. For example, airtight adhesives are made by heat sealing the side wall edges together. Just like insulating bonding, two insulated bondable layers are heat bonded together. It can be created by gluing. Airtightly bonded (e.g. with insulated edges) A package (adhered) contains similar or substantially identical oxygen barrier to the oxygen barrier wall. A container or package with multiple walls can be two or more containers, for example, a second container surrounding and containing the elastomer composite product. It could be the first container. Each container contains a single or multiple layered wall. For example, A first container has a first oxygen barrier wall and a second container has a second It may have a wall with oxygen barrier properties. As a specific example, a container (a wall), which surrounds the material to be packaged and takes its shape optionally, thus A material that provides a lined or wrapped material or a stretch-wrapped material may include a flexible film (e.g., a liner). A second container (or second wall) for storage Lined to protect from breakage and/or deformation during shipping (which may include shipping) It may contain a less flexible or rigid material surrounding the material. In any case, suddenly Even if there are multiple walls or multiple containers, each container has the desired oxygen level of the elastomer composition. barrier properties, for example up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity, or oxygen as it would be exposed to the oxygen permeation rate at other values explained here. May have barrier properties. For example, a composite product, each oxygen barrier a wall that has the characteristics of, for example, a lining that envelops the elastomer composite product and within two walls, such as a second wall that is a container that holds the wrapped composite product can be preserved. Oxygen permeation rate of each wall (each cabin) is 100 cm3/(m2-day-atm) value, but the container containing two walls (e.g., liner and package) together When it arrives, the desired oxygen permeation rate of maximum 100 cm3/(m2-day-atm) is achieved. can be done. For multiple vessels (or multiple walls), total oxygen permeation rate (OTR) It can be determined by the following equation: OTR : 1 / {(1/OTRcidarl) + (l/OTRcidarZ) + . . .} Here, "OTRcidari" and "OTRcidarz" are the oxygen permeability values of each cabin (each wall). indicates the speed. The equation includes more than one wall or more than one oxygen within a wall. barrier layer (e.g., wrapped multiple times around the composite product). stretch film or form-fitting lining, multiple walls or multiple walls within one wall can be considered as a layer).

Optionally, in addition to the container(s) having an oxygen barrier wall, elastomer One or more containers without oxygen barrier properties to preserve the composite product. cap can be used. For example, additional container, composite product in pulp or granule or similar form flexible mesh or bag to support or maintain the shape of the composite product Alternatively, the additional container may be a container with no or poor oxygen barrier properties. wooden or paper or corrugated cardboard box (or other non-barrier material), or It may be sheets or grids, or it may be fibrous like fabric. Additional container(s), additional structural support Oxygen barrier to ensure ease of transportation and/or handling on the exterior or interior (or both) of the container (i.e., the container with an oxygen barrier wall) can be placed.

The containers or packages described herein may be of any desired volume or size. cabin interior The volume of the part (internal volume) can be at least 1 L, at least 10 L, at least 20 L or at least 50 L. Container, 1 L to 20 L, 1 L to 10 L in one large or insulated room or transport It may have a container. In the case of two or more containers, one inside the other, more The larger cabin volume with oxygen barrier is valid. For example, a shipping container holds 20,000 L It can have a volume of up to .

In another aspect, the oxygen barrier properties of at least one wall significantly improve the composite product. of the elastomer composite product over a period of time to prevent degradation. It can be selected by limiting the amount of oxygen it will be exposed to. For example, package or container When the weight of the elastomer composite product present in it is known, the composite product The maximum amount of oxygen by weight can be calculated based on the amount of oxygen. For example, container or package, The maximum amount of oxygen in the package is 75 mmol/kg elastomer composite product, for example, not more than 60 mmol/kg of elastomer composite product, not more than 50 mmol/kg of elastomer composite product, not more than 40 mmol/kg elastomer composite product, not more than 30 mmol/kg elastomer composite product, not more than 20 mmol/kg elastomer composite product, not more than 15 mmol/kg, not more than mmol/kg, up to 6 mmol/kg, up to 5 mmol/kg, up to 4 mmol/kg, up to 3 mmol/kg, maximum 2 mmol/kg or maximum 1 mmol/kg elastomer composite product Thus, it includes at least one wall containing at least one oxygen barrier. An insulated container or package The amount of oxygen present in the package at the time or after the package is insulated It can be measured with an oxygen sensor (many types are commercially available). For example, cabin top a repeat in the space, which can be glued to the outside of the package or formed inside the wall. with a sensor having a needle penetrating the package through the sealable section or insulated an adhesive sensor that can be mounted by placing it inside the package before gluing it Measurements can be made using . Sample oxygen sensors were purchased from Ametek Mocon (Minnesota, USA) commercially available CheckPoint® or OpTech® optical oxygen sensors is included. the relative volumes of the container and composite product, as well as the weight of the composite product, amount of oxygen in the vessel (e.g., in mmol) relative to the weight of the composite product (e.g., per kg) can be determined. For example, the package volume is at least 1 L or at least 10 L or other There may be volumes. Optionally, according to the weight of the composite product in the container or package declared amount of oxygen for at least 5 days (e.g. from the time of insulating bonding) or at least at least 7 days, at least 1 month, at least 3 months, at least 6 months or at least 1 year, e.g. every 5 days to 1 year is maintained throughout the time period. Alternatively, for at least 5 days or longer (e.g., one year) is the amount of oxygen present in the container at any given time period. at declared levels, i.e. no more than 20 mmol/kg of composite product or less is minimized in this way.

The number of moles of oxygen in a closed container can be calculated according to equation (1): ([02]measured * Vair/IOO) * (273 K/Tcap) * (Pcap/ where [02]measured measured oxygen concentration (%), Vair *volume of air in the container (L), Tcap temperature (K) and Pcap oxygen in the container during measurement of oxygen concentration is the pressure (kPa) inside the container when measuring the concentration.

For a container holding a composite product, Vair determines that the volume of the composite product is can be determined by subtracting the volume of the composite product from the volume of the composite product. It can be calculated as weight/specific weight of the composite product. The result of Equation (1) and From the known weight of the composite product, the oxygen content according to the weight of the composite product (mmol/kg composite product) can be determined. In some cases where the cabin is a flexible bag, the cabin Storage under vacuum or partial vacuum allows the cabin to change the shape of the composite product. can make you get it. In this case, the cabin volume can be determined by methods well known in the art. For example, it can be assumed that the cabin volume is the same as the volume of the composite product.

Optionally, the oxygen content can be displayed as oxygen fraction pressure. Here The partial pressures declared are measured at ambient conditions, e.g. at sea level and 20°C indicates the values. Under ambient conditions, the partial pressure of oxygen is less than the atmospheric pressure (Calculated by multiplying by sea level.

Optionally, initially present in the container or package during insulating bonding. the atmosphere has a low oxygen content (e.g., the package is hermetically sealed during or before). For example, by changing the atmosphere inside the package, The oxygen content in the container may be reduced, meaning that the atmosphere in the container is a modified atmosphere.

Optionally, the partial oxygen pressure inside the container or package can be adjusted to a less than 21 kPa, less than 20 kPa, less than 19 kPa, as an atmospheric indicator, less than kPa, less than 4 kPa, less than 3 kPa, less than 2 kPa or less than 1 kPa is low. Optionally, a modified atmosphere (e.g., low partial oxygen pressure) can be achieved. To achieve this, the absolute pressure of the atmosphere in the container must be no more than 90 kPa, for example no more than 80 kPa, no more than kPa, not more than 10 kPa or not more than 5 kPa, on the interior or interior of the package. vacuum can be applied. As another option, the atmosphere in the vessel is non-reactive (e.g., It can be replaced by purging with a gas (which does not react with the composite). to react Examples of gases that do not include noble gases such as nitrogen, argon, helium, and xenon. Other Non-reactive gases include carbon dioxide. Atmosphere, one or more cleaning It may be replaced by three or more cleaning steps (e.g., two or three or more cleaning steps). Another Alternatively, the atmosphere can be used to achieve the low oxygen content values described here. by a combination of one or more vacuum and cleaning steps replaceable.

Alternatively, the low oxygen content of the atmosphere inside the package or container may from the difference in oxygen fraction pressure between the outside of the package and the inside of the package can be determined, where the atmosphere outside is higher than that in the interior. For example, cap or the difference in oxygen partial pressure between the outside and the inside of the package is at least 1 kPa, for example 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 It can be at least 15 kPa, at least 16 kPa, at least 17 kPa or at least 18 kPa.

As another alternative, the low oxygen content in the package (container) (molecular) amount, e.g. number of moles of oxygen per weight of elastomer composite product (e.g. mmol) (e.g. up to 75 mmol/kg elastomer composite product as mentioned herein), oxygen volume (or oxygen volume per kg composite product) or in the cabin interior concentration of oxygen present in the atmosphere, e.g. less than 7%, less than 5%, less than 3% It can be shown as low, less than 2% or less than 1%. Oxygen concentrations It can be measured with an oxygen sensor as mentioned here.

Optionally, during insulating bonding, the oxygen content of the container or package is It can be changed by adding at least one oxygen scavenger to the part. Oxygen holders are placed in a closed cabin10 It removes (traps, retains) oxygen in the atmosphere and thus reduces the oxygen content.

Oxygen scavengers absorb oxygen by reaction (e.g., an oxidation reaction) or It can trap oxygen and remove it. In another alternative, the atmosphere inside the container or package vacuum and/or inert gas exchangeable and elastomer composite product It is also packaged with at least one oxygen scavenger. Obtained by using oxygen scavengers The oxygen content depends on the amount of scavenger used; The oxygen content obtained is here any declared value, for example levels less than 21 kPa or other There may be levels. Oxygen scavengers can be stored together with the composite product, for example in a bag or Can be packaged enclosed. The bag, which must be oxygen-tight, can be used as a composite product. They may be placed adjacent to each other or adhered to an inner wall (inside) of the container or package. Example Oxygen scavengers include metals such as metal powders or iron filings, ascorbic acids and their salts, any of the inhibitors (e.g., antioxidants) described herein, catechol and Other oxygen scavengers known in the art are included. Antifoulants, as known in the art, It can be combined with the elastomer while mixing the elastomer with the filler. For example, The composite product may contain deterioration inhibitor(s) as described herein. Another example Alternatively, at least one wall of the package may contain a material capable of retaining oxygen. Oxygen including oxygen scavengers, oxygen barriers, and package walls containing oxygen-scavenging materials. Examples of holder packages can be found in Ahmed et al., Food, the specification of which is incorporated herein by reference. The oxygen scavenger, as described herein, is an inhibitor dispersed within the composite product.

At least one wall (oxygen barrier wall) consists of one or more layers, such as one or more over-layer laminate, thin-layer, lining, panel etc. may contain. Wall, suitable oxygen barrier A single-layer wall containing a material (oxygen barrier material) that provides or at least one of the layers comprises an oxygen barrier material, i.e. the layer is a It may be a multilayered wall (two or more layers) with an oxygen barrier. One The layer(s) of wall may be a sheet, panel or laminate. Multilayer walls extrusion or co-extrusion, extrusion coating, lamination (e.g., adhesive lamination), use of adhesives or applying one layer over another, bonding The use of layers can be created by metallization.

Oxygen barrier wall(s) (or layer(s)), most commonly polymers and/or metals may contain a variety of materials. Polyamide (PA), polymeric oxygen barrier materials polyethylene terephthalate (PET) and modified PET (e.g., glycol modified PET), polyethylene naphthalate (PEN), poly(ethylene Vinyl alcohol) (EVOH), poly(Vinilidene chloride) (PVdC), polyacrylonitrile, polyvinyl alcohol (PVOH), methyl acrylate, acrylonitrile and methyl acrylate copolymers (e.g., BareX®, a copolymer of acrylonitrile and methyl acrylate impregnated with nitrile rubber resins), cyclo-olefinic copolymer (COC) and mixtures thereof. Multi layered The walls may contain one or more oxygen barrier layers. One or more barriers The layer or wall can be biaxially oriented, e.g. polymer chains It can be stretched along transverse directions to align it with the layer or wall plane. Couple axial steering, additional strength as the thin layer is stretched to guide the chains, toughness, resistance to pressure, etc. (improved tensile properties).

Metal-containing materials to other oxygen barrier materials, such as metal layers is included. Metallized layers (those denoted by the prefix "m", such as mPET) or it can be created by a process known as metallization. In metallization, metals, sub- The layer may be a polymeric material having a desired flexibility or stiffness. It can be applied onto substrates using various methods. For example, metallization, such as aluminum metals are evaporated and then thin layers of metal are applied to a substrate application over a thin layer of film (e.g., vacuum application, chemical vapor application). Other methods of applying metal layers include spraying and Electric plating included. Alternatively, thin layers of metal can be formed and the metal The layer may be bonded to one or more polymeric layers. Metal layers or Metals that can be used as metallized layers include aluminum, tin, nickel, iron, silver and their alloys, e.g. aluminium-zinc alloys, silver-zinc-aluminium alloys, copper-zinc alloys, etc. is included. Polymeric thin layers as well as metals Other materials that can be applied over ceramics (e.g., silicon oxides (SiOX) such as silica), aluminum oxides, zinc oxides, magnesium oxides, titanium oxides, kaolinites, glass and metal oxides such as clays), carbon-based materials such as carbon nanomaterials (e.g., carbon nanotubes and graphene materials including graphene, graphene oxides, reduced graphene oxides) and melamine-based coating materials are included. Metals, ceramics and carbon based Materials such as coatings also contain particles with submicron sizes, e.g. 1 nm to It can be applied as particles of varying sizes. As an alternative, at least one wall does not contain a metallized layer or a metal layer. For example, stainless steel, tin and aluminum will form an airtight seal. Metal containers that can be joined/welded in this way also have oxygen barrier properties. can provide. containing metal, for example a glove box or a room or other room containers glass, ceramic, plastic Etc. It may also contain other materials such as: Rigid containers thermoplastic It can be made from elastomers and thermoplastic vulcanization products. Thermoplastic elastomers (TPE) contain more than one type of polymer: an elastomer (providing elastic properties) and a second polymer that provides strength. Styrene-butadiene-styrene block to TPE samples copolymers, styrene block copolymers such as ethylene acrylic copolymers.

Thermoplastic vulcanization products (TPVs) by vulcanization or crosslinking A material prepared, highly compressible and resistant to heat deformation cross-linked rubbers, which enable the melt processability of thermoplastics It is a class of thermoplastic elastomers that are combined with different properties. TPV samples An ethylene propylene diene vulcanized in a polypropylene (PP) thermoplastic matrix SantopreneTM thermoplastic vulcanization products with (EPDM) rubber (ExxonMobil) is included. Rigid containers with adhesive material or gaskets or o-rings or similar seals It can be bonded insulated with (e.g., nitrile rubber, butyl rubber, and the like).

Oxygen barrier wall or layer optionally embedded within the layer itself May contain oxygen-scavenging materials. These types of oxygen-scavenging barrier layers are typically protective layer that can act as structural and/or insulating bondable layers placed between layers. Alternatively, the thin layer has the ability to retain oxygen, that is, oxygen scavengers are embedded in oxygen barrier material or thin layers of oxygen It is made of a material that can hold.

Suitable oxygen barrier properties, wall type or layer materials on at least one wall or can be achieved by one or more factors, including layer order (for multilayer wall). A lot For laminated walls, typical laminated arrangements have an insulator as the innermost layer. bonding layer (e.g. polypropylene, LDPE, LLDPE or ethylene Vinyl acetate (EVA) polyethylenes), followed by an oxygen barrier layer (e.g., metal layer, polyamide) and an outer It contains a structural layer (e.g., PET, polyethylene) as the layer.

Wall and layer thicknesses also determine the total package weight to reduce shipping costs. Oxygen barrier properties (and other properties) on at least one wall are taken into account. can be selected as required. Wall thicknesses from min. 10 um to max. 10 cm, e.g. hard For packages, it can be up to 5 cm. For flexible packages, wall thicknesses range from 10 µm to It can vary between 50 um. For example, PVdC coated thin layers, EVOH based thin layers, polyamide films (e.g., Nylon) and metallized polymer films 10 µm to µm may have thicknesses ranging from, for example, 15 µm to 30 µm. Oxygen barrier10 It can vary between µm and 20 µm. Rigid packages at least 250 um, e.g. at least 500 um It may have thickness.

Single-layer walls consist of a flexible film, such as a lining or stretch film. may be provided or be a hard film (e.g., metal containers, ceramic containers). flexible thin layer samples, eg at least 30 µm thick, eg 30 µm to 100 µm, 30 µm to PVdC as liner with thicknesses varying from 75 um or 30 um to 50 um Stretch films are included. For multi-layer walls, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, etc., or up to 12 layers or more (e.g., up to 20 layers or more) Any number of layers can be used. These layers, structural features, odor and/or moisture barriers, oxygen barriers, insulating bondable layers (e.g., heat sealable layers) and combinations thereof, including a desired flexibility or hardness, transparency and can provide various features selected to provide oxygen barrier levels. Layer Regardless of the number, the resulting wall has the required oxygen barrier properties.

Referring to properties other than oxygen barrier properties, one or more layers, e.g. strength and/or to prevent deformation or destruction of the oxygen barrier wall may provide rigidity and/or structural support (e.g., puncture resistance). Some materials are more than one may have a function. Examples of these types of layers include: - polyesters such as polyethylene terephalate and polycarbonate, - high density polyethylene (HDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), ultra-low density polyethylene (ULDPE) or linear polyethylenes (PE) such as low density polyethylene (LLDPE) and mixtures thereof, - polypropylenes, - polyVinyl chloride (PVC), - polylactic acid (PLA), - ethylene-(meth)acrylic acid copolymers (e.g. Surlyn® resins, DuPont), - acid copolymer resins (e.g. terpolymers of ethylene, methacrylic acid and acrylate NUCRELTM resins, Dow) and - mixtures of these.

For any of the above, to bond a thin layer of metal to a polymer bonding, vacuum steam application, CVD, spraying, electroplating or any Alternatively, corresponding metal or metallized layers can also be used. One or more layers in a multilayer wall are bonded or insulated to an insulation. It may be a bondable layer (insulating adhesive). Insulated bondable layer, panels (e.g., one or more of the top, side, bottom panel) are connected to each other along the edges. may allow merging. Optionally, insulated bondable layer When applied, the polymer provides adhesion by deforming or melting, heat-insulated It is a stickable layer. Alternatively, insulated bondable layer, layers It could be a laminate that sticks together. Can be bonded to a multi-layered wall with insulation The layer is usually placed on one or both outer edges of a multilayer wall. placed, for example, the insulating bondable layer is the innermost layer (forming the inner wall) or It may be an outer layer (forms the outer wall). Examples of insulating bondable layers the following are included: Polyesters such as PET and metallized layers (e.g. mPET), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and The polyethylenes described above, such as HDPE, and metallized layers, such as mVLDPE, polypropylenes, ethylene-acrylic acid copolymers (e.g., NUCRELTM resins), ethylene-(meth)acrylic acid copolymers (e.g., Surlyn® resins), ethyl vinyl acetate (EVA) and mixtures of these.

Alternatively, to improve adhesion between layers (oxygen barrier adhesives that coat layers and/or structural layers) Adhesives can be coated or laminated.

The insulated bondable layer is a layer that provides barrier properties similar to those of a barrier wall. one or more adjacent insulated units to form airtight insulation can be joined to the bondable layer or bonded in another way. Alternative Additionally, the insulated bondable layer is a layer that provides good adhesion and support to an adhesive. There may be layers. Some insulating bondable layers, e.g. polyesters, polyethylenes (e.g., LDPE, LLDPE, HDPE), polypropylenes, ethylene-(meth)acrylic acid copolymers (EVA), and Like others known in the art, they can also serve as structural layers. One or more layers in a multilayer wall prevent water from entering, such as LDPE, LLDPE. or a moisture barrier to prevent it from coming off (depending on the elastomer composite product). it could be. Other chemical vapors and/or light and/or other undesirable elements Other types of layers (e.g., polyamide and EVOH) may be used to prevent

Wettability, color/transparency, and odor barriers are additional factors in layer selection. For example, multi-layer walls may include the following layer arrangements (cabin-to-cabinet It progresses from left to right towards the outside; "|” indicates the interface between layers): (i) insulating bondable layer | 02 barrier | insulating bondable layer (ii) structural layer | 02 barrier | insulating bondable layer (iii) insulating bondable layer | 02 barrier | structural layer (iv) l. 02 barrier | structural layer | 2. 02 barrier | insulating bondable layer (V) structural and/or insulating bondable layer | l. 02 barrier | 2. 02 barrier | structural and/or insulating bondable layer (Vi) structural and/or insulating bondable layer | 02 barrier | moisture barrier (vii) structural and/or insulating bondable layer | 02 barrier | moisture barrier | structural and/or insulated bondable layer (viii) structural and/or insulating bondable layer | 02 barrier + moisture barrier You can use any of the above layouts, although three- or four-layer layouts are shown. One or more additional layers may be provided to complete the For example, oxygen barrier Adhesive layers between layers and structural and/or insulated bondable layers or laminates can be added. Any number of layers for oxygen barrier walls, e.g. single layer, 2 layer, 3 layer, 4 layer, 5 layer, 6 layer, 7 layer or more more, for example 10-layer and even 20-layer (or more) walls are available in the art is known. A multilayer wall may contain more than one layer of 02 barrier (e.g., 1st and 2nd 02 barrier layer, or even the 3rd or 4th oxygen barrier layer or more). Two or more 02 In cases where there is a barrier layer, the materials forming each 02 barrier layer It may be the same or different. For example, each of the 02 barrier layers consists of polyamide (PA), poly(ethylene) vinyl alcohol (EVOH), poly(vinylidene chloride) (PVdC), polyvinyl alcohol (PVOH), methyl acrylate or Metallized layers such as mPET, mPA, mPE and their mixtures or metal may have (or contain) layers (e.g., aluminum layer); structural layer HDPE, LDPE, It can be VLDPE, ULDPE, LLDPE, polypropylene, PVC, PET and their mixtures; insulated The bondable layer can be LDPE, LLDPE, HDPE, polypropylene and EVA.

Optionally, any or all of the layers or a double oxygen barrier layer It can be axially oriented (“Bo”). Specific examples include: PA | PE | Aluminum foil | PE | LLDPE LLDPE | Nylon | EVOH | Nylon | LLDPE EVA | PA | mPET EVA | PA | mPP | LLDPE BoPP i LDPE i mBoPP i SURLYN Here ”BoPP” refers to biaxially oriented polypropylene, “m refers to metallized layers and "SURLYN" refers to Surlyn® resins. Above One or more additional layers may be provided to complement any of the layouts.

The desired oxygen partial pressures in the insulated vessel can be achieved in various ways. insulated Methods for removing oxygen from containers (or containers to be insulated) are known in the art. is known. Optionally, the interior (or contents or inside) of the container or package is vacuum-sealed. can be subjected to, can be purged with an inert gas (e.g., inert gas), can be subjected to oxygen scavengers can be exposed and combinations of these can be used. For example, the container or package is expose the contents of the compartment to vacuum and then seal the package with insulation. It can be bonded with vacuum insulation using a device made from . Vacuum insulation bonding machines (vacuum sealing adhesive) or vacuum heat sealing bonding machines (vacuum heat sealing adhesive) is known in packaging art such as flexible packaging. One Example of vacuum sealing adhesive to seal the opening of a substantially flat package It contains two surface elements that can be opened and closed. Surface elements rising towards a platform and may include a descending bar, where the open end of the package is placed between the bar and the platform.

Alternatively, such as a top bar pivotably mounted on a bottom bar, Two sticks can be used. In any option, one or both bars are insulated May contain heating elements and/or pressing elements to ensure adhesion. two surfaces It is connected to a vacuum pump between the element and optionally an inert gas source. There is one or more nozzles. After the package is filled with the elastomer composite product, At least one retractable nozzle is placed in the package opening, while the package is not glued. It can be placed between two sticks of adhesive with vacuum-sealed edges. two sticks interlocking or interlocking effectively seals the package opening. It can adhere and fit tightly around at least one nozzle. Vacuum can be applied and optionally an inert gas cleaning cycle can be performed.

After vacuum is applied, the nozzle can be retracted and removed from the package opening. Immediately then, through heating and/or suppression elements to seal the package insulated heat can be applied. For heating elements, the heat is transferred by an insulating bond on the package wall. layer and/or an adhesive coated on the insulated bonding container. It can soften. Alternatively, the package can be placed under vacuum and/or inert gas atmosphere. It may be located in a retractable chamber, where the chamber compresses the open package edges and Contains insulating sticks. This type of vacuum heat sealing adhesive samples containing gas purge sold by AmeriVacs (San Diego, CA). Vacuum insulating adhesive with retractable nozzle included. As an alternative to heat and pressure, welding processes can be used. For example, by heating and melting using C02 lasers polymeric layers can be fused together.

As another example (e.g., flexible containers, although generally for more rigid containers) gas connection between the container or package, the inside of the package, and a vacuum pump It may contain one or more ports or outputs that provide The port is part of the package. It can extend along the wall and provide an insulated connection to the hoses or pipes leading to the vacuum pump. A collar (e.g., large size circular bracelet). The port also closes the cabinet when the vacuum pump is operating. It may include a valve, such as a one-way valve, through which air or other gases can be withdrawn.

The valve optionally has a double valve to fill a bag with nitrogen after emptying the contents. It could be a directional valve. to the desired vacuum level or the desired partial oxygen pressure. is reached, the pump stops operating and the valve stops preventing air or oxygen from entering the container. It does the job. Optionally, for example, a higher oxygen permeability than that of the wall At speed, place a cap or similar on the collar to prevent further oxygen from entering the package. The housing or closing element can be installed insulated. The cover is an oxygen barrier material and attached to the collar by means of an adhesive material (e.g., an adhesive). can be pasted. Again optionally, when there is no cover, the valve area can be sealed with an adhesive. can be covered.

Also included here are the devices for storing or aging an elastomer composite product. The methods are explained. Insulated sealed containers or packages in a warehouse or It can be stored in similar containers and there may be shipping/handling processes during storage. Method, elastomer composite product in insulated sealed containers described herein, e.g. storage in containers or packages containing at least one wall surrounding the composite product may contain at least one wall, the cabin at 23°C and 0% relative humidity not more than It will have an oxygen transmission rate of 100 cm3/(m2-day-atm) and/or the oxygen in the package not more than 75 mmol/kg of elastomer composite product or other It contains at least one oxygen barrier layer within the range. It is explained here An oxygen (02) barrier including at least one layer, at least one of which is an oxygen barrier, such as It is the wall. The methods described herein are designed to achieve at least one rubber property of the elastomer composite product. can ensure its protection or even development. Therefore, there is also an elastomer composite product or a compound formed from a composite product has at least one rubber In order to preserve or improve the properties of the composite product, the composite product must be aged for at least 5 days or at least in an insulated container for at least 14 days or other time periods described herein. Procedures for storing it are explained. For example, on the wall of the storage oxygen barrier under an atmosphere with a low oxygen content in one or more insulated containers realizable.

Herein, methods for storing an elastomer composite product include: It is explained: isolating the elastomer composite product in a container and storage in an insulated container for a period of at least 5 days where: The elastomer composite product is uncured and has at least one elastomer and at least one contains filler; And The container includes at least one wall surrounding the composite product, wherein the at least one wall is It has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. As such, it contains at least one oxygen barrier layer.

Also included here is the use of an elastomer composite product or a composite product. aimed at protecting or improving at least one property of the compound, including: The methods are explained: elastomer composite product in an insulated container for a period of at least 5 days. storage during the period, where: The elastomer composite product is uncured and has at least one elastomer and at least one contains filler; And The container includes at least one wall surrounding the composite product, wherein the at least one wall is It has an oxygen transmission rate of up to 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. As such, it contains at least one oxygen barrier layer.

The method requires that the composite product in the container or package, prior to insulated closure (and storage), atmosphere in the cabin interior to obtain an atmosphere with a low oxygen content. It may involve being subjected to at least one changing stage. Optionally, the interior of the cabin with at least one gas that does not react with the composite product (an inert gas), e.g. By cleaning, the atmosphere is changed. Examples of non-reactive gases are nitrogen, argon, noble gases such as helium, xenon or other unreactive gases such as carbon dioxide, and Mixtures of such gases are included. Cleaning involves removing at least the air present in the package. at least 90% of the atmosphere, some of which is filled with at least one inert gas (e.g. nitrogen, argon, etc.), It involves changing the gas to contain at least 98% or at least 99% inert gas.

Alternatively, the atmosphere can contain at least 90% (or other amounts described herein) elastomer. It contains at least one gas that does not react with the composite product.

As another option, the atmosphere can be used, for example, by methods described herein or known in the art. By evacuating the interior of the container (or applying vacuum into the container) with any It is replaced by the removal of a significant amount of oxygen. Cabin interior, here As described, it can be placed at any desired vacuum level, where the evacuated cabin absolute pressure not more than 90 kPa, e.g. not more than 80 kPa, not more than 70 kPa, not more It can be up to 5 kPa or up to 1 kPa. In addition to gas purging and/or vacuum or Alternatively, a bag containing an oxygen scavenger may be placed in the container, where the scavenger It removes oxygen from the interior and thus reduces the oxygen content inside the container.

Optionally, the atmosphere is used for the composite product in the container (the one that preserves the composite product). cabin interior) is replaced by subjecting the cabin interior to at least one of the following steps: cleaned with at least one gas that does not react with the composite product and applied to the cabin interior. application of vacuum. Modification of the atmosphere involves one or more of these stages. may contain combinations. For example, after the composite product is placed in the cabin interior, The cabin interior can be cleaned with inert gas(es) and then or before Vacuum can be applied to the cabin interior, here cleaning/vacuuming with this inert gas The combination may be repeated as many times as necessary, for example one, two, three, four or more times the cabinet interior (composite product inside the cabinet) is flushed with an inert gas and then Vacuum is applied to the cabin or vacuum is applied to the cabin one, two, three, four or more times. is applied and then the cabin interior is cleaned with an inert gas. Optionally, final stage cabinet after one or more combinations, e.g. vacuum packed of a container or package (regardless of previous combinations applied) under vacuum It may be closed insulated. Alternatively, from one or more combinations The next final stage is cleaning the cabin interior with inert gas, the composite At least 90% of the product contains at least one gas that does not react with the elastomer composite product. The atmosphere may be isolated inside the cabin. As another option, the interior of the cabin One or more stages in which vacuum is applied (purging with inert gas) without) then the container can be insulated. Alternatively, with at least one inert gas One or more cleaning steps can be performed (without applying vacuum) and The container can then be sealed (without applying vacuum).

Store the elastomer composite product in an insulated container or package for at least 5 days or may be stored for other time periods as described. Storage time period insulated can be determined from the closing time. Optionally, the elastomer composite product can be 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 for at least 1 year or two years or more, and potentially indefinitely can be stored. As another option, you can use the elastomer composite product for 5 days to 2 years, 5 days to and other intervals in between over a varying period of time. can be stored.

Optionally, the composite product can be processed immediately after mixing or combining. (within 15 minutes after discharging the composite product from a mixer or combiner) or from a mixer or combiner unless the composite product is significantly degraded. after being emptied, within 1 hour, within 2 hours, within 3 hours, within 6 hours, within 1 day, Low oxygen content (modified atmosphere) within 1 week or 1 month (30 days) It can be stored under certain conditions. For example, composite product packaging or long-term storage or may be stored in air or cold storage prior to transportation. As an alternaive, composite product in air, composite products in packages or in low oxygen content can be transferred to a facility where it can be transferred to other conditions that provide storage. Another option As a result, the composite product has a high oxygen barrier wall that does not allow significant oxygen into the container. It is insulated inside the container to prevent air from entering. insulated in air shut down within 1 hour, within 2 hours, after discharging from a mixer or compounder, Within 3 hours, within 6 hours, within 1 day, within 1 week or within 1 month (30 days) realizable.

The elastomer composite product may not be packaged or stored at any temperature ranging from 20°C to 200°C. Can be stored in container. Optionally, the packaged composite product can be stored in a climate-controlled under ambient conditions in the environment or in a non-climate controlled area (e.g. warehouse, truck) It can be stored (at temperatures ranging from 20°C to 40°C or 20°C to 30°C).

Optionally, the composite product can be stored in the container at high temperatures, for example at least 40°C, Can be stored for at least 5 days. In some embodiments, the composite product is incubated for at least 7 days, at least 2 weeks (14 days), at least 3 weeks (21 days) or at least 1 month to as high as 6 months or 1 year can be stored at temperatures. Optionally, storage at high temperatures for a maximum of 1 month, It is carried out for a maximum of 2 weeks or a maximum of 1 week, for example for 5 days to 1 month.

Optionally, before storage, the composite product can be heated, e.g. oxygen concentration in the atmosphere is less than 7%, less than 5%, less than 2%, or less than 1% by heat in an inert gas or under vacuum, in a substantially oxygen-free atmosphere can be processed. Under these conditions, the heat process should last 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 It can occur over a period of up to one day. Heating, described here high10 or it may occur at other high temperatures described here. Upper temperature limit composite It can be determined by the composition of the product and/or the container used. For example, composite products certain synthetic rubbers (or mixtures containing synthetic rubber) or the majority Depending on whether it contains natural rubber, the composite product can be heated up to 200°C, up to 180°C, box) or in a container or package containing oxygen barrier wall(s).

The composite product is subjected to heat treatment in an oven or glove box or other compartment. can be handled and then transferred to the container or package for insulating sealing and storage; The composite product is exposed to ambient temperatures (e.g. 20-40°C or 20-20°C) before being transferred to the container. °C) or composite product as determined by the probe temperatures described herein. It can be transferred when it has a high temperature such as Alternatively, composite product It can be subjected to heat treatment in the package, which has an oxygen barrier wall, and can be cooled. Depending on the temperature of the composite product, heat stabilized vacuum packaging can be used.

Accordingly, the method includes an oxygen barrier container as described herein prior to storage. or a uncured elastomer composite product in its package for a period of at least 5 days. Elastomer that has been subjected to a heat treatment by heating at a temperature of at least 40°C for a period of comprising forming the composite product, wherein the elastomer composite product is formed from at least one elastomer and at least one filler, wherein at least one of the following applies: (i) the partial pressure of oxygen in the cabin interior is less than 17 kPa, (ii) the amount of oxygen in the cabin interior is not more than 10 mmol/kg elastomer It is a composite product, (iii) the oxygen concentration in the cabin interior is less than 7%, e.g. As another option, the composite product is discharged from the mixer and heated at, for example, 21 kPa (or having a lower oxygen fraction pressure than in the other ranges described herein) modified atmosphere, at least 90% inert gas, such as a nitrogen atmosphere containing or having an oxygen/elastomer ratio of not more than 75 mmol/kg elastomer composite product. below atmosphere or under vacuum (e.g., the absolute pressure inside the cabin is not greater than The insulation is closed below 90 kPa). Purge from mixer and a modified atmosphere10 The time period between under-insulated shutdown is very short (e.g., 5 minutes, 10 minutes, minutes) or up to 30 days, e.g. up to 2 weeks, up to 1 week, up to 1 day, up to up to 12 hours, up to 6 hours, up to 3 hours, up to 2 hours, up to 1 hour or up to It could be minutes. The time period is such that the amount of degradation of the composite product is minimized. It is determined as follows.

As another option, the composite product can be removed from the mixer under a modified atmosphere (e.g., inert gas atmosphere such as nitrogen atmosphere) can be evacuated and placed under a modified atmosphere can be preserved or stored (e.g., evacuated, transported, and stored in a package) can be closed insulated, all stages are carried out under a modified atmosphere).

The composite product discharged from the mixer (discharged in a modified atmosphere or transferred to a modified atmosphere), mixing conditions and/or cooling of the composite product. to 200°C, depending on whether it has been cooled (e.g., immediately after discharge from the mixer). It can have a probe temperature of up to .

The probe temperature of the composite product is typically the bulk temperature of the composite product, e.g. by placing a thermocouple or other temperature measuring device inside the composite product measurable. Optionally, during insulation in the container or package, the composite product can be stored at 20°C. It may have a probe temperature varying between . Typically, after evacuation, The composite product can have a probe temperature ranging from 100°C to 180°C. Alternative It can have a probe temperature ranging from 50°C to 50°C or 20°C to 60°C. Some The elastomer composite product can optionally be made into one or more of the materials described in detail herein. An uncured product containing fillers and elastomers, along with more additives (e.g., unvulcanized or before vulcanization) may be considered a mixture.

The packaged composite product can be considered a mix or master-batch material.

Composite product, optionally a rubber compound or to obtain a rubber product It may be an intermediate product that can be subjected to subsequent curing or vulcanization processes.

The elastomer composite product contains the filler dispersed within the elastomer. This The composite product consists of at least one elastomer in an interlocking or tangential manner with at least one filler. mixer (e.g. Banbury or Brabender mixer), an extruder, a roll mill, in a mixer such as a continuous mixer or other rubber mixing equipment It can be prepared in various ways, including combining it. Fillers and/or elastomers It can be combined in dry form or wet form. Dry mixing processes, solid elastomer mixed with the filler in a dry state (not wetted or dispersed in a liquid). Contains. The combining step consists of at least one first step containing at least one filler (a slurry). a pressurized continuous flow of fluid and at least one second fluid comprising an elastomer latex ensuring an uninterrupted flow; and the first fluid flow and the second fluid flow may involve dispersing the filler in the elastomer latex by combining or may cover. Formed by coagulating a slurry of mixed latex and filler A composite product is created by drying the wet crumbs. These specifications are referenced here Also known as the "mixing" process. The mixer is a continuous mixer or another type of It can be confusing.

As another alternative, PCT Publication No. 1, the specification of which is incorporated herein by reference. WO Under the specified conditions, the mixing process causes the liquid content to form compounds and optionally extrusion, calendering, grinding, granulation, baling, compounding and filler to be low enough to allow additional finishing steps such as sheeting. It provides a composite product containing the material dispersed in the elastomer. This type of compound Formation and finishing stages are performed on the elastomer composite product. can be achieved independently of the mixing method.

Composite products are also described in PCT Publication No. 1, the specifications of which are incorporated herein by reference. WO It can be prepared by continuous mixing.

The composite product, in addition to the filler and elastomer, includes at least one product selected from the following: may contain additives: processing inhibitors, coupling agents, processing aids substances (to facilitate the mixing and processing of rubber, e.g. various oils and plasticizers, wax), activators (to activate the vulcanization process, e.g., zinc oxide and fatty acids), accelerators (to speed up the vulcanization process, e.g. sulfenamides and thiazoles) as vulcanizing agents (or for cross-linking rubbers10 scavengers, e.g. sulfur, peroxides) and other rubber additives, e.g. limiting without retarders, excipients, peptisers, adhesion promoters, tackifiers, resins, flame retardants, colorants and blowing agents. optional Depending on the composition, the composite product does not contain vulcanizing agents, for example, the composite product also Contains at least one additive selected from: inhibitors, binder substances, processing aids, activators, accelerators, retarders, auxiliaries substances, peptidizers, adhesion promoters (e.g., the specification of which is incorporated herein by reference) cobalt salts to promote the adhesion of steel cord to rubber-based elastomers. use), resins (e.g. tackifiers, traction resins), flame retardants, colorants, blowing agents and additives that reduce heat accumulation (HBU). One option Additionally, rubber chemicals may contain processing aids and activators.

As another option, one or more other rubber chemicals such as zinc oxide, oil acids, zinc salts of fatty acids, wax, accelerators, resins and processing oil is selected. Example resins are C5 resins, C5-C9 resins, C9 resins, rosin resins, terpene resins. resins, aromatic-modified terpene resins, dicyclopentadiene resins, alkylphenol US Pat. No. 10,738,178, For example dry mixing or wet mixing or solid elastomer/wet filler After the composite product is initially formed by mixing or other mixing processes, composite products optionally contain one or more antifouling agents, zinc oxide, oil acids, zinc salts of fatty acids, wax, accelerators, resins, coupling agents and can be compounded with additional ingredients such as processing oils. Optionally, composite, Before compounding (if present), the filler must be bonded to the elastomer. spoilage inhibitors added during the initial mixing operations where it is mixed and dispersed in may contain. Deterioration inhibitors prevent rubber from deteriorating by reacting with oxygen Antifoulings are also considered a type of oxygen scavengers, since they can also act as oxygen scavengers. can be done. Degradants (e.g., antioxidants) in the composite product It may be present in an amount ranging from 1% to 2% or 1% to 2%. As an alternaive, deteriorators (e.g., antioxidants) in the composite product (after initial mixing or may be available in some quantity.

Optionally, the composite product may contain any other additives described herein, e.g. may contain curing agents or curers (e.g. sulfur, peroxides). vulcanization with or without (curing) agents, according to the parameters and procedures described herein. The packaged composite product remains uncured until it is subjected to vulcanization processes. acceptable.

Optionally, the composite product may be stored in oxygen barrier containers as described herein. storage or packaging, the composite product is virtually free of any deterioration. This may allow it to be free of preservatives or antioxidants. Oxidation or by oxygen Reactivity is a factor in the degradation of elastomer composite products. get oxygen removal eliminates the need for the addition of spoilage inhibitors or antioxidants. can remove it. Optionally, containing virtually no antifouling composite product, maximum 1%, e.g. maximum 0.5%, maximum Contains large amounts of anti-corrosion inhibitors. Containing virtually no antifouling (e.g., immediate In formulations (containing almost no antioxidants), the formulation may optionally contain one or more more other additives, e.g. zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, coupling agents, processing oils and/or vulcanized may contain harmful substances.

Optionally, uncured composite product with filler dispersed in elastomer consists of, or consists primarily of, or uncured composite product It consists of elastomer and filler dispersed in antifouling or is basically It consists of these. As another option, the uncured composite product is elastomer and It consists of, or is essentially composed of, filler material dispersed in the bonding agent. Consists of or uncured composite product elastomer and anti-deterioration and bonding agent It consists of, or is essentially composed of, filler material dispersed in it. Composite products may contain excess moisture. For example, composite product 3% to 20%, e.g. When inhibitors are not present, mold growth may occur in these types of composites. oxygen barrier Containers and packages containing walls, low oxygen content on the inside of the package may encourage mold growth. of such composite products containing excessive moisture, as it can reduce the (even when it contains almost no spoilage inhibitors).

Store the elastomer composite product in containers containing the oxygen barrier walls described herein. When packaged or stored, the composite product is 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 other time periods described herein, where such Composite products may be referred to as aged or stored composite products.

The resulting stored or aged composite product and/or stored or rubber compounds made from aged composite product, insulated closure (packaging) stored or aged in comparison with the properties and/or environmental conditions at the time to composite products (e.g., ambient oxygen partial pressure, ambient absolute pressure, etc., such as air similar properties after storage (composite products stored in at least one can retain its rubber properties) or even enhanced or improved rubber properties can exhibit. Corresponding compounds made from such stored composite products are also compared to compounds made from composite products during insulated closure and/or ambient composite stored or aged under conditions (e.g., stored in air) may exhibit similar or even improved properties compared to compounds made from the products.

During insulated closure, samples of composite products are subjected to various measurement techniques to be formed into rubber compounds that can be held or from which properties can be measured or obtained It can be compounded as follows. This type of composite products are measured during packaging. properties is a control sample (created from the control sample composite product rubber compounds shall be a control rubber compound). Time periods explained here after storage or aging for a period of time such as stored composite product samples and the properties of the compounds formed can be measured or obtainable.

In some cases, the properties of this type of rubber are preserved, for example, the deterioration in properties maximum 10%, maximum 5%, maximum 3.10% of the value during packaging or insulated closure at most 2% or at most 1%. In some cases, aged or stored composite product and corresponding composites made from aged or stored composite product They exhibit improved values. Characteristics during development, insulating closure or packaging and/or compared to composite products stored or aged under ambient conditions (and for corresponding compounds made from such composite products) at least 5% or at least a beneficial reduction (e.g., the Payne Effect of the composite product or corresponding rubber compound or Rubber compound hysteresis indicated by Payne Ratio or maximum tan 8) or such as tensile strength, tensile stress or modulus ratio of the corresponding compound There may be a beneficial increase in properties. For example, the rheological properties of the composite product (and the compounds formed from such composite products) properties of the composite product in the high oxygen barrier containers described herein. can be improved by storage. An example of this type of property is the Payne ratio or Payne is the Payne Effect of the composite product (not vulcanized), which can be shown by the difference. Payne rate It is defined by the formula G'(0.3%)/G'(51.5%), where G'(0.3%) is at 0.3% strain amplitude measured dynamic storage modulus and G'(51.5%) dynamic measured at 51.5% strain amplitude It is a storage module. Payne difference is the difference between G'(0.3%) and G'(51.5%). Composite The rheological properties of the product, such as the Payne ratio, are measured before vulcanization. before and after the composite product has been stored for different periods of time, as long as measurable. In some cases, insulating closure or storage of the package or container (or a period of at least 5 days (e.g., at least 14 days) from the production of the composite product. At temperatures, the Payne ratio of the elastomer composite product, defined as G'(0.3%)/G'(51.5%), At least 10% (e.g., according to the Payne ratio of the composite product on day 0, when the package was sealed) at least 15% or at least 20%) is low. Optionally, the Payne Ratio of the composite product should be at least For example, the cured compound (such as from aged or stored composite products) rubber compound properties, such as the Payne a reduction (at least 10%) or maximum tan of the rubber compound indicated by 8 rheological properties such as a reduction in hysteresis (at least 10%) or tensile at 300% elongation with at least a 10% increase in mechanical properties such as modulus ratio or tensile stress ratio can be usefully improved as shown.

The composite product is produced after mixing and dispersing the filler in the elastomer. or one or more additives of the composite product (e.g., as described in detail herein detergents, coupling agents, processing aids, activators, accelerators, After additional mixing steps in which it is combined with vulcanizing agents), As long as the composite product is uncured, it can be packaged. Composite product is explained here immediately after discharge from a mixer, or after a period of time, and It can be packaged at a temperature with minimal deterioration.

When packaging composite products with high stack or probe temperatures, the package or container This type can be selected to withstand hot filling processes. Especially the internal volume of the package when pressure is low, for example in vacuum, the composite product is in a package Shrinkage or other deformations may occur when cooled. hot filled Packs are typically flexible and made to deform when cooled. heat stabilized Vacuum packaging can also be used. Alternatively, the package can be made of high Tg plastic. or thick walls (e.g., walls thicker than 250 µm) or very hard surfaces such as a metal container it could be.

The fillers and elastomers that make up the composite product can be used in any manner known in the art. It can be filler and elastomer. 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-expanded SSBR (OESSBR)), functionalized styrene-butadiene rubber, polybutadiene rubber (BR), functionalized polybutadiene rubber, polyisoprene rubber (IR), ethylene-propylene rubber (EPDM), isobutylene-based elastomers (e.g. butyl rubber), halogenated butyl rubber, polychloroprene rubber, nitrile rubbers (NBR), hydrogenated nitrile rubber (HNBR), polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers and mixtures thereof. Other synthetics that can be used in existing methods Hydrogenated SBR and thermoplastic block into polymers (alone or as a mixture) copolymers (e.g., recyclable ones) are included. Ethylene to synthetic polymers, copolymers of propylene, styrene, butadiene and isoprene are included. Other synthetic elastomers, metallocene where the metal is selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Co, Ni and Ti Those synthesized by chemistry are included. Containing modern carbon as defined in ASTM D6866 Polymers made from bio-based monomers, such as monomers, are described here10 U.S. Pat. incorporated by reference. No. Bio-based styrene disclosed in US 9,868,853 polymers made from monomers or butadiene, isoprene, ethylene, propylene, famecene and Polymers made from bio-based monomers, such as their comonomers, can also be used.

Optionally, composite product, natural rubber, styrene-butadiene rubber, butadiene rubber, exposed to oxygen, such as diene-based elastomers, including isoprene rubber and mixtures thereof It may contain at least one elastomer that deteriorates upon exposure. Composite product is also known in the art It may also contain other elastomers that are substantially insensitive to oxygen, such as Another Alternatively, at least one elastomer of natural rubber (e.g., at least 20%, at least 30%, at least 40%, at least May contain a small amount of synthetic elastomer. Optionally, at least one elastomer contains natural rubber and also styrene-butadiene rubber, butadiene rubber, isoprene rubber or other materials known in the art or at least one additional elastomer such as any of the synthetic elastomers disclosed herein.

Any filler known in the art of elastomer composite products can be used.

The filler may be granular or fibrous or plate-like. For example, a granular filler matter consists of separate parts. These types of fillers are usually graded 321 or lower. or an aspect ratio of 221 or less or 1.521 or less (e.g., length2diameter) may have. Fibrous fillers, such as 221 or higher, 321 or higher, 421 or may have a higher or larger aspect ratio.

The filler may contain at least one material selected from 2-carbon materials, carbon black, silica, bio-based fillers such as nanocellulose and lignin, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, recovered carbon and recycled carbon black (e.g., rCB, as defined in ASTM D8178-19) fillers obtained from recycled materials, graphenes, graphene oxides, granules, specifications incorporated herein by reference), carbon nanotubes, carbon nanostructures (CNS), fragments of carbon nanostructures, fragmented multi-walled carbon nanotubes (PCT Application No. 1, the specification of which is incorporated herein by reference). coated materials or their chemically treated materials (e.g., chemically treated carbon black).

Other suitable fillers include carbon nanostructures (CNSs, singular CNS), e.g. branched, branched from the inside to the outside, intertwined, entwined and/or with common walls multiple carbon nanotubes cross-linked into a shared polymeric structure (CNT) is included. CNS fillers, specifications incorporated herein by reference black, silica and silicon treated carbon black and carbon black and silicon treated carbon Filler mixtures such as black mixtures can also be used. filler chemical chemically treated (e.g., chemically treated carbon black, chemically treated silica, (carbon black treated with silicon) and/or chemically modified. Filling The material may be or contain carbon black having a bonded organic group.

The filler may have one or more coatings on it (e.g., silicone). coated materials, silica coated material, carbon coated material). Filling The material may oxidize and/or have other surface treatments. Filling that can be used No specification regarding the type of material (e.g. silica, carbon black or other fillers) There is no limitation.

The filler is described in PCT Pub., the specification of which is incorporated herein by reference. No. WO It may contain a fibrous filler containing (e.g., nano-sized carbon filaments). Other fibrous fillers are commercially available poly(p-) as KeVlar® paste (Du Pont). phenylene terephthalamide) paste is included.

Other suitable bio-sourced or bio-based materials (derived from biological sources), recycled materials or materials that can be considered renewable or sustainable Other fillers include: hydrothermal carbon (HTC, where the filler contains lignin processed by hydrothermal carburization as described), rice husk silica, methane carbon obtained from pyrolysis, processed polysaccharide particles, starch, diatomaceous earth, crumb rubber and functionalized crumb rubber. Sample processed polysaccharides, their specifications The ones described are included. For example, polysaccharides can be selected from: poly alpha-1,3-glucan; poly alpha-1,3-1,6-glucan; 90% or more (more than 1% by weight with x-1,3-glycosidic linkage a water-insoluble alpha-(1,3-glucan) polymer having a degree of polymerization; dextran; a composition comprising a poly alpha-1,3-glucan ester compound; and weight average polymerization in water with a degree (DPW) of about 10 to about 1000 and a cellulose II crystal structure insoluble cellulose. Optionally, at least one filler may include rice husk silica, lignin, It is selected from nanocellulose and hydrothermal carbon.

Bio-based (derived from a biological source) and recycled materials (e.g. recycled materials) type of filler that can be used (e.g., silica, carbon black, or There are no limitations regarding other fillers (other fillers described here). Coated Examples of fillers are described in US Pat. No. Includes those described in ,519,298. Chemically processed fillers Examples include, for example, U.S. Pat. ,922.1, described in 18, having at least one organic group attached (e.g., diazonium reaction through) fillers (e.g., carbon black) are included.

The filler consists of at least one part of the carbon black aggregate as an internal part of the carbon black. a type containing silicon, such as silicon oxide or carbide, distributed throughout the May contain carbon black treated with silicone. Silicone treated carbon blacks, coated or are not otherwise modified carbon black aggregates, but rather biphasic aggregates They represent particles. One phase still exists as graphite crystallite and/or amorphous carbon is carbon, while the second phase is silica (and possibly other silicon-containing species). Therefore, silicon-containing species phase of silicone-treated carbon black, at least part of the aggregate KTM silicone treated carbon blacks It is a special aggregate section distributed throughout. ecoblac Available from Cabot Corporation. The production and development of these silicon-treated carbon blacks US Pat. No. at 6,028,137 is explained. Silicone treated carbon black is mainly used as aggregate of carbon black. may contain silicon-containing regions on its surface, but are still part of the carbon black and/Or silicone treated carbon black dispersed throughout the carbon black aggregate May contain areas containing silicone. Carbon black treated with silicon may be oxidized.

At least one filler (e.g., carbon black, silica, silicone treated carbon black, or all other fillers described and their combinations) in at least one elastomer It can be dispersed in an amount ranging from 40 phr to 80 phr or 40 phr to 60 phr. Clear carbon-based nanomaterials, e.g. graphenes, graphene oxides, reduced graphene oxides,10 carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon nanostructure pieces, segmented multi-walled carbon nanotubes, at least one at least 0.1 phr in the elastomer, alone or with carbon black, silica, silicone wrought carbon black and other fillers and combinations described herein. or can be co-dispersed with more non-carbon-based nanomaterials. carbon based It can be dispersed in amounts ranging from 1 phr to 3 phr or 1 phr to 2 phr. Specifications intervals can also be used.

Optionally, at least one elastomer in the elastomer composite product is at least 30% natural contains at least 99% natural rubber) and at least one filler in the elastomer composite product Filler carbon black, e.g. at least 20%, at least 30%, at least 40%, at least 50%, at least uncured composite product if almost all of the material is carbon black It may be a product formed by adding at least one binding agent. For example, the composite product is at least a filler, elastomer (or elastomer latex) and at least one binding agent or the composite product may also be prepared by mixing at least one binder may contain. PCT, filed December 8, 2021, the specification of which is incorporated herein by reference BasV. No. In the presence of certain binders such as those disclosed in PCT/USZ1/62433 The prepared composite products must be aged over time, for example at least 5 days at a temperature of at least 20°C, 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 at least 6 months (at least 180 days) to 1 year (12 months) or even less than 2 years. In this way reduced spoilage maximizes the benefits achieved by the storage/packaging methods described herein. It can be obtained at least partially as a supplement. Optionally, the composite product also includes at least one contains a binder, for example, an uncured compound containing filler and elastomer. The composite product or master-batch material is prepared according to any method known in the art and then at least one coupling agent and optionally at least one additive (e.g., one or more compounds with antifouling or other additives as described herein. After being subjected to forming or other processing steps, a vulcanization product is created.

Optionally, the coupling agent(s) may be composed of compounds having at least two functional groups. can be selected here first functional group -NRIRZ, -N(R1)(R2)(R3)+A', - S-SOgM1 and formula (I) and is selected from the structures represented by the formula (H), N(1)(II) where A' is chloride, bromide, iodide, hydroxyl, nitrate or acetate, X = NH, 0 or S, Y = H, OR4 is an integer selected from NR4R5, - SnR4 and n1-6 and second functional group thiocarbonyl, nitrile oxide, nitron, nitrile imine, - S-SOgMZ, - Sx-Rö, - SH, - C(R6)=C(R7) - C(0)R8› - C(R6)=C(R7) - COzRS, - C(R6)=C(R7) - COzMZ R1-Rs are each independently selected from H and C1-C8 alkyl; M1 and Mz are each independent is selected from H, Na+, K+, Li+, N(R')4+, where each R' is independently selected from H and Ci-Czo alkyl and X is an integer selected from 1-8.

Without wishing to be limited to any theory, the process of mixing with wet filler while improving the filler dispersion, the bonding agent between the filler and elastomer with filler and/or elastomer to create a stronger interaction between It is believed that it can interact with Optionally, the coupling agent may include the first and second at least two functional groups in which the functional group can interact with the elastomer and/or filler. may have functional groups. Interaction such as ionic interactions, dipole-dipole interactions, hydrogen bonding, covalent bonds etc. through adsorption or a May contain chemical bonds. In the composite product, the binder is added to the mixer. in the same form as when filled or, for example, with filler and/or elastomer If it interacts through chemical bonding, it may exist in a different form.

Two, three or four or more coupling substances containing at least two functional groups may contain functional groups. In any of these embodiments, the coupling agent - NRlRz, - N(R1)(R2)(R3)+A', - S-SO3Ml and the structures represented by formula (I) and formula (H) (1) (11) where A' is chloride, bromide, iodide, hydroxyl, nitrate or acetate, X = NH, 0 contains a selectable first functional group, Or S, Y = H, OR4, NR4R5 or SnR4 and n is an integer selected from 1-6. In some directions, the first functional group consists of -NRIR2 (e.g. -NHRI or -NH2), -CO2M1 and -S-SOgM1 can be selected.

The coupling agent also includes thiocarbonyl, nitrile oxide, nitron, nitrile imine, - S-SO3M2, - Sx-Rö, - SH, may contain a second functional group. In some aspects, the second functional group - S-SOgM2 and - Can be selected from CR6=CR7-C02M2. Functional group - cole, - S-SO3M1, - S-SOgMZ and - When CR6=CR7-CO2M2, they can be selected from acids or their salts, for example, M1 and Mz can each be independently selected from H, Na+, K+, Li+, and N(R')4+ (e.g., each R' moiety is independently H and C1-Czo alkyl, such as C1-C12 alkyl or C1-C6 alkyl or C1-C4 ammonium salts selected from alkyl, e.g., monoalkyl, dialkyl, trialkyl or tetralkyl ammonium salts). Two or more M1 or two or more M2 groups of the binder where each M1 or M2 is independently composed of H, Na+, K+, Li+ and N(R')4+ can be selected.

In the embodiments described herein, Rl-Rg is each independently formed from H and C1-Cg alkyl. is chosen; M1 and Mz are each independently selected from H, Na+, K+, Li+, N(R')4+ and is a selected integer.

Optionally, the first functional group may interact with carbon black. Carbon black, including, but not limited to, carboxylic acid (and salts thereof), hydroxyls (e.g., phenols), oxygen-containing substances such as esters or lactones, ketones, aldehydes, anhydrides and benzoquinones groups, may have one or more types of surface functional groups. Another Alternatively, the second functional group may interact with the solid elastomer. Thick Elastomers can be natural elastomers, synthetic elastomers and mixtures thereof. For example, solid elastomers natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber,10 isobutylene-based elastomers, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, It can be selected from silicone elastomers and their mixtures. Optionally, solid elastomer It can be chosen from natural rubber, styrene-butadiene rubber and polybutadiene rubber. Thick The elastomer may have olefin groups and/or be functionalized with various groups.

Optionally, the first functional group consists of - NRIR2 (e.g. - NH2) and - S-SO3M1 and the second functional group can be selected from - S-SO3M2 and -CR3=CR4-CO2M2.

The coupling agent may contain more than two functional groups. With this type of bonding agents, every an additional functional group, such as third, fourth Etc. functional group described here The first and second functional groups can be selected from the list. Optionally, a composite product More than one type of binder can be used to prepare it.

The coupling agent also provides at least one spacer between the first and second functional groups. may contain. For example, one or more spacers connect to each other and ultimately to the first and second spacers. It may depend on the functional group. Optionally, at least one spacer - (CH2)n-, - (CH2)yC(O) -, - C(R9)=C(R1°) -, - C(O) -, - N(R9) - and - C6H4 -, where y is 1- 1 is an integer selected from 0, and R9 and Rlo are each independently H and C1-C6 alkyl. is selected. Exemplary binders are selected from the following: formula (1), formula (2) and formula (3). related compounds, HzN-Ar-N(H)-C(O)-C(R6)=C(R7)-CO2M2 (i) HzN-(CH2)n-8803M2 (2) M103S-S-(CH2)n-S-803M2 (3).

M1 and M2 are as defined herein, R6 and R7 are independently selected from H and C1-C8 alkyl (e.g., independently selected from H and C1-C6 alkyl or independently selected from H and C1-C4 alkyl).

Optionally, M1 and M2 can each independently detect H, Na+ and N(R')4+, such as H and is selected from Na+ and R6 and R7 are the same, eg R6 and R7 are each H. A related to formula (1) An example of the bonding agent is commercially available as Sumilink® 200 bonding agent. sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate and formula (2) An example of a bonding agent is Sumilink® 100 bonding agent (Sumitomo). It is commercially available S-(3-aminopropyl) thiosulluric acid. A related to formula (3) An example of a bonding agent is DuralinkTM HTS tire additive (Eastman Chemical C0.) can be obtained from the market. Other coupling agents include cystamine and thiourea.

Optionally, the uncured composite product contains at least one filler, an elastomer (or latex) and at least one binding agent, such as filler and elastomer (or latex). during a first stage mixing process or a slurry of filler and latex or in combination with a composite product obtained by mixing compounding (productive or non-productive) and/or forming an uncured composite It is a product of mixing during additional processing of the product. Binding substances composite products containing and methods for creating such composite products It is described in PCT/U S21/62433. For example, uncured composite product, filler, known dry mixing, such as mixing an elastomer and at least one binder It is the product obtained from the processes. As another example, the uncured composite product is create a mixture of at least solid elastomer, wet filler and binder mixing (in one or more mixing stages) and at least one by removing part of it from the mixture by evaporation or its specifications are referenced herein. It is a product obtained as described. As another example, uncured composite product, It is prepared by mixing a wet filler and a solid elastomer as described and PCT Edition filed on December 8, 2021, the specification of which is incorporated herein by reference. No.

It is combined with at least one coupling agent as described in PCT/U S21/62433. Composite added to the product, curd, or compound or filled into the mixer (or as described herein). by any of the methods) the amount of binder is 10 phr or less, such as 6 phr or An amount or specification ranging from 4 phr, 0.1 phr to 3 phr, or 0.1 phr to 2 phr PCT Edition filed December 8, 2021, incorporated herein by reference. No.

There may be other quantities disclosed in PCT/U S21/62433.

Elastomer composite product in any form, such as sheets, blocks or sawdust smaller pieces, such as bales of smaller pieces, such as bales of sawdust can be stored. Small parts of the composite product, the specification of which is incorporated herein by reference US Pat. No. It can be formed using a granulator, as described in US 7,341,142.

The form of the elastomer composite product can affect the amount of oxygen present in the container. For example, a randomly arranged bale of sawdust may have a porosity of at least 25%.

When mixed with elastomer filler, some degradation of the rubber may occur.

In some cases, carbon black, silica, silicone treated carbon black, or as described herein elastomer composite with fillers dispersed like any filler For products, the containers, packages and/or storage methods described herein may be useful.

The filler distribution and spreading within the elastomer network is a "spreading state" or can be represented by macro-extension. Optionally, macro-dispersion, particle sizes, A "d90" particle size distribution where particles > 2 µm are determined by measuring the % area contribution It can be shown with . For an imaging field, the field contribution of particles can be determined and a The total viewing area (umz) in the image consists of the number of pixels and image resolution. can be determined. An image has a width and height, each given as a number of pixels. dimensions and the corresponding area can be given as (pixels)2. For a field, The resolution can be given as (um/pixel)2. The imaging area is the product of: (area) * (resolution).

Optionally, d90 is the area-equivalent diameter of the filler particles in the composite product is more than 10 µm.

Optionally, the composite product must be rated at least 50 kPa, for example at least 100 kPa or at least 200 kPa where G'(10%) is a dynamic storage modulus measured at 10% strain amplitude. EXAMPLES The following tests are performed to obtain performance data for each of the vulcanization products. used: at 23°C, 50% relative humidity and It was evaluated with . Strain gauges were used to measure tensile stress.

The M3 00/M100 ratio is stated as the tensile stress ratio (or modulus ratio).

The maximum tan is determined using a parallel plate geometry with a diameter of 8 mm in torsion mode. Measured with ARES-G2 or ARES 2K rheometer (Manufacturer: TA Instruments).

The vulcanization product sample was 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 scans, and maximum measured tan ö (“max tan ö”), also referred to as “tan 8” unless otherwise stated has been reported. The Payne ratio of the compound is the dynamic storage modulus (G') at 0.1% strain. and it was calculated from the ratio of G' value at 50% strain, that is, G'(0,1%)/G'(50%).

Rheological properties were analyzed with a rubber process analysis tool (RPA, D-RPA 3000, MonTech Rubber It was determined by Testing Solutions). A sample of rubber composite products (5 g) has been cut. Throughout the test procedure, the temperature was set at 1000C and a cut-off frequency of 1 Hz. used. The test program remained constant for 5 minutes, followed by 10 cycles at 50% strain. shear cycle, followed by 30 minutes at 0.3% strain and finally one at 0.3-51.5% strain. Strain scanning was performed. Payne ratio of the composite product is 0.3% strain the ratio of the dynamic storage modulus (G') and the G' value at 51.5% strain, i.e. G'(0.3%)/G'(51.5%) was calculated.

In this Example, the elastomer composite product is prepared by the liquid mixing process, the same storage of different parts of the elastomer composite product under air, nitrogen and vacuum The results are announced.

The composite product, except as specified herein, is manufactured under US Pat. No. 8,586,651, siVi in Example 2 It was prepared using the following process. Elastomer latex (MVL Field LateX, diluted and not sludge) It had a dry rubber content of 28% by weight and the filler slurry was rates such that a final carbon black quantity of 55 phr is achieved at the desired production rate. is set. The average amount of carbon black in the resulting composite product was 55 phr.

The dehydrated composite product was kneaded, mixed with 2 phr of antioxidant (6PPD) and mixed into a in a continuous mixer (Farrel UnimiX Continuous Mixer (FCM) with two no. 15 rotors equipped; operated at 190-320 rpm, Farrel Corporation, Ansonia, CT) dried and additionally kneaded, cooled and dried in an open mill.

The composite product has a length of approximately 80 mm, a width of 8 mm and a thickness of 8 mm. sawdust by processing a 90 mm strip in a granulator to create small pieces has been made. Methods, specification, for cutting strips with a granulator US Pat. No. It is described in No. 7,341,142. More sawdust They were then divided into various samples stored under the conditions listed in Table 3.

After storage, all elastomer composite products conform to the formulation and 300 mL C. W. Brabender tank equipped with cam blades according to the protocol shown in Table 2 It was compounded in the internal mixer. Accelerator BBTS is Akrochem, Akron, (N-tert-butyl-2 benzothiazole sulfenamide) from Ohio was used, Compounding conditions were It was as follows: initial temperature = 40°C; rotor speed = 60 rpm; fill factor = Formulation (phr) For Elastomer Composite Product NR Latex 100 6PPD 2 For Compounding Elastomer composite product 157 Zinc Oxide 4 Stearic Acid 2 6PPD 0.5 Accelerator BBTS 0.8 Time (seconds) Description Add 0 elastomer composite products, start timer Add 120 zinc oxide, 6PPD and stearic acid Add 240 BBTS and sulfur Pour 300 - check compound temperature and weight The compounds were then rolled into sheets in a 2-roll mill operating at 10.5 m/min at 50°C. four times through the mill with a nip gap of approximately 5 mm. times (rolled end to end). The samples were placed in a heated press at 150°C for 30 minutes. is cured.

In Table 3, storage conditions of each composite product (before compounding) and The properties of the composite product and the resulting compounds (vulcanization products) are given.

"Time" in Table 3 refers to the number of days the sample was stored under the specified conditions. states.

In Table 3, "Atm" indicates whether the sample was stored under air, nitrogen ("N2") or vacuum ("Va"). states. For samples stored under vacuum, composite products were metalized bags (Marvelseal® 360 barrier film, Berry Global, Inc., biaxial an oriented Nylon/PE/aluminum foil/PE/LLDPE (insulating adhesive layer), The relative humidity was set at 23°C (73°F). Three hours after production of the composite product Inside, the bags are purged with nitrogen, vacuumed to 84.7 kPa and insulated. has been closed. For samples stored under nitrogen, within three hours of production The composite products were placed in metallized bags, vacuumed, purged with nitrogen and sealed at ambient pressure within three hours of production. with gas cleaning and vacuum application steps with an AmeriVacs AVN retractable nozzle It was carried out with a vacuum heat insulated sealer.

In Table 3, "Temperature" refers to the storage temperature of the composite product. "60°C", Refers to samples stored at 60°C (50% relative humidity), obtained by placing samples (including samples stored in bags) in an oven. Specified time period After storage at 60°C for 60 °C, the samples were incubated overnight before compounding. It was allowed to equilibrate to room temperature throughout. "20°C”, temperature controlled at 20 ± 3°C Refers to samples stored in air-conditioned rooms.

The properties of the reference composite product were measured before insulating (Day = 0, i.e. no storage). Values given in Table 3 for samples stored in an air-conditioned environment These are the average values obtained from six samples. given for samples stored at 60°C. Values are average values obtained from four samples. The composite indicated by "(C)" All properties reported are for vulcanization products, except those stated for products. (day) Rate (C) (kPa) (kPa) tan ö (MPa) (MPa) M100 Or The data in Table 3 shows the composition of the stored composite product and the resulting compound, i.e. It shows the properties of vulcanization products produced from composite products. Composite Referring to product characteristics, Payne ratio is stored in air for a period of 90 days usefully for samples stored under nitrogen and vacuum, compared to samples is falling. With reference to the properties of the compound, under all temperature conditions, nitrogen and vacuum Maximum tan values and Payne Ratio of packaged samples are maintained or can be seen to decrease. In contrast, in air over a 90-day period (standard 21%) with oxygen content) the maximum tan for all samples stored increases. This effect occurs in air nitrogen or vacuum in response to an increase in the maximum tan value for stored samples. storage at 60°C as seen by the corresponding decrease for samples stored below is evident in this case. Existing composite products and corresponding compounds in air compared to samples stored (i.e. not stored in an oxygen barrier container) It provides unexpected hysteresis recovery.

In this Example, the composite product is prepared by dry mixing processes, the same elastomer Results of storing different parts of the composite product under air, nitrogen and vacuum is explained.

All samples were supplied as VULCAN® 7H carbon black (“V7H”, Cabot Corporation). Made with ASTM class N234 carbon black. Standard quality RSS3 as elastomer Natural rubber (Hokson Rubber, Malaysia) was used. The technique of this natural rubber statements are widely available, e.g., Lippincott and Peto, Inc. by (Akron, Ohio, USA) Available in Rubber World Magazine's Blue Book.

Mix the composite product with a BR-1600 Banbury® mixer (“BR1600”; Manufacturer: Farrel). It was mixed in step 1. The resulting composite products were stored in a 439 mL C. W. Brabender internal It was compounded in a single step in the mixer. Table 4, mixing and compounding shows formulations for fetching. As wax beads, Akrochem, Akron, AkrowaXTM 5031 wax beads from Ohio were used.

Formulation (phr) For Elastomer Composite Product NR 100 6PPD 2 For Compounding Elastomer Composite Product 152 Zinc Oxide 3 Stearic Acid 2 6PPD 0.5 Antioxidant DQ Pellets 1.5 wax beads 1.5 Accelerator BBTS 1.4 The mixing protocol is shown in Table 5, where the mixing conditions are as follows: temperature control unit (TCU) temperature = 50°C; rotor speed = 80 rpm, filling rate = Stage Time or Temperature Stage Description Add 0 s NR 120 s Sweep / Add Remaining Filler 150 s Sweep l40°C Add 6PPD Sweep / Scrape l60°C Drain The resulting composite products were processed with a roller operating at 50°C and approximately 37 rpm. formed into sheets on the mill, then a pinch gap of approximately 5 mm Six end roller passes have been made. Composite product layers in air or nitrogen divided into several samples for storage below. Samples in nitrogen environment For this purpose, the elastomer composite products were placed in a glove box purged with nitrogen. (oxygen concentration less than 2%). All samples were collected in an air-conditioned (20°C) environment. has been stored.

The compounding protocols are shown in Table 6, where the compounding conditions are as follows: TCU temperature = 40°C, rotor speed = 60 rpm, filling rate = Time (seconds) Description 0 Slowly add the composite product (60 s filling + 60 s kneading) Add 120 Zinc Oxide, Stearic Acid and 6PPD 300 Empty The obtained compounds were milled in a 2-cylinder mill operating at 50°C and 37 rpm. and then milled four times with a nip gap of approximately 5 mm. times (rolled end to end). The samples were placed in a heated press at 150°C for 30 minutes. is cured.

Compound and composite product properties are shown in Table 7, where "Atm" is used in Example 1 is as defined. Properties of the reference composite product before insulating measured (Day = 0, i.e. no storage). (day) Rate (kPa) (kPa) tan ö (MPa) (MPa) From the data in Table 7, it can be seen that the composite products stored under nitrogen were exhibited lower Payne Ratio values compared to samples stored in visible. For compound (vulcanization product) properties, samples stored in air The maximum tan values are for a 180-day period. On the other hand, nitrogen Maximum tan values for samples stored under air was significantly lower compared to the values of the samples. under nitrogen The stored samples were also stored in air (i.e., in an oxygen barrier container). slightly higher tensile stress ratio (M3 00/M100) compared to (non-stored) samples. and had a lower Payne ratio.

In this Example, the composite product is made by mixing a wet filler with a solid elastomer. Different parts of the same elastomer composite product are prepared under air or nitrogen. The results of storage are explained. The composite product was stored in layers.

All samples were supplied as VULCAN® 7H carbon black (“V7H”, Cabot Corporation). Made with ASTM class N234 carbon black. Standard quality RSS3 as elastomer Natural rubber (Sri Trang Agro-Industry Public Company Limited, Thailand) was used. By grinding black pellets, 99.0% particle size smaller than 10 microns Fluffy carbon black particles with diameter were formed. This fluffy carbon black It was then wet pelletized in a pin pelletizer. The resulting wet carbon black (rewet carbon black) had a moisture content of 57%.

To create vulcanization products, composite products undergo a two-stage mixing process. It was prepared through a two-stage compounding process followed by a two-stage compounding process.

The formulations are shown in Table 8; The amount of carbon black is given on a dry basis.

Formulation (phr) Elastomer Composite Product CB Vulcan® 7H 50 6PPD 2 Compounding 1 Elastomer Composite Product 152 Zinc Oxide 3 6PPD 0.5 Antioxidant DQ Pellets 1.5 wax beads 1.5 Compounding 2 Accelerator BBTS Powder 1.4 The first stage of the composite product mixing process was carried out on a Kobelco machine equipped with 4WN rotors. It was carried out in a BB-72 Teget Mixer (66 L capacity) at a filling rate of 66%.

The mixing chamber, rotors and driver were heated with a TCU set to 75 0.

The hammer pressure was 15.5 MPa. After the first stage mixing, the composite product on a Kobelco TSR-125 twin Screw discharge extruder (Kobelco) equipped with fixed blades Kobe Steel Group) was processed. The first site mixing protocol is shown in Table 9. Achieved batch times 9.2- It has been 9.4 minutes. The probe temperature range of the first-stage composite product is 123-13 l°C and humidity Its content was 4%.

Mixer Description rpm 45 Add rubber to the mixer within 20 s 45 Knead the rubber up to 10°C 60 Add 1/2 filler in 20 s Mix up to 80 l30°C 60 Add l/4 filler in 20 s Mix up to 80 l30°C 60 Add l/4 filler in 20 s Stir to 80 l68°C 60 Add 6PPD in 20s Mix until 80 175 0 and empty the batch The second page mixing protocol is shown in Table 10. The second part of the composite product mixing field in a Kobelco BB-16 Teget Mixer equipped with 6WI rotors (14 L capacity) (Kobelco Kobe Steel Group), was carried out at a 40% filling rate.

The mixing chamber and rotors are kept at constant temperature using a TCU set at 5 0°C. has been kept. The mixing process will not apply any pressure to the contents of the mixer. This was done by lifting the hammer to the highest position. composite product The delay between the first and second stages of the mixing process was at most 2 hours. First After kneading, the second composite product mixing area creates a feedback loop. PID control, which allows automatic control of the batch temperature via (proportional integrated difference). Via the openable lid of the mixer An inserted thermocouple measures the batch temperature, which is sent to a PID controller. controller Its output is used to control the speed of the mixer's rotors. Second field composite The product mixing protocol is shown in Table 10. Probe of the second field composite product The temperature range was l33-140°C and the moisture content was 1%.

Mixer rpm Description Add composite product to mixer Knead for 90 seconds while removed from the sahmer. While it is removed from the sahmer, knead it for 390 seconds. Party -50 temperature using a setpoint of l35°C, PID is automatically controlled via on a TSR-l25 twin Screw discharge extruder (Kobelco Kobe Steel Group) equipped with has been processed. After 27 days in ambient conditions, the composite products conform to the conditions given in Table I3. It was stored in layers underneath. Samples were stored at 20°C (air-conditioned) storage temperature and in air or in a glove box purged with nitrogen (“N2”) (oxygen concentration Two-stage compounding process with BR1600 mixer under the following conditions carried out: TCU temperature = 50°C (1st and 2nd stage), rotor speed = 80 rpm (l. (second stage) or 60 rpm (2nd stage), filling rate = 68% (1st stage) or 65% (2nd stage), hammerhead pressure = 2.8 bar (1st and 2nd stage). Phase 1 and 2 compounding protocols are shown in Tables 11 and 12, respectively.

Time (seconds) Step 1 Compounding Description 0 Add composite product Add the formulation "Compounding 1" 90 Clean/Sweep 150 Evacuate in 150 s, adjust rpm until temperature is <125°C Step 2 Compound Formation Explained (second) 1/2 stage 1 composite product/"compounding 2" formulation/remaining stage Add 0 1 composite product sweep it 90 Drain, adjust rpm until temperature is <115°C After each compounding phase, the compounds were heated at 50°C and approximately 37 rpm. It was rolled into sheets in a 2-roll mill and then rolled to a thickness of approximately 5 mm. It was passed end-to-end through a roller mill with a pinch gap six times. SaIha 2 Vulcanization product properties are shown in Table 13. Reference composite product properties measured before insulated closure (Day = 0, i.e. no storage).

Time (day) Atin Temperature max to m M M300/M100 Payne Ratio From the data in Table 13, the maximum tan value for sheets stored in air at 20°C It can be seen that the values maintain or increase throughout the 180-day period. On the other hand, nitrogen The maximum tan value of the samples stored below the 180-day storage period It then decreased significantly. Additionally, samples stored in nitrogen at 20°C smaller decreases in tensile stress compared to samples stored in air exhibits. Additionally, the Payne ratio of samples stored under nitrogen only There was a decrease in their values.

In this Example, the composite product consists of a wet filler, a solid elastomer and a binder. Different parts of the same elastomer composite product are prepared by mixing the substance with the results of storage in layers under air or vacuum and the composite product An evaluation of the properties of the prepared compound is described.

All samples were supplied as VULCAN® 7H carbon black (“V7H”, Cabot Corporation). Made with ASTM class N234 carbon black. Moisture of wet carbon black pellets content was 56% and 99.5% had a particle size diameter of less than 10 µm. grind through an 8" model Micro meat grinder to create fluffy carbon black particles. It is prepared by grinding. This fluffy carbon black is then soaked to form pellets. The pin was wetted with a pelletizer. Standard quality RSS3 natural rubber (Von) as elastomer Bundit Co. Ltd., Thailand) was used. Technical descriptions of this natural rubber are widely available. as, e.g., Lippincott and Peto, Inc. Rubber published by (Akron, Ohio, USA) Available in World Magazine's Blue Book. Sumilink® from the market is used as a binding agent. 4-[(4-aminophenyl)amino]-4-oxo-2-butenoate was used.

Composite products become a single-stage compound after a two-stage mixing process. Prepared through the fetching process. The formulations are shown in Table 8; carbon The amount of black is given on a dry basis. The formulations used are in Table l4 is shown. The amount of carbon black is calculated on a dry basis.

Formulations (phr) Phase 1 Formulation V7H wet 50 8200 2 6PPD 2 For Compounding zinc oxide 3 stearic acid 2 wax beads 1.5 6PPD 0.5 The first stage of the two-stage mixing protocol is summarized in Table 15. Time intervals indicates the duration of the session. First field mixing, BB-16 equipped with 4WN rotors on a mixer (16.2 L capacity) under the following conditions: TCU temperature = 90°C, filling rate = 66%, hammer pressure = 112 barg.

Duration or rotor speed Description Temperature (deVir/minute) s 50 feed rubber into mixer 1 10°C Knead 60 rubber to 1 10°C p 60 1st add filler addition (75%) 130°C Add s 60 S200 and then 2nd addition of filler s 60 20 seconds to allow the hydraulic system to reach pressure Mix at 60 rpm/minute throughout mix until s 60 add 6PPD Mix to 85 discharge temperature (160°C). s 50 Empty after 30 s The moisture content of the composite product after the 1st stage mixing was 4.96% (after mixing time = 7 min 20 s, probe temperature = 125°C). After the first stage mixing, the composite product a TSR-125 twin Screw discharge extruder (Kobelco Kobe Steel) equipped with fixed blades Group).

The second field mixing protocol is shown in Table 16 and mixing is performed with 6WI rotors. on the equipped BB-16 blender (14.4 L capacity), under the following conditions realized: TCU temperature = 65°C, filling rate = 35%, hammer pressure = 112 barg. After the initial kneading, mixing, as described in Example 3, It was carried out under PID temperature control by lifting it to position.

Duration or Rotor speed Description Temperature (rpm) 20s 35 Add composite product to mixer 90 s 35 knead 90 s while removed from the ram -54 PID temperature control with variable removed from the hammer knead under it; batch temperature with 135°C set point Empty the drain mixer and close the opened lid after 30 seconds. After the second stage mixing, the composite product is rolled by roller mold to form sheets. on a TSR-l25 twin Screw discharge extruder (Kobelco Kobe Steel Group) equipped with has been processed. The resulting layers were cooled under ambient air for 27 days.

The composite products are then laminated under air or vacuum for 90 days at 20°C. For samples stored under vacuum, composite products placed in metallized bags (Marvelseal® 360 barrier film) and gassed. cleaned and then with AmeriVacs AVN vacuum heated sealer with retractable nozzle It is vacuumed.

After the storage period, the stored composite products are listed in Table 14. formulation and equipped with CAM blades according to the protocol shown in Table 17. by compounding in a 439 mL C. W. Brabender prep mixer. vulcanization products were created. Accelerator BBTS is Akrochem, Akron, (N-tert-butyl-2 benzothiazole sulfenamide) from Ohio was used. The conditions for forming compounds are as follows: It was as follows: initial temperature = 40°C; rotor speed = 60 rpm; fill factor = Time (seconds) Step 1 Compounding Description 0 Add composite product Add 120 Zinc Oxide, stearic acid and 6PPD 240 Scrape/Sweep - Add BBTS and Sulfur 300 Empty After the compounding phase, the composite products are processed at 50°C and approximately 37 rpm. It was rolled into sheets in a 2-roll mill and then rolled to a thickness of approximately 5 mm. It was passed through the clamping gap six times. The final compounds were processed at 60°C. It was turned into a 2.4 mm thick layer on a 2-roll mill. Final The compounds were cured in a heated press at 150°C for 30 minutes.

Prepared from three composite product samples, each aged for 90 days. The properties of vulcanization products are shown in Table 18. "Atm", the sample's air It refers to the atmosphere in which it is stored or under vacuum.

Zaman Payne M100 M300 Atm max G', G', M300/M100 (day) Rate (MPa) (MPa) tan o (MPa) (MPa) From the data in Table 5, the maximum diagnostic value for sheets stored under vacuum at 20°C values decreased significantly after the 90-day storage period. visible. In addition, there was a decrease in the Payne ratio values of layers stored under vacuum. has been seen.

In this Example, different parts of the same elastomer composite product were tested at 0% relative humidity and 23°C. The result of storing in packages with OTR values varying between is shown.

In Table 19 below, wall structure, OTR (at 0% relative humidity and 23°C (73°F)) and wall thickness The features of the tested packages are listed, incl. Packages A through D from ILC Dover, Inc. They are flexible, transparent bags. Reported OTR values are 23°C (73°F), 0% per ASTM D3985 Package Wall materials (cc/m2/24 hours PE / EVOH / PE / LLDPE (insulated 81 0.527 A adhesive) LLDPE / Nylon / EVOH / Nylon / LLDPE 76 2 33 B (insulating adhesive), C EVA/Nylon/EVA (insulating adhesive) 51 233 Composite products tested Table 1, Elastomer Composite Product in Example 1 It was prepared according to its formulation. Formulation of rubber composite products Table 1, Same as example 1, since no compounding process is performed in this example There is no compounding material.

After 15 days of storage in air, composite products (150 g, specific gravity 1.112 g/cc) stored in packages and subjected to the conditions specified in Table 20. To compare ("Kars") samples were stored in air. The remaining samples are listed in Table 19 stored in one of bags A, B, C or D with the relevant OTR values.

Samples were stored in a unique package atmosphere (“Package Atm”) and a 60°C oven. ("Day") combination under the "Package Atmosphere" column. “Sealing” means sealed containers within the package without any change in atmosphere. refers to composite products. "Vak/N2" is the pressure of the package to achieve a pressure of 84.7 kPa. vacuuming (containing the composite product), then purging the bags with nitrogen and unpacking the package. It refers to composite products stored after being closed in isolation. with gas cleaning and vacuuming steps using an AmeriVacs AVN retractable nozzle vacuum cleaner. It was carried out with a heat insulated sealer. All samples were stored for long periods under ambient conditions. for 14 or 21 days in an oven at 60°C to simulate long-term storage. has been stored.

Oxygen content is reported as the total gas concentration (%) in the upper space of the bag. was made and determined by two separate methods. For clear bags (bags A to D), the using optical fluorescence to measure oxygen content using sensors placed inside the clean package non-invasively with an OpTech®-02, Model P oxygen headspace analyzer (“OpTech”) It was measured as follows. Measurements were taken on day 0, then after the bags had reached room temperature. It was carried out on day 14 and/or day 21 during storage at 60°C. For all bags, The oxygen content in the headspace is also added to a resealable section on the outer surface of a bag. by applying and sealing the bag from the septum with a Dansensor® CheckPoint® 3S, OZ-Premium, Solid state Measured by puncturing with a sensored oxygen headspace analyzer ("CheckPoint"). Both type oxygen analyzer is also available from Ametek Mocon (Minnesota, USA).

Package OTR, Package Atm Day 02 conc. (%), 02 conc. (%), 02 cm /m /24 hours (Checkpoint) day 0 (OpTech) ( Kars. N/A Air 0 21 Kars. N/A Air 14 21 Kars. N/A Air 21 21 Package OTR, Package Atm Day 02 conc. (%), 02 conc. (%), 02 cm /m /24 hours (Checkpoint) day 0 (OpTech) ( Package OTR, Package Atm Day 02 conc. (%), 02 conc. (%), 02 cm3/m2/24 hours (Checkpoint) day 0 (OpTech) ( In Table 20, all comparison (“Compare”) samples are shown as a result of storage in air. It has an upper space concentration of 21% oxygen. All OTR values 0% relative humidity and is reported at 23°C (73°F). All Checkpoint data points in the "Day" column It indicates the measurements taken on the specified day. OpTech measurements, related ”OpTech” It was held on the days specified in the columns. Oxygen content, measured oxygen concentration It is expressed as .

From the data in Table 20, the general trend is that both CheckPoint and OpTech data show etc., the lower the OTR value, the lower the oxygen content measured in the headspace. shows that it is.

The oxygen content in bags A and B (which have the lowest and second lowest OTR respectively), sealed in air ("Insulated Enclosure") or modified atmosphere ("Vac/N2"), but decreased or maintained throughout the storage period.

The oxygen content of bag C, which is insulated in air, also increases during the storage period. decreased, but not as much as bag A and B. "Insulated Shutdown" stored under air The oxygen content of bag D did not decrease over time. Under modified atmosphere When stored, the oxygen concentration increases over time for both bag C and bag D. increases and the final oxygen concentration values are independent of the storage method. can be seen to be significantly higher than those in bags A and B.

In this Example, for the storage of composite products containing curing agents (green compounds) The usability of packages with high barrier wall features is demonstrated.

Composite products according to the Elastomer Composite Product formulation in Table 1, Example 1 has been prepared. Rubber compounds (green compounds) Compound in Table 1, Example 1 Prepared according to the formulation and protocol in Table 2, Example 1. More green compounds It was then turned into sheets in a 2-roll mill operating at 10.5 m/min at 50°C and then run through the mill four times (end to end) with a nip gap of approximately 5 mm. rolled) passed through.

The same elastomer composite product, i.e. the green compound (layer before curing), may have different Portions were stored at 30°C under the conditions specified in Table 21. In Table 21, "Am", Indicates whether the sample is stored in air or under vacuum ("vacuum"). It indicates the number of days stored under certain conditions. For samples stored under vacuum, green compounds, Marvelseal® 360 barrier thinner within three hours of compounding are placed in bags with a layer. Bags purged with nitrogen, pressure up to 84.7 kPa Vacuumed and insulated. Gas purging and vacuuming steps are one AmeriVacs AVN vacuum heat seal sealer with retractable nozzle has been carried out. Reference composite products measured before sealing with insulation (Day = 0, i.e. no storage).

After storage, the compounds were cured in a heated press (150°C) for 30 minutes.

Vulcanization product properties are also shown in Table 21.

Judging from its compound properties, it is stored under all temperature conditions and under vacuum. rubber compounds in which maximum tan values are maintained or reduced It can be seen that it provides Additionally, these rubber compounds also have a tensile stress ratio (M300/M100) has shown an increase. In contrast, in air over a 90-day period (standard 21%) with oxygen content) increased to the maximum tan for all samples stored. It should be interpreted in both singular and plural senses. "containing", "having", "comprising" and ranges are used to specify each value within the range, unless otherwise stated. It is used as a short method and each separate value is specified separately in the specification. It is added like. All procedures described herein are prohibited unless otherwise stated or evident from the context. It can be performed in any convenient order as long as it does not conflict in any way. any or all The use of examples or example expressions (e.g., "like") here only makes the invention better. It is intended to be illustrative and does not impose any limitations on the scope of the invention unless otherwise requested. It does not constitute a limitation. Any statement in the specification, any unclaimed element, It is accepted that it does not indicate that the invention is important for its application.

Claims (59)

STEMS l. A packaged elastomer composite product comprising an insulated sealed package containing the composite product in an atmosphere with a partial oxygen pressure of less than 10 kPa, characterized in that the composite product is uncured and contains at least one elastomer and at least one filler, the package is at least one layer surrounding the composite product. comprising a wall, at least one wall comprising at least one oxygen barrier layer such that the package has an oxygen transmission rate of not more than 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. 2. It is the packaged elastomer composite product in claim 1, and its feature is that the partial oxygen pressure of the atmosphere is at most 7 kPa. 3. It is the packaged elastomer composite product in claim 1, and its feature is that the partial oxygen pressure of the atmosphere is at most 5 kPa. 4. It is a packaged elastomer composite product according to any one of claims 1-3, characterized in that the atmosphere contains at least 90% of at least one gas that does not react with the elastomer composite product. 5. It is the packaged elastomer composite product in claim 4, characterized in that at least one gas that does not react with the elastomer composite product is selected from nitrogen, argon, helium, xenon and carbon dioxide. 6. The packaged elastomer composite product according to any one of claims 1-5, characterized in that at least one oxygen barrier layer consists of polyamide, polyethylene, polyethylene terephthalate, polyethylene naphthalate, aluminum, poly(ethylene Vinyl alcohol), poly(Vinilidene chloride), polyacrylonitrile and It contains a material selected from mixtures of these and their metallized layers. 7. The packaged elastomer composite product according to any one of claims 1-5, characterized in that at least one oxygen barrier layer is selected from polyamide, poly(ethylene vinyl alcohol), poly(Vinilidene chloride), polyacrylonitrile, metals and mixtures thereof, and metallized layers thereof. contains material. 8. The packaged elastomer composite product according to any one of claims 1-5, characterized in that at least one oxygen barrier layer includes a metallized layer or a metal layer. 9. The packaged elastomer composite product according to any one of claims 1-5, characterized in that at least one wall does not contain a metallized layer or a metal layer. 10. The packaged elastomer composite product according to any one of claims 1-5, characterized in that at least one oxygen barrier layer contains a material selected from metals, metal alloys, ceramics, carbon-based nano-materials and melamine-based materials. 11. The packaged elastomer composite product according to any one of claims 1-10, characterized in that at least one wall is a monolayer wall with an oxygen barrier layer. 12. The packaged elastomer composite product according to any one of claims 1-10, characterized in that at least one wall contains two or more layers, at least one of the layers being an oxygen barrier layer. 13. The packaged elastomer composite product according to any one of claims 1-12, characterized in that at least one wall is flexible. 14. The packaged elastomer composite product according to any one of claims 1-12, characterized in that at least one wall is hard. 15. It is a packaged elastomer composite product according to any one of claims 1-14, characterized in that the volume of the inner part of the package is at least 10 L. 16. It is a packaged elastomer composite product according to any of the claims 1-14, characterized in that the volume of the inner part of the package is at least 50 L. 17. The packaged elastomer composite product according to any one of claims 1-16, characterized in that the composite product contains a deterioration inhibitor in the amount of at least 0.5 phr. 18. The packaged elastomer composite product of any one of claims 1 to 16, wherein the composite product contains an antifouling agent in an amount ranging from 0.5 phr to 10 phr. 19. The packaged elastomer composite product of any one of claims 1 to 16, wherein the composite product contains an antifouling agent in an amount ranging from 0.5 phr to 3 phr. 20. The packaged elastomer composite product according to any one of claims 1-16, characterized in that the composite product contains virtually no antifouling agents. 21. The packaged elastomer composite product of claim 20, characterized in that the composite10 product has a weight varying between 3% and 20% based on the total weight of the composite product. 22. The packaged elastomer composite product according to any one of claims 1-21, characterized in that the package also includes at least one oxygen scavenger. 23. The packaged elastomer composite product of claim 22, characterized in that at least one oxygen holder is located in an oxygen-permeable bag. 24. The packaged elastomer composite product of claim 23, characterized in that the plastic bag is adhered to an inner wall of the package. 25. The packaged elastomer composite product according to any one of claims 22-24, characterized in that at least one oxygen scavenger is selected from metal powders, ascorbic acids and their salts and catechol. 26. The packaged elastomer composite product according to any one of claims 1-25, characterized in that at least one filler contains carbonaceous materials, carbon black, silica, bio-based fillers, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphene. , graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, recovered carbon or combinations of these and their selection from coated and chemically processed materials. 27. The packaged elastomer composite product according to any one of claims 1-25, characterized in that at least one filler is selected from rice husk silica, lignin, nanocellulose and hydrothermal carbon. 28. The packaged elastomer composite product according to any one of claims 1-25, characterized in that at least one filler is selected from carbon black, silica and silicone treated carbon black. 29. The packaged elastomer composite product according to any one of claims 1-28, characterized in that 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. It is selected from -propylene rubber, isobutylene-based elastomers, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, Iloroelastomers, perIloroelastomers, silicone elastomers and their mixtures. 30. The packaged elastomer composite product according to any one of claims 1-28, characterized in that at least one elastomer is selected from diene-based elastomers. 31. The packaged elastomer composite product according to any one of claims 1-28, characterized in that at least one elastomer is selected from natural rubber, polyisoprene rubber, butadiene rubber and mixtures thereof. 32. The packaged elastomer composite product according to any of claims 1-28, characterized in that at least one elastomer contains at least 30% natural rubber and at least one filler contains at least 50% carbon black. 33. The packaged elastomer composite product according to any one of claims 1-32, characterized in that the composite product also contains curing agents. 34. It is a packaged elastomer composite product according to any of the claims 1-33, and its feature is that the composite product has a Payne ratio of at least 1.1, the Payne ratio is G'(0.3%)/G'(51.5%), G'(0.3%) is the dynamic storage modulus measured at 0.3% strain amplitude and G'(51.5%) is the dynamic storage modulus measured at 51.5% strain amplitude. 35. The packaged elastomer composite product according to any one of claims 1-34, characterized in that the composite product has a d90 macro-dispersion of at most 80 um, and d90 is the area-equivalent diameter (um) of the filler particles in the composite product. 36. The packaged elastomer composite product of any one of claims 1-35, wherein the composite product is a heat-treated composite product. 37. It is a packaged elastomer composite product according to any of the claims 1-36, and its feature is that the amount of oxygen in the package atmosphere is maximum 75 mmol/kg elastomer composite product. 38. The packaged elastomer composite product according to any one of claims 1-37, characterized in that the composite product is packaged for a period of at least 5 days. 39. The packaged elastomer composite product of any one of claims 1-37, characterized in that the composite product is packaged for a period of at least 14 days. 40. A method of storing an elastomer composite product comprising isolating the elastomer composite product in a container and storing the composite product in the insulated container for a period of at least 5 days, characterized in that the elastomer composite product is uncured and contains at least one elastomer and at least one Contains fillers; and the cabin includes at least one wall surrounding the composite product, at least one wall such that the cabin has an oxygen transmission rate of not more than 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. It contains an oxygen barrier layer. 41. The method in claim 40, characterized in that, before insulating closure, the method further includes cleaning the interior of the cabinet with at least one gas that does not react with the composite product and/or applying vacuum to the interior of the cabinet. 42. The method of claim 40 or 41, characterized in that the insulated enclosed cabin has an atmosphere containing at least 90% of at least one gas that does not react with the elastomer composite product. 43. It is the method in claim 40 or 41, and its feature is that the insulated, closed cabin is vacuumed. 44. The method of any one of claims 40-43, characterized in that the composite product is stored in the insulated sealed container for a period of at least 14 days. 45. The method of any one of claims 40-44, characterized in that before insulating closure, the method further comprises subjecting the composite product to heat treatment at a temperature of at least 40°C. 46. The method according to any one of claims 40-45, characterized in that during insulated closure, the probe temperature of the composite product is at least 40°C. 47. The method of any one of claims 40-46, characterized in that the composite product is prepared by combining at least one solid elastomer and a wet filler comprising a filler and a liquid; The liquid is present in an amount of at least 15% by weight, based on the total weight of the wet filler. 48. A method for preserving or improving at least one property of an elastomer composite product or a compound formed from the composite product, comprising storing the elastomer composite product in an insulated container for a period of at least 5 days, the characteristic being that the elastomer composite product is uncured and at least comprising an elastomer and at least one filler; and the cabin includes at least one wall surrounding the composite product, at least one wall such that the cabin has an oxygen transmission rate of not more than 100 cm3/(m2-day-atm) at 23°C and 0% relative humidity. It contains an oxygen barrier layer. 49. The method of claim 48, wherein the elastomer composite product is stored in the insulated sealed container for a period of at least 14 days. 50. The method of claim 48 or 49, characterized in that the stored elastomer composite product or a compound formed from the stored elastomer composite product has a Payne ratio at least 10% lower than the Payne ratio of the composite product before the insulated closure of the package, the Payne ratio G' (0.3%)/G'(51.5%), G'(0.3%) is the dynamic storage modulus measured at 0.3% strain amplitude and G'(51.5%) is the % It is the dynamic storage modulus measured at a strain amplitude of 51.5. 51. The method according to any one of claims 48-50, characterized in that the maximum tan value of the composite formed from the stored elastomer composite product is at least 10% lower than the maximum tan value of the composite product before the insulated closure of the package. 52. Request 1Err0r! It is a packaged elastomer composite product in any of the Reference source note f0und.-39, characterized in that the composite product is the product formed by adding at least one coupling agent while mixing at least one elastomer with at least one filler. 53. Prompt 40Err0r! It is the method in any of Reference source note f0und.-51, characterized in that the composite product is the product formed by adding at least one coupling agent while mixing at least one elastomer with at least one filler. 54. The method according to any one of claims 40-51, characterized in that the composite product also contains at least one binder. 55. The packaged elastomer composite product of claim 52 or the method of claim 53 or 54, characterized in that at least one coupling substance is - NRlRz, - N(R1)(R2)(R3)+A', - S-SO3Ml and The first functional group selected from the structures represented by formula (I) and (H), where A' is chloride, bromide, iodide, hydroxyl, nitrate or acetate, X = NH, 0 or S, Y = H, OR4, NR4R5, - SnR4 and n is an integer selected from 1-6 and thiocarbonyl, nitrile oxide, nitron, nitrile imine, - S-SO3M2, - Sx-R6, - SH, - C(R6)=C(R7) - C(0 )R8› - C(R6)=C(R7) - C02R8, - C(R6)=C(R7) - containing the second functional group selected from COzMZ and each of R1-Rs being independently H and Ci-Cg selected from alkyl; M1 and Mz are each independently selected from H, Na+, K+, Li+, N(R')4+, each R' is independently selected from H and Ci-Czo alkyl and X,In l-8 It is an integer chosen from . 56. The method of claim 55, characterized in that the coupling agent further comprises at least one spacer between the first and second functional group, at least one spacer being - (CH2)n-, - (CH2)yC(O) -, - C(R9). )=C(R1°) -, - C(O) -, - N(R9) - and - C6H4 -, R9 and Rlo are each independently selected from H and Cl-Cg alkyl, and y is It is an integer chosen from 1-10. 57. The packaged elastomer composite product of claim 52 or the method of claim 53 or 54, characterized in that at least one coupling substance is thiourea, cystamine and HzN- from compounds of formula (1), formula (2) and formula (3). Ar-N(H)-C(O)-C(R6)=C(R7)-C02M2 (i) H2N-(CH2)n-8803M2 (2) M103S-S-(CH2)n-S-SO3M2 (3) is to be selected. 58. The packaged elastomer composite product or method according to any one of claims 55-57, characterized in that M1 and Mz are each independently selected from H, Na+ and N(R')4+ and R6 and R7a are independently selected from H and It is selected from C1-C6 alkyl. 59. The packaged elastomer composite product or method of claim 57 or 58, characterized in that the binder is selected from compounds of formula (1) and R6 and R7 are each H. It is 2-butenoate.