Particulate carbon material prepared from renewable raw materials and process for its preparation

Abstract

The present invention relates to a granulated carbon material which can be produced from renewable raw materials, in particular lignin-containing biomass, having a 14 C content corresponding to the renewable raw material 14 C content, a 14 C content preferably greater than 0.20 Bq / g of carbon, particularly preferably greater than 0.23 Bq / g of carbon, and, respectively, less than 0.45 Bq / g of carbon; a carbon content of between 60 and 80 mass-%, calculated on dry matter without ash; a minimum of 5 m 2 / g and a maximum of 200 m 2 / g of STSA surface area of the primary particles; and an oil absorption number (OAN) of between 50 and 150 ml / 100g. The invention likewise relates to a process for its production and to its use.

Description

[0001] This application is a divisional application of patent application No. 201680068049.8 (International Application No. PCT / EP2016 / 078176), filed on November 18, 2016, entitled "Particulate carbon material that can be prepared from renewable raw materials and a method for preparing the same". Technical Field

[0002] This invention relates to a particulate carbon material, a method for preparing said carbon material, and the application of said material in polymer mixtures. Background Technology

[0003] Particulate carbon materials have a wide variety of applications. One application is as a filler for polymers such as elastomers, thermoplastics, or thermosetting plastics. Fillers are used in the manufacture of rubber products made of elastomers to influence the rubber-related properties of the cross-linked rubber products, which are measured, for example, as tensile strength, hardness, stiffness, or breaking strength. Furthermore, this modifies product properties, such as rolling resistance, wear, and wet grip in vehicle tires. Influencing rubber-related properties through fillers is also known as reinforcement.

[0004] Currently, the most widely used filler materials are carbon black and silica. Carbon black is mostly prepared by the pyrolysis of natural gas, petroleum particles, and / or coal-based oil, generating a huge amount of carbon dioxide during the preparation process, depending on the quality of the carbon black. Precipitated silica is prepared by water glass, which also generates a large amount of carbon dioxide during its preparation.

[0005] Amidst the depletion of fossil carbon resources (see petroleum and coal tar as raw materials for carbon black), the conservation of chemical agents (see sulfuric acid in silica precipitation), and primarily the avoidance of carbon dioxide emissions from fossil sources (see carbonate decomposition in water glass preparation; see combustion of oil or gas in the pre-combustion chamber of a carbon black reactor and partial combustion of carbon black raw materials during carbon black formation), there is a growing demand for the preparation of industrial products based on renewable raw materials. In renewable raw materials, all carbon originates from atmospheric carbon dioxide. Therefore, in the energy utilization of renewable raw materials, the carbon dioxide balance is as neutral as possible. In the material utilization of renewable raw materials, fossil carbon is not released during preparation and even—at least during the duration of utilization of the corresponding product—atmospheric carbon is bound to the carbon-containing material.

[0006] The following describes, for example, particulate carbon materials based on renewable raw materials that can be used as fillers, which, compared with classically prepared fillers such as carbon black and silica, exhibit surprisingly good properties when used as fillers in elastomers.

[0007] The meanings of the terms used in this invention are described below:

[0008] The filler material is a particulate solid added to an elastomer, thermoplastic, or thermosetting plastic. Depending on the characteristics of the filler material, for example, when added to an elastomer, the rubber-related properties of the cross-linked rubber mixture (e.g., through vulcanization) are affected to varying degrees by the filler material, which is typically added together with other additives before cross-linking.

[0009] A typical filler material is silica. Silicate basically refers to precipitated silica, which is primarily used in rubber products. Additionally, there is atomized silica gel.

[0010] Other typical filler materials are carbon black. Here, "carbon black" always refers to industrial carbon black, i.e., carbon black with defined properties and technically targeted preparation. Carbon black is primarily produced through incomplete combustion or pyrolysis. Here, carbon black does not refer to combustion byproducts as in the cases of diesel carbon black or chimney black.

[0011] The reinforcing effect of carbon black and / or silica is closely related to the primary particle size of the filler. The primary particle size is directly related to the specific surface area.

[0012] In this context, carbon black with low surface area is called unreactive carbon black, carbon black with medium surface area is called semi-reactive carbon black, and carbon black with high surface area is called activated carbon black, where "activation" refers to the degree of reinforcing effect of the corresponding carbon black in the rubber. See also ASTM D 1765 for details. Typically, unreactive carbon black has a surface area of ​​<30 μm. 2 With a BET surface area of ​​ / g, semi-activated carbon black has 30m² 2 / g to 70m 2 / g BET surface area and activated carbon black has 90m 2 / g to >150m 2 / g BET surface area. The importance of surface area as a guiding parameter is also evident in the fact that the first digit of ASTM carbon black describes the particle size or surface area. In the case of silica, the difference is not as pronounced. Silica with a significant reinforcing effect typically has >100m 2 / g BET surface area. In the following text, "filler material" refers to a product that at least achieves the properties of activated carbon black. In the following text, properties at least similar to those of activated carbon black are also referred to as reinforcing effects. A typical activated carbon black is N990.

[0013] The surface area of ​​a particle consists of its outer surface area and its inner surface area. The measurement variable is the specific surface area of ​​the granular material. Specific surface area can be measured as the outer surface area using the statistical thickness surface area (STSA) or, according to Brunauer, Emmett, and Teller (BET), as the total surface area consisting of the outer and inner surface areas using the nitrogen surface area. The difference between the inner and outer surface areas is primarily caused by the porosity of the material. In addition to the area encapsulating the particles, the inner surface area also includes the area present in the pores. Coarse-grained materials with a relatively small outer surface area (i.e., STSA surface area) can still have a high total surface area (i.e., BET surface area) if they are highly porous.

[0014] Therefore, to describe the fineness of a material beyond its specific surface area, strictly speaking, only the STSA surface area should be considered. Conversely, the difference between the BET surface area and the STSA surface area is a measure of the porosity of fine-grained materials, as this difference represents the surface area of ​​the pores. The larger the difference, the fewer pores the material has. In non-porous materials, BET also describes fineness well.

[0015] The determination of the BET and SRSA surface areas was performed according to ASTM standard D 6556-14. In this invention, however, sample preparation / venting for STSA and BET measurements is performed at 150°C.

[0016] Similarly, in "rubber technology" (Fritz) Franz Sommer, 3rd ed., Carl Hanser, Munich 2013, p. 289, describes the method and its importance using a classic example of carbon black. The most important method for determining specific surface area is the measurement of nitrogen adsorption according to the Brunauer, Emmett, and Teller (BET method). Here, a sample of carbon black is first heated in a vacuum to remove the adsorbed material on the surface. After cooling, the sample is loaded with nitrogen at the boiling temperature (77 K) and the volume of adsorption and the corresponding equilibrium vapor pressure are determined. At low pressure, a monolayer is formed first, and additional layers accumulate on the monolayer as the pressure increases. The specific surface area can be determined by evaluating the adsorption isotherm using a partial nitrogen pressure of 0.1 to 0.3 according to the BET method. Single-point measurements are sufficient for routine determinations.

[0017] Surface area determination using N2 adsorption yields a larger surface area for microporous carbon black because nitrogen molecules can also enter the pores. This effect can be avoided by using surfactants with larger pore sizes (CTAB method) or by determining N2 adsorption and further evaluation at higher partial pressures (0.2 to 0.5) (STSA method).

[0018] STSA method (Statistical Thickness Surface Area): The evaluation uses the same measurement data as in the BET method; however, the measurements are performed at higher partial pressures (0.2 to 0.5). The STSA method is based on the so-called t-plot evaluation method according to Boer, later modified by Magee. Here, it is based on the fact that adsorption occurs locally differently at different stacking heights, thus having a statistical thickness. The STSA surface area is also expressed in m... 2 / g indicates and is a measure of the “outer” surface area of ​​carbon black particles; however, the STSA surface area is primarily a measure of surface area used for rubber applications.

[0019] When comparing the properties of carbon black or silica in crosslinked rubber products, it is meaningful to compare fillers with similar specific surface areas, given the known correlation between specific surface area and properties. Here and below, similar surface area means that the BET or STSA values ​​of non-porous materials differ from each other by no more than approximately 10 μm². 2 / g to 20m 2 / g.

[0020] Carbon black and silica consist of primary particles. These primary particles do not exist in isolation, but rather grow into aggregates from geometric units visible in a graphical display, where they are bound together by strong chemical bonds. These aggregates can also coalesce into agglomerates, where multiple aggregates are linked together by weak forces. Agglomerates can be broken down by dispersion. The degree of aggregate formation has historically been described by DBP adsorption or, more recently, by oil absorption. See ASTM D2414 for details. Oil absorption values, abbreviated as OAN (oil absorption number), are also discussed. High DBP adsorption or oil absorption values ​​characterize materials with strongly branched aggregates. In carbon black, the so-called structure primarily has a direct impact on its reinforcing effect.

[0021] The properties of carbon black or silica in rubber applications are typically determined by measuring characteristic variables of the rubber. These characteristic variables describe the specific properties of rubber compounds in a cross-linked, such as vulcanized, state. For this purpose, in this literature, rubber articles should be understood as finished articles made of rubber after cross-linking or vulcanization. These finished rubber articles are also referred to in the current literature as rubber parts, molded bodies, articles made of elastomeric materials, or rubber products. The wide diversity of rubber parts across various applications necessitates a large number of different variables used to describe them. Depending on the application, a variable may be evaluated as a positive value, while elsewhere it may be evaluated as a negative value. Tensile strength (ASTM D 412, DIN 53504), breaking strength (DIN 53455), and tensile strength at 50%, 100%, 200%, and 300% strain (DIN 53504) (hereinafter referred to as modulus 50%, modulus 100%, modulus 200%, or modulus 300%), tensile strength, and tensile strength are primarily considered as characteristic variables of the rubber. In addition, hardness (ASTM D 2240), for example, can play a role. For these variables, high but not excessive values ​​are considered positive.

[0022] Another characteristic value for rubber is the loss coefficient tanδ, which is the quotient of the loss modulus E” and the storage modulus E’ of the elastomer material. The tanδ value differs in the high-temperature range, particularly at 60°C, and in the low-temperature range, particularly at 0°C. The tanδ at 0°C is used to evaluate the wet grip of the tire, while the tanδ at 60°C can infer the sliding friction of the tire. In this context, a smaller value is preferred for tanδ at 60°C, and a larger value is preferred for tanδ at 0°C. The value of tanδ is determined based on dynamic mechanical analysis (temperature scan). In the case described here, dynamic mechanical analysis (DMA) is performed on an Eplexor 150N dynamic thermomechanical spectrometer using a prism-shaped molded part with dimensions of 2 mm × 10 mm × 35 mm for temperature changes.

[0023] Untreated silicic acid is a filler material with polar functional groups that can interfere with crosslinking in sulfur-crosslinked systems. This interference can be based, for example, on the adsorption of vulcanizing agents onto the polar functional groups on the filler surface. Furthermore, the different surface energies of the polymer and the filler can, for example, hinder good dispersion of the filler in the polymer and, upon reheating of the mixture (e.g., during vulcanization), lead to undesirable reagglomeration of already dispersed filler particles (so-called filler flocculation). This is the basis for adding reagents to silicic acid. In the simplest case, the polar groups of silicic acid react with suitable basic compounds, thereby deactivating or masking these groups. The silicic acid itself is thus activated in its function as a reinforcing filler, that is, the surface chemistry of the silicic acid is matched to the surface chemistry of the polymer through this activation or masking. See Fritz for further details. Franz Sommer, 3rd edition, Carl Hanser Publishers, Munich 2013, pp. 301-302.

[0024] To improve the properties of rubber, silicic acid is often used in conjunction with coupling agents. Coupling agents are bifunctional compounds that bind to both silicic acid and rubber, thereby creating a bond between them. This is particularly important because silicic acid and rubber are chemically incompatible. A typical coupling agent used when silicic acid is used in rubber is bis(triethoxysilylpropyl)tetrasulfide.

[0025] In plastic applications, adhesion promoters are used, which also facilitate the bonding between the polymer and another component, which can be another polymer or a filler material. In the current literature, coupling agents should also be understood as adhesion promoters.

[0026] In the field of powder characterization, particle size or particle size distribution is frequently mentioned. This is primarily determined through laser diffraction or sieving analysis. Typically, it provides the percentage share of the total number (Q0 distribution) or volume (Q3 distribution) of expanded particles with a defined geometry to the total number of particles. This is usually expressed in μm. Particle size here includes the size of particles that exist separately under specific conditions. The particle size is related to the dispersion medium and dispersion quality. Particle size is not distinguished between particles that are, for example, the result of macroscopic baking by foreign substances, particles that are the result of microscopic agglomeration under insufficient dispersion consumption, or particles in the form of isolated aggregates or primary particles. The particle size describes the expansion of the outwardly bounded body, even if the body may consist of multiple connected particles. The mass distribution can be calculated from the volume distribution using the material density (apparent density).

[0027] The form of the filler material can be fibrous, plate-like, or spherical. Aspect ratio can be considered as a distinguishing criterion. For this purpose, the extent in different spatial directions can be determined, for example, by electron microscopy (TEM, REM). Aspect ratio is also frequently discussed, as the quotient of the maximum and minimum extent. This aspect ratio can be given in the form of x:y and as a calculated quotient. Thus, as a calculated quotient, a sphere has an aspect ratio of 1, an elliptical formation has an aspect ratio of approximately 1.5 to 2, and a fibrous-like formation has an aspect ratio greater than 10.

[0028] In the following text, conventional carbon black, made from fossil-derived raw materials, i.e., based on coal tar, natural gas, or crude oil, will be referred to as classic carbon black. Conversely, if carbon black is made from renewable raw materials, then we will discuss bio-based carbon black.

[0029] First, all raw materials from fossil sources are derived from crude oil, such as fractions, distillation residues, or crude oil components processed through cracking. All products arising from the distillation, coking, or liquefaction of lignite, coal, or anthracite are also fossil raw materials. Natural gas is also a fossil raw material. What all fossil carbon sources have in common is that... 14 The carbon content is lower than that of renewable raw materials. 14 The carbon content is reduced because the fossil carbon source no longer participates in ongoing isotopic exchange.

[0030] Conversely, renewable raw materials are products derived entirely from the direct use of plants or animals. If we consider the production process of carbon black, then this can primarily consist of vegetable oils or animal fats. More broadly, and thus for the purposes of this document, various types of biomass fall under the category of renewable raw materials.

[0031] Biomass is all organic matter that is available from or occurs as waste from the use of plants or animals; including reaction products and wastes prepared from or separated therefrom. Without limitation, wood, straw, sugar, starch, vegetable oil, leaves, bark, bagasse, empty fruit clusters, fermentation residues, green waste (Gruenschnitt), or organic municipal waste can be considered typical forms of biomass. Commonly, organic materials with shorter reaction times than peat are referred to as biomass. Waste from industrial uses of plants, in particular, also falls under the category of biomass. For example, the processing of large quantities of wood in the cellulose industry produces lignin-containing waste, such as soda ash. A common characteristic of all biomass is that its… 14 The carbon content is higher than that of fossil raw materials. 14 C content, because the biomass participates in continuous isotope exchange.

[0032] One type of biomass is lignin, which is produced in some wood processing processes. Lignin is a naturally occurring polymer that is primarily derived from the basic frameworks of isopropanol, coniferyl alcohol, and sinapyl alcohol. Depending on the wood processing process, hydrolyzed lignin or lignin sulfate is produced in large quantities as KRAFT lignin, which is typically soluble in alkali. Depending on the pH value in the corresponding processing, hydrogen atoms in the typical hydroxyl groups of lignin can be proportionally replaced by metal cations. Lignin sulfate is, more precisely, a chemical derivative of lignin because it has additional sulfate groups inserted during processing.

[0033] HTC is an abbreviation for hydrothermal carbonization. Here, hydrothermal carbonization refers to the treatment of substances in an aqueous phase under pressure-sealed conditions and at elevated temperatures. It is feasible to carry out the reaction in liquid water by increasing the pressure, where the temperature is well above 100°C, i.e., above the boiling point of water at atmospheric pressure.

[0034] According to existing technology, reinforcing fillers are primarily used to improve the rubber properties of rubber products. The two most commonly used fillers for rubber applications are carbon black and silica. Carbon black is obtained almost exclusively from fossil raw materials. Since the product of this invention is, for example, a particulate carbon material obtained from renewable raw materials that can be used as a filler, classic carbon black obtained from fossil raw materials is not considered prior art. Silicate is a filler obtained from inorganic silicon compounds. Therefore, silica is also not considered prior art.

[0035] The research activity focuses on developing alternative filler materials composed of renewable raw materials. A key part of this research effort targets the refining of renewable raw materials to replicate the properties of carbon black as well as possible. This specifically involves adjusting the carbon content to over 90%, but also including a portion of graphitic carbon. Therefore, materials produced in this way are also called bio-based carbon black. In most cases, a parallel objective is to provide filler materials composed of renewable raw materials that can at least partially replace classic carbon black. Furthermore, there are development efforts aimed at using renewable raw materials directly as filler materials after cleaning, fractionation, or pulverization.

[0036] As is known, for example, from WO 2010 / 043562 A1, carbon black can also be prepared from renewable raw materials. The disclosed carbon black, as a filler material, should primarily possess an improved modulus for rubber applications in the case of a particularly narrow aggregate size distribution. The carbon black characterized in WO 2010 / 043562 A1 falls within the range of classic carbon blacks N220 and N375 in terms of its basic properties. The carbon black described herein is prepared using a classic furnace process, in which natural gas is used in a pre-combustion chamber, resulting in the release of fossil carbon. The carbon black obtained in this manner has a maximum S content of 2.5%, a maximum volatile component content of 2.5% according to DIN 53552, and thus roughly a C content of over 95% carbon.

[0037] WO 2014 / 096544 A1 claims protection for a carbon product, said carbon product being composed of a material having a molecular weight greater than 500 μm. 2 Porous carbon particles with a surface area of ​​ / g and an average pore volume of less than 1ml / g are formed, said carbon particles being composed of primary particles, such as aggregates, having a particle size of less than 250nm. The carbon products are obtained from the hydrothermal carbonization of biomaterials having a carbon content greater than 40% by dry weight. Lignin, tannins and betulin, hydrolyzed lignin, and products from the manufacture of paper, board, biofuels, or brewing products are referred to as raw materials. Here, the carbon content of the products described in the examples is between 77.31% and 86.44%. The intense coalification of the materials illustrated in the examples indicates that other elements, primarily oxygen and hydrogen, must be depleted. This inevitably leads to the disadvantage of impoverished surface chemistry of the material, that is, fewer functional groups on the surface. Fewer surface groups adversely affect the possible bonding mechanisms for polymer formation.

[0038] It is also known that renewable raw materials such as lignin or lignin derivatives without or with coupling agents are used directly in rubber blends in order to influence the rubber properties in the crosslinked state.

[0039] Therefore, DE 10 2008 050 966A1 describes a rubber compound containing lignin derivatives, particularly lignin sulfonate derivatives, up to alkali or alkaline earth metal salts of lignin sulfonate. Furthermore, rubber compounds prepared using these lignin sulfonate derivatives can also contain carbon black or silica. This application also claims protection for a tire made from the aforementioned rubber compound. A disadvantage is that, as shown in the example disclosed in DE 10 2008 050 966 A1, lignin derivatives are always used except for 40 phr of carbon black or 80 phr of silica / 5 phr of carbon black. In this document, the term silica is used for silicic acid. Therefore, improvements are only achieved in combination with classic filler materials, resulting in improvements to the characteristic variables of the rubber.

[0040] The knowledge gained from using silicic acid is particularly relevant when using renewable raw materials in rubber blends with the aid of coupling agents.

[0041] Regarding silicic acid, it is generally known that in sulfur-crosslinked systems, fillers with polar functional groups, such as untreated silicic acid, interfere with crosslinking. It is also known that this interference can be mitigated by adding suitable reagents, such as amines or glycols, by blocking or masking the functional groups. See Fritz for further details. Franz Sommer, 3rd edition, Carl Hanser, Munich 2013, pp. 301-302.

[0042] In cases of silicic acid reinforcement, it is known that the effect of silicic acid can be significantly improved by coupling agents. Here, functionalized alkoxysilanes are used, which, on the one hand, can bind to silicic acid by forming Si-O-Si bonds when mixed with alkoxysilyl groups, and on the other hand, can bind to the rubber polymer later, with the assistance of added sulfur during vulcanization, thanks to other functionalities. Silicic acid and silicates are suitable as distinctive reinforcing fillers. Treating silicic acid with silanes significantly improves its mechanical and processability properties (see Fritz). Franz Sommer: Rubber Technology, 3rd Edition, Carl Hanser Publishers, Munich 2013, pp. 112-113, Chapter 2.5.4.3 Filler Materials.

[0043] Similarly, silanes are known as coupling agents in renewable raw materials used as filler materials in applications.

[0044] Therefore, EP 2 223 928 A1 describes a functionalized lignin, wherein groups contained in the lignin react with a functionalizing agent, and the agent can be an anhydride, ester, or silane. Furthermore, a rubber compound is disclosed comprising functionalized lignin as a filler material, the lignin possibly being mixed with classical carbon black or silica, and optionally containing a lignin for functionalization or a coupling agent for silica.

[0045] It is also known that fine-particle materials are produced by hydrothermal carbonization (HTC) (these materials can be used as filler materials).

[0046] For example, refer to WO 2014 / 122163 A1, which describes a method for preparing carbon-rich biomass materials, the resulting biomass materials, and their applications. The charge, i.e., the lignocellulose material, is treated at elevated temperatures, preferably up to 120°C to 320°C, under partially oxidizing conditions; that is, under substoichiometric conditions where oxygen is preferably present in the range of 0.15 mol / kg to 0.45 mol / kg of dry lignocellulose material, and the solid product is optionally separated from the reaction mixture after the reactor is opened. The charge has a moisture content between 10% and 70% and a size between 0.2 mm and 100 mm. The pressure used is between 1 bar and 100 bar absolute values. The reaction time is specified as 2 min to 500 min. It is preferred to use 0.1 kg to 1 kg of water or steam / kg of lignocellulose. The carbon concentration is increased by 8% to 25%. The resulting material has a maximum carbon content of 45% to 60%, excluding 5% to 8% hydrogen and 35% to 50% oxygen. It merely proposes that combustion, especially combustion in the grinding state to ash, be applied.

[0047] Furthermore, a method for obtaining carbonized lignin with a defined particle size distribution from a lignin-containing liquid is known, wherein the lignin-containing liquid undergoes hydrothermal carbonization, thereby converting the lignin into carbonized lignin, and the carbonized lignin is separated from the lignin-containing liquid. The lignin-containing liquid undergoes hydrothermal carbonization at a temperature ranging from approximately 150°C to approximately 280°C, and the particle size distribution of the carbonized lignin is determined by adjusting the H₂ content in the lignin-containing liquid. + The ion concentration is adjusted before and / or during hydrothermal carbonization. Therefore, it is known that the H+ of liquids containing lignin... + Adjusting the ion concentration can affect the particle size distribution of the obtained product, that is, the size of the agglomerates. Summary of the Invention

[0048] The object of this invention is to provide a particulate carbon material composed of renewable raw materials, for example, which can be used as a filler, and which, after crosslinking, exhibits properties similar to those of classic carbon black in terms of BET / STSA surface area, for example, when added to rubber compounds. The object of this invention is also to provide an efficient method regarding the use of energy and additives, by which the material according to the invention can be prepared.

[0049] The objective is achieved by particulate carbon materials having the characteristics of embodiments of the present invention and a method for preparing said carbon materials having the characteristics of embodiments of the present invention.

[0050] Accordingly, a particulate carbon material is provided that can be prepared from renewable raw materials, particularly lignin-containing biomass, and said carbon material provides the following characteristics:

[0051] - Corresponding to renewable raw materials 14 C content 14 The carbon content is preferably greater than 0.20 Bq / g, particularly greater than 0.23 Bq / g, and preferably less than 0.45 Bq / g.

[0052] - Carbon content between 60% and 80% by mass based on dry matter excluding ash;

[0053] -Minimum 5m 2 / g and a maximum of 200m 2 / g of STSA surface area; and

[0054] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g.

[0055] As described above, lignin-containing biomass is preferred, and in particular, lignin-containing biomass with a Klason lignin content exceeding 80% is used as a renewable raw material (the lignin content is determined using the Klason method, where polysaccharides are degraded through a two-stage acid hydrolysis and then weighed as a lignin residue remaining as Klason lignin). Lignin appears as a byproduct of the fractionation process of woody biomass. During the fractionation process, lignin is typically introduced into solution and then separated from the insoluble components of the woody biomass (e.g., the KRAFT process) or the woody biomass is depolymerized, leaving lignin primarily as a solid residue (e.g., by hydrolysis). Thus, depending on the fractionation process, lignin dissolves in a lignin-containing liquid, such as black alkali, or generally exists as a mechanically dehydrated solid. If lignin dissolves in a lignin-containing liquid, then lignin can be extracted from said liquid, typically using an acid or an acidic gas, and obtained as a mechanically dehydrated solid (e.g., see the LignoBoost process).

[0056] Corresponding to renewable raw materials 14 C content 14 The carbon content distinguishes current particulate carbon materials, which can be used as fillers in elastomers, thermoplastics, or thermosetting plastics, from classic carbon black obtained from fossil raw materials. Currently, particulate carbon materials have a carbon content greater than 0.20 Bq / g, particularly preferably greater than 0.23 Bq / g; however, a carbon content less than 0.45 Bq / g is preferred. 14 C content.

[0057] The biomass that increased in 1950, the time when humanity began large-scale nuclear weapons testing. 14 The carbon content is 0.226 Bq / g. The biomass increased to 0.42 Bq / g during the nuclear weapons testing period and has now returned to approximately its original level. The carbon content was measured at 0.238 Bq / g in 2009. To combine the carbon material according to the invention with artificially enriched... 14 Materials with different C contents are distinguished, therefore, in the carbon materials according to the present invention 14 The carbon content is at most 0.45 Bq / g.

[0058] A carbon content of greater than 60% and less than 80% by mass, preferably greater than 65% and less than 75% by mass, more preferably greater than 68% and less than 74% by mass, and even more preferably greater than 70% and less than 73% by mass (carbon content by elemental analysis according to DIN 51732; ash content at 815°C according to DIN 51719) based on dry matter excluding ash, distinguishes the particulate carbon material of the present invention, which can be used as a filler material, from renewable raw materials such as wood flour, which are typically used directly as fillers and have a lower carbon content. Furthermore, a carbon content of greater than 60% and less than 80% by mass, based on dry matter excluding ash, distinguishes the present particulate carbon material from products prepared from renewable raw materials, such as sugars, starches, and cellulose, prepared by fractionation, extraction, distillation, or crystallization, which typically have a lower carbon content of 40% to 50% by mass, based on dry matter excluding ash. Furthermore, the preferred embodiment of the particulate carbon material of the present invention differs from lignin separated from biomass by the KRAFT process, which typically has a carbon content of 65% by mass on dry matter without ash.

[0059] A carbon content of greater than 60% and less than 80% by mass on ash-free dry matter further distinguishes the particulate carbon material of the present invention from classical carbon black or bio-based carbon black variants prepared according to conventional carbon black manufacturing processes, which are prepared via conventional carbon black manufacturing methods, but also, for example, via pyrolysis, partial oxidation, carbonization, or similar methods. These variants typically have a higher carbon content of approximately 95% by mass and more on ash-free dry matter. In the case of highly oxidized carbon black having a volatile component content of 20% according to DIN 53552 and an additional 2.5% sulfur at 950°C, the carbon content is roughly greater than 88% on ash-free dry matter.

[0060] Compared to carbon black, the low carbon content of the product of the present invention has the advantage of partially retaining the surface functionalization produced by renewable raw materials and being usable in applications, for example, via coupling agents.

[0061] Minimum 5m 2 / g and a maximum of 200m 2 / g, preferably at 8m 2 / g and 100m 2The STSA surface area between / g further distinguishes the particulate carbon material of the present invention from non-porous lignin or non-porous particulate materials prepared by hydrothermal carbonization, which typically have a surface area of ​​less than 2m². 2 / g of BET surface area, of which the (not usually measured) STSA surface area is of course slightly smaller.

[0062] Furthermore, the particulate carbon material of the present invention is thus distinguished from particulate materials made of renewable raw materials that have a high BET specific surface area due to their strong porosity, such as hydrolyzed carbon, carbon obtained by partial oxidation, carbon obtained by hydrothermal carbonization, and activated carbon, by the following: the present particulate carbon materials are largely non-porous and very fine-grained, as determined by STSA surface area detection.

[0063] Among the current variants of particulate carbon materials, STSA has a surface area of ​​10 m². 2 / g and 80m 2 Between / g, preferably between 12m 2 / g and 70m 2 Between / g, more preferably between 15m 2 / g and 70m 2 Between / g, especially preferably between 20m 2 / g and 70m 2 Values ​​between / g.

[0064] The BET surface area of ​​the current particulate carbon material advantageously deviates from the STSA surface area by a maximum of 20%, preferably a maximum of 15%, and more preferably a maximum of 10%. The pore volume of the particulate carbon material is advantageously <0.1 cm³. 3 / g, more preferably <0.01cm 3 / g, especially preferably <0.005cm 3 / g. Therefore, current granular carbon materials differ from fine-particle porous materials, such as bio-derived ground powdered activated carbon, which typically has a particle size greater than 500 μm. 2 In addition to a BET surface area of ​​ / g, it can also have a maximum of 10m² 2 / g STSA surface area.

[0065] The advantage of the high surface area of ​​STSA compared to lignin and HTC carbon is the high fineness of the product, which enables a high degree of interaction between the current product and, for example, polymers. The advantage of the current product being virtually non-porous is that, for example, additives and crosslinking chemicals do not lose their effectiveness by entering the pores, compared to carbon materials utilizing porosity.

[0066] However, the average size of the primary particles of the particulate carbon material is advantageously limited to a value greater than 8 nm, preferably greater than 10 nm, and more preferably greater than 15 nm.

[0067] The primary particles of the particulate carbon material advantageously have a non-uniform size distribution. Therefore, smaller particle fractions have a size greater than 8 nm, preferably greater than 10 nm, more preferably greater than 15 nm up to 250 nm. Larger particle fractions have a size greater than 250 nm.

[0068] Primary particles advantageously grow into aggregates, whereby the size of the primary particles differs from the size of the aggregates. Thus, the size of the primary particles is preferably less than 250 nm. In this preferred case, the primary particles are smaller than the aggregates, preferably on average at most half their size, more preferably on average at most a quarter their size. To clarify, it should be added that in this preferred embodiment, primary particles can also exist individually and then theoretically be equivalent to aggregates. However, in this preferred embodiment, this is only a rare case, preferably less than 25%, more preferably less than 20%, and especially preferably less than % of the total. This is particularly applicable to primary particles having a size exceeding 250 nm.

[0069] Because the size of primary particles and aggregates is not available or only insufficiently available by means of particle size analysis, such as laser diffraction or sieving analysis, it is possible to determine the size, for example, by using photographs taken with a scanning electron microscope.

[0070] Oil absorption value (OAN) between 50 ml / 100 g and 150 ml / 100 g distinguishes current particulate carbon materials from carbon materials pulverized, for example, by grinding or steam explosion, which have a smaller OAN value due to the lack of aggregates or due to aggregates destroyed by the grinding process.

[0071] In another variant of the current particulate carbon material, the OAN value is between 65 ml / 100g and 150 ml / 100g, more preferably between 70 ml / 100g and 130 ml / 100g, even more preferably between 75 ml / 100g and 130 ml / 100g, and particularly preferably between 80 ml / 100g and 120 ml / 100g. The OAN adsorption capacity is determined according to ASTM standard D 2414-00.

[0072] The advantage of a high oil absorption value compared to carbon products with a lower oil absorption value is the presence of aggregates, which advantageously influence the interaction between the current particulate carbon material and, for example, polymers.

[0073] In one variant, the current particulate carbon material has a moisture content of less than 5% by mass, preferably less than 3% by mass, and more preferably less than 2% by mass. The current low moisture content or dry state of the carbon material enables its addition, for example, to polymers as a filler, because it avoids the formation of vapor bubbles at high temperatures. Furthermore, the increased moisture content of the carbon material is interfering with the application of coupling agents.

[0074] In another embodiment, the 15% suspension of the particulate carbon material in distilled water has a conductivity of less than 5 mS / cm, preferably less than 3 mS / cm, and particularly preferably less than 2 mS / cm. The conductivity (determined as the conductivity of the measuring probe of the PCE-PHD1 instrument at 20°C to 25°C) is currently used, particularly from Na... + Ca 2+ SO4 2- CO3 2- S 2- HS - The ion content or concentration of ions is a measure of the ion content. The advantage of low conductivity is a small proportion of water-soluble ions, which can also be separated from the current product, for example, when used in polymers.

[0075] One embodiment of the particulate carbon material also has a pH value >6, preferably >7, more preferably >8 in a 15% suspension in distilled water. The pH value of the 15% suspension of the particulate carbon material in distilled water is preferably less than 10, more preferably less than 9. The neutral or slightly alkaline pH of the current product is advantageous, for example, its good compatibility with other components of the polymer mixture.

[0076] Another advantage is that the current particulate carbon materials have a D / G signal ratio in Raman spectra between 0.20 and 0.90, preferably between 0.40 and 0.75, and more preferably between 0.45 and 0.70, as a measure of the proportion of graphitic carbon.

[0077] The D / G area ratio of the D band to the G band in Raman spectroscopy can be considered as a measure of the proportion of graphitic carbon in the material. The D band (disorder band) is located above 1300 cm⁻¹ to about 1360 cm⁻¹, and the G band (graphite band) is located between about 1580 cm⁻¹ and 1590 cm⁻¹. To calculate the D / G area ratio, the Raman spectrum is integrated with respect to the D band and through the G band, and then scaled proportionally.

[0078] The advantage of the given D / G ratio is that the material can be used like classic carbon black in some applications (depending on its proportion of graphitic carbon), and also has other functionalities (depending on its proportion of amorphous carbon and the elements bonded to it).

[0079] In another embodiment, the current particulate carbon material has low solubility in alkaline solutions.

[0080] Therefore, the current particulate carbon materials advantageously possess high alkali resistance. High alkali resistance is currently understood to mean less than 40%, preferably less than 30%, particularly preferably less than 15%, and especially less than 10% of the particulate carbon material of the present invention dissolves. To determine alkali resistance, it is preferable to proceed as follows:

[0081] - Weigh solid, dry, granular carbon material, said carbon material first weighed with five times its weight.

[0082] Rinse twice with distilled water of good quality;

[0083] -Suspended in distilled water, resulting in a dry matter content of 5%.

[0084] - The pH of the distilled water was raised to approximately 9 by adding a caustic soda solution.

[0085] - Increase the temperature of the pH-adjusted suspension, composed of current carbon materials and distilled water, to approximately 80°C.

[0086] - Stir for more than 2 hours under the above conditions.

[0087] - After the suspension has cooled to room temperature, repeat the process that begins with adjusting the pH value until the pH value again corresponds to approximately 9 after the suspension has cooled to room temperature.

[0088] - The suspension was centrifuged at 9000 rpm for 15 minutes.

[0089] - Separate the liquid phase and dry the remaining solid residue, and

[0090] -Weigh and dry the residue.

[0091] The alkali resistance, expressed as a percentage, is determined by dividing the dry weight of the weighed residue by the dry weight of the weighed particulate carbon material and multiplying by 100. The solubility of the particulate carbon material, expressed as a percentage, is determined by subtracting the alkali resistance from 100.

[0092] In this respect, the difference between the particulate carbon material according to the invention and lignin is that its alkali resistance is significantly improved. This has the advantage that current particulate carbon materials, for example, when used as fillers in rubber or plastic products, are not easily washed away when in contact with water from the rubber or plastic products.

[0093] The particulate carbon material according to the invention advantageously possesses surface chemical properties similar to those of silicic acid. Similar surface chemical properties to silicic acid refer to the high OH- group density of the current carbon material. The oxygen content of the current ash-free particulate carbon material is particularly between 20% and 30% by mass, preferably between 20% and 25% by mass.

[0094] In this respect, the particulate carbon material of the present invention is distinguished from carbon black obtained from renewable raw materials, for example, through intense carbonization (pyrolysis, oxidation, hydrothermal carbonization, etc.), by the fact that the functional groups of the renewable raw materials used to prepare the present particulate carbon material are not separated as much as possible by heat treatment, but can also be provided for binding to polymers or coupling agents.

[0095] On a dry matter basis, the ash content of the particulate carbon material is preferably at least 1% by mass but less than 8% by mass, more preferably at least 2% by mass and less than 6% by mass, even more preferably at least 3% by mass and less than 6% by mass, and especially at least 4% by mass and less than 6% by mass (ash content at 815°C according to DIN 51719).

[0096] In a further variation of the current particulate carbon material, the D90 of the Q3 distribution of particle size (as a measure of the size of particles existing separately under specific conditions) is less than 30 μm, preferably less than 20 μm, more preferably less than 15 μm, even more preferably less than 10 μm, and especially less than 5 μm. In a further variation of the current particulate carbon material, the D99 of the Q3 distribution of particle size is less than 30 μm, preferably less than 20 μm, more preferably less than 15 μm, even more preferably less than 10 μm, and especially less than 5 μm. In a further variation of the current particulate carbon material, the D99 of the Q3 distribution of particle size is greater than 1 μm, preferably greater than 2 μm.

[0097] The advantage of the maximum Q3 distribution of particle size given above is that the particulate carbon material of the present invention does not produce lattice defects when used in polymers, for example, due to the maximum size of the separately existing particles. These lattice defects, for example, cause premature breakage or fracture of the polymer or cause surface defects during extrusion.

[0098] Here, assuming 1500 kg / m 3 Under the condition of material density (apparent density), the average sphere diameter determined by means of STSA surface area is advantageously the highest one-third, more preferably the highest one-quarter, and especially the highest one-sixth of the average diameter (D50) of the separately existing particles measured by the Q3 distribution of particle size. Here, the average sphere diameter is calculated by means of the following formula:

[0099] 1. STSA surface area = Sphere surface area ÷ (Sphere volume × Material density)

[0100] 2. Surface area of ​​a sphere = PI × average diameter of the sphere^2

[0101] 3. Sphere volume = 1 / 6 × PI × average sphere diameter^3

[0102] By substituting 2. and 3. into 1., the following relationship is obtained:

[0103] Average sphere diameter = 6 ÷ (STSA surface area × material density)

[0104] The particle size distribution of the particulate carbon material was measured using laser diffraction in a 10% suspension containing distilled water. Before and / or during the particle size distribution measurement, the sample to be measured was ultrasonically dispersed until a stable particle size distribution was obtained through multiple measurements.

[0105] The STSA surface area of ​​current particulate carbon materials is preferably as independent as possible of its particle size Q3 distribution and characterizes the fineness of the primary particles.

[0106] In a preferred embodiment, the current particulate carbon material has

[0107] - Corresponding to renewable raw materials 14 C content 14 C content, the 14 The carbon content is preferably greater than 0.20 Bq / g, especially greater than 0.23 Bq / g, however, it is preferably less than 0.45 Bq / g.

[0108] - Carbon content between 60% and 80% by mass based on dry matter excluding ash;

[0109] -Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area;

[0110] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g; and

[0111] - D90 with a Q3 distribution of particle size less than 20 μm, preferably less than 15 μm.

[0112] Current particulate carbon materials advantageously possess a shape that corresponds as closely as possible to the shape of classic carbon black. The similarity between current particulate carbon materials and classic carbon black shapes is given, for example, by the following means: [The text abruptly ends here, likely due to an incomplete sentence or missing information.]

[0113] - Composed of primary particles with low porosity.

[0114] - Multiple of them grow into aggregates and

[0115] -The aggregates are at least partially agglomerated.

[0116] In this respect, current particulate carbon materials, which can also be used as fillers, can be distinguished from fillers obtained according to prior art, such as by grinding renewable raw materials, in the following way: the filler has a distinct structure similar to that of classic carbon black. The shape can be determined, for example, by REM photographs.

[0117] The particulate carbon material that can be used as a filler material preferably has a non-fibrous morphology, which means that the aspect ratio is less than 10, preferably less than 5.

[0118] In another preferred embodiment, the current particulate carbon material has

[0119] - Corresponding to renewable raw materials 14 C content 14 C content, the 14 The carbon content is preferably greater than 0.20 Bq / g, especially greater than 0.23 Bq / g, however, it is preferably less than 0.45 Bq / g.

[0120] - Carbon content, calculated as greater than 60% and less than 80% by mass of dry matter excluding ash;

[0121] -Minimum 5m 2 / g and a maximum of 200m 2 / g of STSA;

[0122] Oil absorption value (OAN) ranging from -50ml / 100g to 150ml / 100g;

[0123] - Surface chemical properties similar to those of silicic acid; and

[0124] - The shape should correspond as closely as possible to the classic shape of charcoal black.

[0125] By combining the advantageous properties of classic carbon black in terms of its shape with the properties of silica in terms of its surface chemistry, this preferred embodiment of the current particulate carbon material has a similar potential for interaction between filler and polymer as classic carbon black, and achieves this potential by additionally supplementing it via a mechanism similar to that in the case of silica, for example, through coupling agents.

[0126] Particulate carbon materials can be used, for example, as fillers or reinforcing fillers. The particulate carbon materials according to the invention can be used, for example, in rubber and rubber blends or plastics.

[0127] Another subject of the invention is a polymer mixture characterized in that it comprises at least one polymer and at least one particulate carbon material according to the invention. The polymer can be a thermoplastic, thermosetting, or elastomer.

[0128] A list of polymers is given, for example, on page 10, line 20 to page 12, line 36 of WO 2010 / 043562 A1, into which particulate carbon materials according to the invention can be incorporated. Preferred polymers are selected from the list of plastics or rubbers comprising: polyester, polyethylene, polypropylene, polyester carbonate, polyamide, polyimide, polyesteramide, polyetherimide, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polymethacrylate, polystyrene, styrene-maleic anhydride, polycaprolactone, polybutylene terephthalate, polyepoxides; cellulose products such as cellulose acetate or cellulose nitrate, vulcanized fibers, polylactic acid, polyhydroxyalkanoates, chitin, casein, gelatin; formaldehyde resins such as melamine-formaldehyde resin, urea-formaldehyde resin, melamine-phenol resin, phenol-melamine resin; silicone polymers, natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, isobutylene-isoprene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer, chloroprene, fluororubber or acrylic rubber, and mixtures thereof.

[0129] Another subject of the invention is a rubber compound, characterized in that the rubber compound comprises at least one rubber and at least one particulate carbon material according to the invention.

[0130] The granular carbon material can be used in an amount of 10% to 150% by mass, preferably 20% to 120% by mass, more preferably 40% to 100% by mass, and especially preferably 50% to 80% by mass, based on the mass of the rubber used.

[0131] The rubber compound preferably contains at least the particulate carbon material according to the invention and further contains naturally occurring mineral fillers, siliceous fillers, calcareous or lime-containing fillers.

[0132] The rubber compound preferably comprises particulate carbon material and a coupling agent according to the present invention, preferably an organosilane. The organosilane can be, for example, bis(trialkoxysilyl) oligomers or polysulfides, such as bis(triethoxysilylpropyl) disulfide or bis(triethoxysilylpropyl) tetrasulfide, meropentasilanes, aminosilanes, silanes having unsaturated hydrocarbon groups, such as vinylsilanes. Finally, silanes having large saturated hydrocarbon groups, such as dodecyltriethoxysilane, can also act as coupling agents; however, it is not covalent bonds but more precisely van der Waals bonds used to couple to the polymer to a certain extent.

[0133] The organosilane is preferably used in an amount of 2% to 16% by mass, more preferably 4% to 14% by mass, and especially preferably 6% to 12% by mass, based on the mass of the particulate carbon material used.

[0134] When organosilanes are used in conjunction with a form of particulate carbon material according to the invention, which has an STSA surface area similar to copper-inactive carbon black, the selected rubber-related characteristic values ​​are preferably achieved in the crosslinked state of the rubber mixture, and these characteristic values ​​are similar to those achieved when semi-active carbon black or silica is used in conjunction with organosilanes.

[0135] When organosilanes are used in conjunction with the particulate carbon material according to the invention, it is preferable that the crosslinking state of the rubber mixture not only reaches but also exceeds the selected rubber characteristic value, which is achieved when using carbon black having an STSA surface area similar to that of the particulate carbon material.

[0136] In another preferred variant, the rubber compound comprises particulate carbon material according to the invention and a masking agent, preferably an organosilane, amine, or glycol. In this context, for example, triethanolamine, hexamethylenetetramine, di-o-toluidine, or diphenylguanidine can be used as an amine. Ethylene glycol, tetraethylene glycol, or polyethylene glycol can be used as a glycol. The organosilane can be a triethoxysilane-alkylsilane, such as triethoxymethylsilane, triethoxyethylsilane, or triethoxypropylsilane. The agent cannot be inserted into the crosslinking via a sulfur bridge. However, under functional group-depleting conditions, the agent reacts with the surface of the carbon material according to the invention, causing the agent to slightly impair sulfur crosslinking. Therefore, triethoxyalkylsilanes do not act as coupling agents. Besides avoiding interference with sulfur crosslinking, such silanes naturally act as compatibilizers, matching the surface energy of the filler particles to the surface energy of the polymer matrix, thus preventing significant improvements in dispersibility.

[0137] Up to 100% of the carbon black in the rubber compound can preferably be replaced by the current particulate carbon material, and the characteristic values ​​of the selected rubber in the crosslinked state still achieve similar properties to those of carbon black.

[0138] Furthermore, up to 100% of the silica in the rubber compound can preferably be replaced by the current particulate carbon material, and still achieve similar properties to silica in terms of characteristic values ​​of the selected rubber in the crosslinked state, wherein organosilanes are preferred.

[0139] Preferred rubber-related characteristic values ​​are modulus 50% and modulus 200% as determined in tensile tests. Higher values ​​are preferred for modulus 50% and modulus 200%.

[0140] Another preferred rubber-related characteristic value is the loss coefficient tanδ (the quotient of loss modulus E” and storage modulus E’) determined in dynamic mechanical analysis (temperature scan) at temperatures between 40°C, preferably 50°C, more preferably 60°C and 100°C. This characteristic value is a common estimate of sliding friction in the tire industry. Within the given temperature range, smaller values ​​for tanδ are preferred, more preferably, tanδ is reduced by at least 10% relative to the carbon black reference, and even more preferably, tanδ is reduced by at least 15% relative to the carbon black reference. An additional preferred rubber-related characteristic value is the loss coefficient tanδ determined in dynamic mechanical analysis (temperature scan) at 0°C. This characteristic value is a common estimate of wet grip in the tire industry, wherein higher values ​​for tanδ at 0°C are preferred, and more preferably, tanδ is increased by at least 10% relative to the carbon black parameter.

[0141] In a preferred embodiment, in addition to the particulate carbon material, the rubber mixture also contains carbon black, preferably semi-active or active carbon black.

[0142] The rubber compound preferably contains at least particulate carbon material, and at least one carbon black preferably contains semi-active or active carbon black and naturally occurring mineral fillers, siliceous fillers, calcareous or lime-containing fillers.

[0143] The rubber compound preferably contains at least particulate carbon material, at least one carbon black preferably comprising semi-active or active carbon black and naturally occurring mineral filler, siliceous filler, calcareous or lime-containing filler and at least one organosilane.

[0144] The advantage of using granular carbon materials together with carbon black is that it can improve the specific rubber-related characteristics of vulcanized rubber compounds.

[0145] In another embodiment, in addition to the particulate carbon material according to the invention, the rubber mixture preferably also contains silicic acid, preferably precipitated silicic acid and pyrolytic silicic acid, and may also contain naturally occurring mineral fillers, siliceous fillers, calcareous or lime-containing fillers and organosilanes.

[0146] In addition to natural rubber (NR), synthetic rubbers are also suitable for preparing rubber mixtures according to the invention. Preferred synthetic rubbers are described, for example, in W. Hofmann, Rubber Technology, Genter Publishers, Stuttgart 1980, or in WO 2010 / 043562, page 15, line 4 to page 15, line 24. More preferred synthetic rubbers are also given in the following list: styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene, isobutylene-isoprene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer (NBR), chloroprene, fluororubber, or acrylic rubbers, and mixtures thereof.

[0147] The rubber mixtures according to the invention can contain other rubber additives, such as reaction accelerators, anti-aging agents, heat stabilizers, light protectants, anti-ozone agents, processing aids, plasticizers, tackifiers, foaming agents, dyes, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as diphenylguanidine, triethanolamine, polyethylene glycol, alkoxy-terminated polyethylene glycol, or hexanetriol, which are known to the rubber industry.

[0148] Sulfur, organic sulfur donors, or free radical precipitates can be used as crosslinking agents. The rubber compounds according to the invention can also contain vulcanization accelerators.

[0149] The mixing of rubber with particulate carbon materials, possibly carbon black, possibly silica, possibly rubber additives, and possibly organosilanes can be performed in conventional mixing equipment, such as roller crushers, closed mixers, and mixing extruders. Such rubber mixtures are typically prepared in closed mixers, where rubber, particulate carbon materials, possibly carbon black, possibly silica, possibly rubber additives, and possibly organosilanes are first mixed at 100°C to 170°C in one or more sequential thermomechanical mixing stages. Here, the order and timing of addition of individual components can have a decisive influence on the properties of the resulting mixture. The rubber mixture obtained in this manner is then typically crosslinked in a closed mixer or on a roller crusher at 40°C to 120°C using crosslinking chemicals and processed into a so-called coarse mixture for subsequent process steps, such as molding and vulcanization.

[0150] The vulcanization of the rubber compound according to the invention can be carried out at a temperature of 80°C to 200°C, preferably 130°C to 180°C, and possibly at a pressure of 10 bar to 200 bar.

[0151] The rubber compound according to the invention is suitable for manufacturing rubber articles, i.e., articles made of cross-linked or vulcanized elastomers, so-called molded bodies, for example for manufacturing pneumatic tires, tire treads, tire sidewalls, cable sheaths, hoses, drive belts, conveyor belts, roller covers, tires, shoe soles, shock absorbers, seals, profiles and damping elements.

[0152] Another subject of the invention is a rubber compound characterized in that it comprises at least one plastic and at least one particulate carbon according to the invention. In this context, carbon represents a thermoplastic or thermosetting plastic.

[0153] The granular carbon material can be used in an amount of 10% to 150% by mass, preferably 20% to 120% by mass, and more preferably 30% to 100% by mass, based on the mass of the plastic used.

[0154] The rubber compound preferably contains particulate carbon material and additives or coupling agents according to the invention.

[0155] Adhesion enhancers are preferably based on maleic anhydride or other organic acids, preferably unsaturated carboxylic acids. For example, silanes with particularly large hydrocarbon residues are preferred, such as triethoxydodecylsilane, which can be used as adhesion enhancers.

[0156] The adhesive is preferably used in an amount of 2% to 16% by mass based on the mass of the plastic used, more preferably 4% to 14% by mass, and especially preferably 6% to 12% by mass.

[0157] The plastic can be, for example, polyethylene (PE), polypropylene (PP), polyvinyl acetate (PVA), or thermoplastic elastomer (TPE). The plastic mixtures according to the invention are preferably used in the manufacture of cables, pipes, fibers, films, especially agricultural films, engineering plastics, and injection-molded articles.

[0158] The current particulate carbon material is prepared by the method according to the invention, which in particular achieves the adjustment of the STSA surface area and OAN value to the above-mentioned range.

[0159] According to the present invention, a multi-stage, particularly four-stage, method for hydrothermal treatment, particularly carbonization, of renewable raw materials, especially renewable raw materials having a share of greater than 80% crazin lignin is provided, said method being provided by means of:

[0160] -In the first step, a liquid containing renewable raw materials is provided.

[0161] - The liquid undergoes hydrothermal treatment in the second step at a temperature between 150°C and 250°C.

[0162] - In the third step, the solids present after hydrothermal treatment are separated from the liquid as much as possible, and

[0163] - In the fourth step, residual moisture in the solid is removed as much as possible through drying, thereby obtaining granular carbon material.

[0164] The STSA surface area and OAN value of the particulate carbon material obtained in the fourth step are determined by...

[0165] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0166] - pH value of liquids containing renewable raw materials,

[0167] - The concentration of inorganic ions in a liquid containing renewable raw materials.

[0168] - The temperature of hydrothermal treatment, and

[0169] Residence time in hydrothermal treatment

[0170] Controlled by mutual coordination, thereby adjusting the minimum 5m 2 / g and a maximum of 200m 2 STSA surface area / g and OAN value of minimum 50ml / 100g and maximum 150ml / 100g.

[0171] It is preferable to consider the conductivity of the liquid containing renewable raw materials as a substitute for the inorganic ion concentration of the liquid containing renewable raw materials.

[0172] By coordinating the proportions of pH, conductivity, and organic dry matter, as well as the temperature and residence time during hydrothermal treatment, conditions are created during the hydrothermal treatment process to obtain the particulate carbon material of the present invention. In particular, the pH and conductivity change during hydrothermal treatment and are formed during the process to produce the current particulate carbon material.

[0173] The STSA surface area and OAN value of the particulate carbon material obtained in the fourth step are preferably obtained through...

[0174] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0175] - pH value of liquids containing renewable raw materials,

[0176] - The concentration of inorganic ions in a liquid containing renewable raw materials.

[0177] - The temperature of hydrothermal treatment, and

[0178] - The residence time in hydrothermal treatment is controlled by mutual coordination, and the desired STSA surface area is adjusted in the following way: that is, under the condition of desired increase of STSA surface area.

[0179] - Reduce the concentration of the organic dry weight of renewable raw materials in liquids containing renewable raw materials and / or

[0180] - Increase the pH of liquids containing renewable raw materials, and / or

[0181] - Reduce the concentration of inorganic ions in liquids containing renewable raw materials.

[0182] The desired STSA surface area is also preferably adjusted by increasing the hydrothermal treatment temperature and / or extending the residence time in the hydrothermal treatment to increase the desired STSA surface area.

[0183] Preferably, if the yield of dried granular carbon material is very small, preferably less than 10%, more preferably less than 20%, even more preferably less than 30%, and especially preferably less than 40%, based on the dry weight of the renewable raw materials, the temperature of the hydrothermal treatment and / or the residence time in the hydrothermal treatment can be increased to increase the surface area of ​​the STSA as desired.

[0184] The STSA surface area and OAN value of the particulate carbon material obtained in the fourth step are preferably obtained through...

[0185] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0186] - pH value of liquids containing renewable raw materials,

[0187] - The concentration of inorganic ions in a liquid containing renewable raw materials.

[0188] - The temperature of hydrothermal treatment, and

[0189] - The residence time in hydrothermal treatment is controlled by mutual coordination, and the desired STSA surface area is adjusted by: i.e., under the condition of desired reduction of STSA surface area.

[0190] - Reduce the concentration of the organic dry weight of renewable raw materials in liquids containing renewable raw materials and / or

[0191] - Lower the pH of liquids containing renewable raw materials and / or

[0192] - Reduce the concentration of inorganic ions in liquids containing renewable raw materials.

[0193] The desired STSA surface area is more preferably adjusted by reducing the hydrothermal treatment temperature and / or shortening the residence time in the hydrothermal treatment while desiring to reduce the STSA surface area.

[0194] Temperature and residence time refer not only to the maximum temperature maintained above a specific residence time, but also to the temperature-time profile experienced in the second step. However, if a temperature-time profile is not mentioned below, then temperature refers to the maximum temperature maintained above a specific residence time. In the following text, temperature and residence time are collectively referred to as process conditions.

[0195] The method of the present invention offers the following advantages over the prior art: the formation of the desired fine particles is not completed in the first step, but rather during the hydrothermal treatment in the second step, conditions are created that induce the formation of particulate carbon material with corresponding STSA surface area and OAN value. This method allows for the simultaneous induction of particle formation and reaction, the resulting particulate carbon material differing from the renewable raw materials used, for example, in terms of its carbon content or alkali resistance.

[0196] The method of the present invention has a particular advantage here: by...

[0197] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0198] - pH value of liquids containing renewable raw materials,

[0199] - The concentration of inorganic ions in a liquid containing renewable raw materials.

[0200] - The temperature of hydrothermal treatment, and

[0201] Residence time in hydrothermal treatment

[0202] In the second step, through optimized adjustments and coordination, the polymerization of renewable raw materials is largely suppressed or limited to obtain particulate carbon materials with corresponding STSA surface areas and OAN values. This directly affects the size of primary particles, as detected by STSA surface area, in addition to particle size distribution—the size distribution of agglomerates or particles that exist separately under specific conditions. Furthermore, the establishment of porosity in the material is suppressed, which is evident through the small difference between the STSA surface area and the BET surface area of ​​the particulate carbon material.

[0203] Preferably, in order to

[0204] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0205] - pH value of liquids containing renewable raw materials,

[0206] - The concentration of inorganic ions in a liquid containing renewable raw materials.

[0207] - The temperature of hydrothermal treatment, and

[0208] Residence time in hydrothermal treatment

[0209] To adjust and coordinate, consider one or more of the following measurement variables:

[0210] -The specific gravity of the liquid containing renewable raw materials after the second step;

[0211] - The electrical conductivity of the liquid containing renewable raw materials after the second step;

[0212] -The pH value of the liquid containing renewable raw materials after the second step;

[0213] - The pH difference between the liquid containing renewable raw materials before and after the second step;

[0214] - The difference in electrical conductivity of the liquid containing renewable raw materials before and after the second step;

[0215] The STSA surface area and OAN value of the particulate carbon material obtained in the fourth step are advantageously obtained through...

[0216] - The concentration of the organic dry weight of the renewable raw materials in the liquid containing the renewable raw materials is preferably adjusted to a value between 5% by mass and 40% by mass, more preferably between 10% by mass and 20% by mass.

[0217] - The pH value of the liquid containing renewable raw materials is preferably adjusted to ≥7, more preferably ≥8, particularly preferably ≥8.5, and more preferably ≤11 at 20°C to 25°C.

[0218] - The concentration of inorganic ions in the liquid containing renewable raw materials is preferably adjusted to be between 10 mS / cm and 200 mS / cm, more preferably between 10 mS / cm and 150 mS / cm, more preferably between 10 mS / cm and 50 mS / cm, even more preferably between 10 mS / cm and 40 mS / cm, and particularly preferably between 10 mS / cm and 25 mS / cm (determined by the conductivity of the measuring probe of PCE-PHD1 at 20°C to 25°C).

[0219] - The temperature of the hydrothermal treatment is preferably adjusted to a maximum value between 200°C and 250°C, more preferably a maximum value between 210°C and 245°C, and / or

[0220] The residence time in hydrothermal treatment is preferably adjusted to be between 1 minute and 6 minutes, preferably between 30 minutes and 4 hours, and especially preferably between 1 hour and 3 hours.

[0221] This method controls the STSA surface area to 5m². 2 / g and 200m 2 The OAN value is adjusted between 50ml / 100g and 150ml / 100g.

[0222] Advantageously, the renewable raw material is completely dissolved in the liquid containing the renewable raw material in the first step. Alternatively, the renewable raw material is not completely dissolved in the liquid containing the renewable raw material in the first step; however, in which...

[0223] - The concentration of the organic dry weight of renewable raw materials in a liquid containing renewable raw materials.

[0224] - pH value of liquids containing renewable raw materials and

[0225] -Inorganic ion concentration in liquids containing renewable raw materials

[0226] The process is adjusted so that, before the formation of a separable solid in the third step, the renewable raw materials are first completely dissolved due to the increased temperature during the hydrothermal treatment in the second step.

[0227] The advantage of having renewable raw materials completely dissolved in a liquid containing renewable raw materials is that solid-solid transitions are suppressed, and in the third step, the separable solids are completely formed from the solution, i.e., a liquid-to-solid transition occurs.

[0228] Advantageously, the method operates continuously, wherein the process conditions for hydrothermal treatment are kept constant in the second step and the pH and conductivity of the liquid containing the renewable raw material are continuously adjusted in the first step to compensate for fluctuations in the quality of the renewable raw material.

[0229] The advantage of this approach is that it avoids the need for significantly more costly adjustments to process conditions in the second step.

[0230] In a particular variation of the method, the temperature and residence time in the second step are adjusted to achieve the desired temperature at 5m. 2 / g and 200m 2 STSA surface area between / g and OAN value between 50ml / 100g and 150ml / 100g,

[0231] First, an inorganic ion concentration slightly higher than the concentration obtained after adjusting the organic dry matter content of the renewable raw materials in the liquid containing the renewable raw materials and adjusting the pH value is required.

[0232] - Subsequently, the inorganic ion concentration can be further increased by adding salt until it reaches an inorganic ion concentration that matches the process conditions of the second stage, as measured by conductivity.

[0233] The advantage of this method is that conductivity can be used to fine-tune the quality of liquids containing renewable raw materials, because conductivity can be measured more simply and reliably than pH.

[0234] The concentration of the organic dry weight of the renewable raw material in the liquid containing the renewable raw material, the pH value of the liquid containing the renewable raw material, and / or the concentration of inorganic ions in the liquid containing the renewable raw material are advantageously adjusted in the first step.

[0235] Alternatively, adjusting the concentration of the organic dry weight of the renewable raw material in the liquid containing the renewable raw material, adjusting the pH value of the liquid containing the renewable raw material, and / or adjusting the concentration of inorganic ions in the liquid containing the renewable raw material are advantageously carried out in the first and second steps.

[0236] Alternatively, adjusting the concentration of the organic dry weight of the renewable raw material in the liquid containing the renewable raw material, adjusting the pH value of the liquid containing the renewable raw material, and / or adjusting the concentration of inorganic ions in the liquid containing the renewable raw material are advantageously carried out in the second step.

[0237] In the following embodiment, the adjustment of the concentration of the organic dry matter of the renewable raw material in the liquid containing the renewable raw material, the adjustment of the pH value of the liquid containing the renewable raw material, and / or the adjustment of the concentration of inorganic ions in the liquid containing the renewable raw material are also carried out in the second step. Advantageously, in the first step, the renewable raw material is completely dissolved in the liquid containing the renewable raw material, and during the hydrothermal treatment in the second step, the formation of desired fine particles is induced not only by the selected process conditions but also additionally by increasing the concentration of the organic dry matter of the renewable raw material in the liquid containing the renewable raw material, decreasing the pH value of the liquid containing the renewable raw material, or increasing the concentration of inorganic ions in the liquid containing the renewable raw material.

[0238] The advantage of this method is that the conditions that cause the formation of particles with the desired fineness can be specifically generated in the second step, thereby improving the stability of the method and potentially reducing the residence time in the second step.

[0239] Furthermore, after the desired fine particle formation in the second step is completed, it advantageously leads to a decrease in the concentration of organic dry matter in the liquid containing the particulate carbon material, an increase in the pH of the liquid containing the particulate carbon material, or a decrease in the concentration of inorganic ions in the liquid containing the particulate carbon material. This has advantageously been achieved in the second step or later in the third step.

[0240] This method ensures that, after the desired fine-grained material formation is complete, no other solids are formed, for example, during the cooling phase at the end of the second step or by increasing the concentration of organic dry matter in the liquid containing particulate carbon material, for example, through evaporation in the third step.

[0241] During hydrothermal treatment, the pressure corresponds at least to the saturated vapor pressure of the liquid containing the renewable raw materials.

[0242] In a preferred embodiment,

[0243] - The concentration of the organic dry weight of the liquid containing lignin in the first step is between 10% and 20% by mass.

[0244] - The pH of the liquid containing lignin in the first step is greater than 8.5 and less than 10.5.

[0245] - The inorganic ion concentration of the liquid containing lignin in the first step results in an electrical conductivity between 10 mS / cm and 25 mS / cm.

[0246] - In the second step, the maximum temperature of the hydrothermal treatment is between 210℃ and 240℃, and

[0247] -In the second step, the residence time of the lignin-containing liquid in the hydrothermal treatment is between 120 minutes and 240 minutes, thereby...

[0248] - The STSA surface area, measured after dehydration in the third step and drying in the fourth step, of the particulate carbon material produced in this manner has a value of 5 m². 2 / g and 50m 2 The values ​​are between / g and the OAN values ​​are between 50ml / 100g and 100ml / 100g.

[0249] The method according to the invention can also include rinsing immediately after dehydration in the third step or pulverizing immediately after drying in the fourth step.

[0250] The drying in the fourth step is preferably performed at a temperature below the softening point of the particulate carbon material, preferably below 150°C, and more preferably below 130°C.

[0251] Advantageously, in the fourth step, the D90 of the Q3 distribution of the particle size of the granular carbon material after drying is adjusted to less than 30 μm, preferably less than 20 μm, more preferably less than 15 μm, and especially preferably less than 10 μm by pulverization.

[0252] In particular, the method is capable of performing the task without the need for the addition of copolymerizable compounds or polymerization initiators, and without the need for biomass fermentation.

[0253] The method operates in the liquid phase, where it always operates below the critical point of water. Attached Figure Description

[0254] The present invention will now be described in detail with reference to embodiments. The accompanying drawings show:

[0255] Figure 1 A graph showing stress-strain curves of rubber-related characteristic values ​​of a crosslinked rubber article composed of SBR and particulate carbon material according to the present invention, and of a corresponding reference rubber-related characteristic value, in a tensile test.

[0256] Figure 2 A graph showing the correlation between the loss factor tanδ (logarithmically scaled) and the temperature at a fully cross-linked article composed of SBR and particulate carbon material according to the invention, or at a temperature having N 660.

[0257] Figure 3 A graph showing stress-strain curves comparing rubber-related characteristic values ​​of crosslinked rubber articles made of SBR in tensile tests, wherein the rubber articles are respectively provided with untreated lignin, provided with particulate carbon material according to the invention but without coupling agent, and provided with particulate carbon material according to the invention and provided with coupling agent.

[0258] Figure 4 A graph showing stress-strain curves comparing rubber-related characteristic values ​​of crosslinked rubber articles made of SBR in tensile tests, the rubber articles comprising particulate carbon material according to the invention but without other additives, comprising particulate carbon material according to the invention and an agent for masking functional groups, and comprising particulate carbon material according to the invention and a coupling agent.

[0259] Figure 5 A graph showing the stress-strain curves in a tensile test is presented, which serves as a comparison of the rubber-related characteristic values ​​of an article composed of an elastomer material mixture based on natural rubber and polybutadiene rubber NR / BR and particulate carbon materials, each with different mixing processes, with reference rubber-related characteristic values.

[0260] Figure 6A graph showing a stress-strain curve comparing the rubber-related characteristic values ​​of a crosslinked rubber article made of NBR and containing particulate carbon material according to the invention without a coupling agent, and a reference rubber-related characteristic value, in a tensile test. Detailed Implementation

[0261] The embodiments describe the method according to the invention for obtaining particulate carbon material according to the invention, its properties, and its performance in cross-linked rubber.

[0262] Examples 1 to 11 are used to prepare particulate carbon materials composed of lignin.

[0263] The first step provides a liquid containing renewable raw materials.

[0264] First, water (1) and lignin (2) are mixed and a lignin-containing liquid with an adjusted organic dry weight (3) content is prepared.

[0265] Subsequently, lignin is completely dissolved in the lignin-containing liquid. For this purpose, the pH is adjusted to the desired value (7) by adding an alkali or acid (6). The preparation of the solution is supported by vigorous and thorough mixing at a suitable temperature (4) for a sufficient time (5). A specific concentration of inorganic ions, measurable as conductivity (9), is adjusted by adding an alkali or acid and by additionally adding a salt (8) and / or by the ash content derived from lignin. The composition and properties of the lignin-containing liquid prepared in this manner are illustrated in Table 1.

[0266]

[0267]

[0268] Table 1 lists the components of the lignin used in Table 2.

[0269] C 62.8 64.0 67.2 H 4.8 5.2 5.5 O (calculated) 24.8 24.0 24.0 N 0.3 0.0 0.0 S 1.3 1.5 1.8 Na 2.5 1.9 0.3 Ash content (no Na) 3.6 4.1 1.2

[0270] Table 2

[0271] In the second step, the liquid containing renewable raw materials is subjected to hydrothermal treatment to obtain a solid.

[0272] The solution prepared in the first step is heated from the initial temperature (10) to the reaction temperature (12) over a heating time (11), and the reaction temperature is maintained over a reaction duration (13). Then, it is cooled to the final temperature (15) over a cooling time (14). A solid is obtained as a result. Depending on the above process conditions, the pH (16) and conductivity (17) of the liquid containing the solid change.

[0273] With appropriate adjustments to the organic dry matter content, pH value, and inorganic ion concentration in the first step, and with appropriate selection of the process conditions in the second step, the following conditions are set in the second step, wherein the particulate carbon material is deposited from the solution in a coarse form. The method conditions for the second step are listed in Table 3.

[0274] - ℃ min ℃ min min ℃ - mS / cm 1 80 90 240 150 3600 80 9.0 19.7 2 80 90 240 150 3600 80 9.1 21.4 3 80 90 240 150 3600 80 8.6 20.2 4 80 90 240 150 3600 80 8.4 21.1 6 30 40 225 324 40 30 8.4 13.2 7 30 40 225 408 40 30 8.3 13.5 8 30 41 230 270 41 30 8.3 13.5 9 30 41 230 300 41 30 8.2 13.7 10 30 42 235 162 42 30 8.7 12.9 11 30 41 230 180 41 30 8.6 20.9

[0275] Table 3

[0276] In the third step, the coarse granular carbon material is dehydrated and rinsed if possible. The coarse granular carbon material is separated from the treated liquid as much as possible by dehydration (18). Immediately afterwards, the coarse granular carbon material is rinsed with several times the volume of water and dehydrated again (19). The method conditions for the third step are summarized in Table 4.

[0277]

[0278]

[0279] Table 4

[0280] In the fourth step, the coarse granular carbon material is dried and may be ground, dehydrated, and possibly rinsed.

[0281] The dehydrated, coarse, granular carbon particles and the residual liquid are dried at an elevated temperature (20, see Table 5) to obtain granular carbon material. Subsequently, the granular carbon material is deagglomerated (21, see Table 5).

[0282]

[0283]

[0284] Table 5

[0285] The mass of the particulate carbon materials obtained from Examples 1 to 11: The results clearly show the particulate carbon materials obtained according to the present invention (see Table 6):

[0286]

[0287]

[0288] 1 = In a suspension containing 15% alkali; 2 = Alkali resistance of the dissolved material, expressed as a percentage;

[0289] 3 = Derived from Raman spectroscopy; 4 = Derived from particle size determination using laser diffraction.

[0290] 5 = calculated from STSA and particle density; nb = uncertain

[0291] Table 6

[0292] Used to prepare rubber composed of SBR and granular carbon materials from Examples 1 and 2, or with carbon black N660. Examples 12A to 12D of the article and reference example

[0293] The carbon materials obtained according to Examples 1 and 2 were introduced into the rubber mixture as fillers and vulcanized with the aid of other additives. The composition of the rubber mixture is shown in Table 7.

[0294]

[0295]

[0296] phr: Parts per 100 parts of rubber, expressed as elastomer mass.

[0297] DPG, CBS: Vulcanization accelerators

[0298] Si69: Coupling agent

[0299] Table 7

[0300] Lanxess's SBR solution (sSBR) Buna VSL4526-0 was used as the SBR. The SBR, except for butadiene, was a copolymer composed of 26% by mass of styrene. Its Mooney viscosity was 65 ME (ASTM D 1646). Zinc oxide, stearic acid, and sulfur were from Fischer Scientific. 2-N-cyclohexylbenzothiazole sulfinamide (CBS) was from Lanxess. 1,3-Diphenylguanidine (DPG) from Sigma-Aldrich LLC (USA) was used. Process oil TDAE (VIVATEC 500) from Klaus Dahleke KG was used. The antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer TMQ was supplied by CH, located in Krefeld. Provided. N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) was purchased from abcr GmbH & Co. KG (a joint venture) in Karlsruhe. It was supplied by Evonik Industries under the name... The bis(triethoxysilylpropyl)tetrasulfide sold is used as a coupling agent.

[0301] SBR at 145℃ and a packing factor of 0.7 (corresponding to 56cm²) 3The material was placed in a closed mixer (Haake Rheomix 600P, ThermoFisher Scientific, Karlsruhe) in a volumetric manner. The filler material was then added in two stages. After the possible addition of silane Si69, the mixture was held in the closed mixer at a temperature between 140°C and 165°C for 10 minutes and then for 60 minutes. -1 Mixing at high speeds is used to achieve complete silanization.

[0302] The addition of antioxidants and vulcanizing additives was carried out on a two-roll mill (Polymix-110L, Servitec Maschinen Service GmbH, Wustermark) at an initial temperature of 50°C and a constant friction ratio of 1:1.2.

[0303] Rubber blends referenced and rubber blend A (Table 7) were crosslinked using a vulcanization process commonly used for carbon black applications. Rubber blends B, C, and D (Table 7) were crosslinked using a vulcanization process commonly used for applications involving silica with Si69. Samples were vulcanized in a laboratory press TP1000 (Fontijne Grotnes BV, Vlaardingen, Netherlands) at 160°C and 150 kN. Optimal vulcanization time t 90 Determined using a rubber process analyzer (Scarabaeus SIS-V50, Scarabaeus GmbH, Wetzlar).

[0304] Mechanical characterization was performed on DIN S2 samples according to DIN 53504 using a Zwick / Roell-Z010 material testing machine (Zwick GmbH & Co KG, Ulm) with an optical strain sensor at a transverse speed of 200 mm / min at room temperature. Figure 1 The charts present stress-strain curves of rubber-related characteristic values ​​of rubber products obtained in tensile tests, from Examples A to Examples D in Table 7.

[0305] Especially in the cases of Examples B, C, and D (where a coupling agent was added), the stress-strain curves exhibit characteristics similar to those of the filler material N660. Therefore, the values ​​of the 50%, 100%, and 200% moduli in Examples B and C are at least as high as the reference values. It is also shown that when the strain is in the lower range (up to 100%), increasing the filling degree of the particulate carbon material according to Example 2 from 40 phr (B) to 60 phr (D) causes an increase in stress values, i.e., an increase in the 50% and 100% moduli. Furthermore, it is evident that, with the same filling degree, increasing the STSA surface area and OAN value of the particulate carbon material from the values ​​in Example 2 to those in Example 1 results in an improvement in tensile strength and causes higher values ​​for the 50%, 100%, and 200% moduli (see B and C). It is also evident that, in Example 2, having a 12.6 m... 2 Particulate carbon materials with a surface area of ​​ / g of STSA have shown superior performance in tensile tests compared to those passing through 34m 2 / g±5m 2 The stress-strain curves are similar to those of classic carbon black N660, characterized by the surface area of ​​STSA per g.

[0306] exist Figure 2 Table 8 shows the temperature-dependent loss coefficient tanδ (the quotient of the loss modulus E” and the storage modulus E’ of the elastomer material) determined in the dynamic mechanical analysis (temperature scan).

[0307] The mixture with N660 (reference) and the mixture with particulate carbon material of Example 2 but without coupling agent (Example 12A) showed similar glass transition temperatures (T0). g,SBR = -2.91℃; see Figure 2 (The peak value of the tanδ curve versus temperature). Both mixtures also exhibit similar stiffness in the flat region of the rubber above the glass transition temperature. The tanδ curves are adjacent to each other, although the curve of the reference mixture is slightly lower than that of Example 12A from about 76°C, indicating a roughly smaller energy loss.

[0308] The application of the particulate carbon material combined with the coupling agent in Example 2 (Example 12B) resulted in a noteworthy change. Compared to the reference and 12A, the glass transition temperature of the mixture in Example 12 shifted upward to T0. g,SBR = -0.48℃. Under weak dynamic strain (0.5%), the energy loss characteristics of mixture 12B are significantly improved compared to the reference with N660, which can be seen at lower curve changes in the temperature range above the glass transition temperature.

[0309] It can be seen that for tanδ above the glass transition temperature, the elastomer material containing particulate carbon material and coupling agent in Example 2 has a smaller value relative to the reference with N660, which can be expected to result in relatively reduced sliding friction in tires made of this material.

[0310] Reference with N660 0.1020 1.4342 Example 12A 0.1035 1.4023 Example 12B 0.0840 1.6208

[0311] Table 8

[0312] In addition, Figure 2 It is evident that the tanδ of Example 12B is higher than that of the reference at 0°C, which can be expected to result in improved wet grip of tires made from the mixture of Example 12B.

[0313] Comparative Example 13 of Manufacturing Rubber Products Composed of SBR and Untreated Lignin

[0314] According to existing technology, untreated lignin has already been used in rubber compounds. The following comparative examples show the different roles of untreated lignin and the carbon material according to the invention in rubber compounds.

[0315] For comparative purposes, lignin 3 from Table 2 was introduced as a filler into the rubber compound and vulcanized with the aid of other additives. The composition of the rubber compound corresponds to that in Example 12B; however, untreated lignin 3 is now used instead of the particulate carbon material in Example 2. The rubber compound used in Example 13 was crosslinked using a common vulcanization process for the co-application of silica and Si69.

[0316] The stress-strain curves, representing examples of rubber-related properties of the obtained rubber articles from tensile tests, are presented together with the results of Examples 12A and 12B. Figure 3 The charts are listed below.

[0317] It can be seen that even when using the coupling agent silane Si69, the effect caused by untreated lignin (Example 13) in the rubber mixture is significantly weaker than the effect caused by the carbon material according to the invention itself (Example 12A), and even more significantly weaker than the effect of the combination of the carbon material according to the invention with silane Si69 (Example 12B).

[0318] Used to determine the product in Example 2 14 Example 14 of C content

[0319] In order to determine 14 The carbon content, the material in Example 2, was provided to the A. Mickiewicz University Foundation. Ridiocarbon Laboratory, ul. 46, 61-612 Poznań. The methods used are described by the laboratory director, Tomasz Goslar, on the institute's website. The main components of lignin are summarized below.

[0320] Used to leverage AMS technology 14 The method for determining the age using C-type dating involves the following steps:

[0321] a) Chemical pretreatment

[0322] b) Producing CO2 and graphitizing it.

[0323] c)AMS 14 C measurement

[0324] d) Calculate and calibrate 14 C's age

[0325] a) In principle, a method of chemical pretreatment is described in Brock et al., 2010, Radiocarbon, 52, 102-112.

[0326] Plant residue samples were treated with 1M HCl (80°C, 20+ min), 0.025M to 0.2M NaOH (80°C), and then with 0.25M HCl (80°C, 1 h). After treatment with the appropriate reagents, the samples were rinsed with distilled water (Millipore) until pH = 7. If bubble formation was still visible in the sample, the first HCl treatment was performed for a longer time (20+ min). The NaOH treatment was repeated several times, generally until no further staining of the NaOH solution occurred (staining is caused by humic acid dissolved in NaOH); however, if there was a risk of complete sample dissolution, the NaOH treatment was interrupted.

[0327] b) In the case of organic samples, CO2 is prepared by burning the samples.

[0328] Along with CuO and silver fluff, the samples were burned in a sealed quartz tube (under vacuum) at 900°C for 10 hours. The resulting gas (CO2 + water vapor) was then dried in a vacuum instrument and reduced with hydrogen (H2) using 2 mg of iron powder as a catalyst. The resulting mixture of carbon and iron was then pressed into a dedicated aluminum holder, as described in Czernik J., Goslar T., 2001, Radiocarbon, 43, 283-291. Standard samples, e.g., those without... 14 Samples of C (coal or IAEA C1 Carrara Marmor) and "International Modern" 14Sample of "C Standard" (oxalic acid II).

[0329] c) The measurements described here are taken at the AMS University of A. Mickiewicz in Poznań. 14 Executed in Laboratory C.

[0330] In carbon samples 14 The C content was measured using a Compact Carbon AMS spectrometer (manufacturer: National Electrostatics Corporation, USA), as described in the literature Goslar T., Czernik J., Goslar E., 2004, Nuclear Instruments and Methods B, 223-224, 5-11. The measurement was based on... 14 C 13 C and 12 A comparison of the intensity of the C ion beam for each sample and each standard (modern standard: "oxalate II" and non-oxalate). 14 The intensity of the carbon (C) standard “background” is measured. In each AMS process, 30 to 33 samples of unknown age are measured alternately with 3 to 4 modern standard measurements and 1 to 2 background measurements. If the organic sample is identified in age, then the background is presented through the coal.

[0331] d) Traditional 14 C-age was used for correction of isotopic fractionation (according to Stuiver, Polach 1977, Radiocarbon 19, 355), based on the results in an AMS spectrometer. 14 C / 12 The proportion of C is determined simultaneously. 13 C / 12 The proportion of C is calculated (Note: δ) 13 The measured value of C is related to isotopic fractionation during CO2 reduction and isotopic fractionation within the AMS spectrometer, and the measured value itself cannot be correlated with δ values ​​determined on gas samples using conventional mass spectrometry. 13 (Comparison of C values). Calculated 14 The uncertainty of age C, aided by the uncertainty arising from counting statistics, may vary from person to person. 14 C / 12 The dispersion (standard deviation) of the results for C is determined. Additionally, measurements taken on a standard sample are considered. 14 C / 12 The uncertainty of the proportion of C. The report proposes a traditional... 14 The 1-sigma uncertainty of the C-age is the best approximation of the absolute uncertainty of the measurement.

[0332] 14 The calibration of age C was performed using OxCal procedure version 4.2 (2014), the basic principles of which are described in Bronk Ramsey C., 2001, Radiocarbon, 43, 355-363, while the current version is described in Bronk Ramsey C., 2009, Radiocarbon, 51, 337-360 and Bronk Ramsey C. and Lee S., 2013, Radiocarbon, 55, 720-730. Calibration relative to... 14 The latest version of the C calibration curve, namely INTCAL13 (Reimer PJ et al., 2013, Radiocarbon, 55(4), 1869-1887), was used.

[0333] The analysis yields the age of the carbon samples for archaeological purposes. However, the measurement results can also serve as an indication of specific reactivity. In the current case of Example 2, the analysis of specific reactivity yields a value of 243.30 Bq / kgC ± 0.52 Bq / kgC, or Bq / kg carbon.

[0334] Used to prepare particulate carbon materials from SBR and Example 2 in the presence of a reagent that masks functional groups. Example 15 of the constructed rubber products:

[0335] The carbon material obtained according to Example 2 was introduced as a filler into the rubber compound and vulcanized with the aid of other additives. The composition and processing of the rubber compound corresponded to the composition and processing described in Example 12B (Table 7), however, wherein silane Si69 was replaced by triethoxymethylsilane in an equimolar amount, which corresponds to the use of 1.06 phr. Further processing was also carried out similarly to Example 12.

[0336] Triethoxymethylsilane cannot be inserted into the crosslinking via sulfur bridges. However, in the case of functional group depletion, the triethoxymethylsilane reacts with the surface of the carbon material according to the invention. The functional group reacting with the silane is replaced outward by a methyl group, which results in compatibilization of the filler surface with the nonpolar rubber matrix compared to the unmodified raw material.

[0337] In rubber, carbon materials according to the invention treated with triethoxymethylsilane produce, for example, higher tensile strength compared to carbon materials without silane, however, as is expected, lower than carbon materials combined with silane Si69 that are coupled together.

[0338] Figure 4 The stress-strain curves in the tensile test, which serve as an example of obtaining the rubber-related properties of rubber products, show that, in the selected rubber system and for the selected application, functional groups can be masked.

[0339] Used to prepare rubber products composed of NR / BR and granular carbon materials as shown in Example 2, or with carbon black N660. Examples 16A and 16B, and references:

[0340] The carbon material obtained according to Example 2 was introduced as a filler into a mixture of NR and BR and vulcanized with the aid of other additives.

[0341] Here, in A and in the reference, firstly, a mixture of NR and BR (Pre-Mix) is prepared in a closed mixer (Haake Rheomix 600P, Thermo Fisher Scientific, Karlsruhe) at a start-up temperature of 120°C, and then said mixture is crosslinked with the corresponding filler materials and other components. Conversely, in B, similarly in a closed mixer (start-up temperature 35°C, 60 min... -1 In a closed mixer (at a rotational speed), a masterbatch consisting of BR, filler material, and silane is first prepared. Then, the masterbatch is further processed with NR and the remaining components (also in a closed mixer, at a start-up temperature of 120°C, for 60 minutes). -1 (Spindle speed). The quantity composition of the two processing variations is the same.

[0342] The stress-strain curves of the rubber-related properties of the rubber products obtained in tensile tests, as examples A and B, are shown in... Figure 5 The charts are listed below. These charts show that the carbon material according to the invention can be used for reinforcement in NR / BR blends. Furthermore, it is evident that the order of processing affects the properties of the filler material in articles composed of the corresponding NR / BR rubber blends in the cross-linked state. In this way, the modulus and tensile strength can be affected.

[0343] Examples of preparation of rubber products made of NBR using particulate carbon materials or N990 as described in Example 4 17A and Example 17B and Reference

[0344] The carbon material obtained according to Example 4 was introduced into the NBR as a filler and vulcanized with the aid of other additives but without coupling agents. The composition of the rubber compound is shown in Table 9.

[0345]

[0346]

[0347] Table 9

[0348] The mixture was tested in a Haake Rheomix 600 (tangential rotor geometry, 78cm). 3 (The initial temperature was 40℃ and the time was 100 minutes) -1The rotor speed was prepared. First, the NBR polymer was mixed for 2 min. Then, stearic acid, ZnO, possibly the materials from Example 4, and talc were additionally mixed for 2 min. Additionally, N990 and Mesamoll II were further mixed for 4 min, the antioxidant was further mixed for 3 min, and the vulcanizing chemicals were further mixed for 2 min. The optimal vulcanization time was determined using a rubber process analyzer, and the mixture was vulcanized at 160°C (t). 90 The minute value is (+1 / mm layer thickness).

[0349] The Shore A hardness was determined according to DIN 53505:2000-08, the tensile test was performed according to DIN 53504:2009-10, and the sample was stored in Lubrizol OS 206304 oil at 70°C for 72 hours according to ISO 1817:2008-08.

[0350] The values ​​shown in Table 10 are determined here.

[0351] Shore A hardness 83 84 85 Tensile strength (MPa) 9.9 11.1 11.4 Elongation at break (%) 235 253 248 Modulus (MPa) 50% 4.7 5.3 5.6 100％ 6.6 7.5 8.0 200％ 9.7 10.8 11

[0352] Table 10

[0353] To clarify: When N990 is partially or completely replaced by the carbon material according to the invention in Example 4 without the addition of a coupling agent, similar or even slightly improved values ​​are achieved in the tensile test, see [reference needed]. Figure 6 The same applies to the changes in values ​​shown in Table 11 after storage in oil. To achieve similar values ​​when replacing inactive carbon black such as N990, the carbon material according to the invention, by its mass according to Example 4 without coupling agent, is used. It is sufficient for use.

[0354]

[0355]

[0356] Table 11

[0357] As can be seen from the above description, the embodiments of the present invention cover, but are not limited to, the following technical solutions:

[0358] Option 1. An application of a particulate carbon material that can be prepared from renewable raw materials, said application being the use of said particulate carbon material in a polymer mixture, rubber mixture, or plastic mixture, wherein said particulate carbon material has:

[0359] - Corresponding to the renewable raw materials 14 C content 14 C content, the 14Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g

[0360] -Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area,

[0361] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g, and

[0362] - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass.

[0363] Option 2. The application of the particulate carbon material according to Option 1, wherein the particulate carbon material is used as a filter, particularly in rubber or plastic mixtures.

[0364] Option 3. The application as described in Option 1 or 2,

[0365] The renewable raw material mentioned above is lignin-containing biomass.

[0366] Option 4. The application according to any one of Options 1 to 3, wherein the particulate carbon material is prepared by hydrothermal treatment, particularly hydrothermal carbonization, of renewable raw materials.

[0367] Option 5. A polymer mixture comprising at least one polymer and at least one particulate carbon material that can be prepared from renewable raw materials, wherein the particulate carbon material has:

[0368] - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g

[0369] -Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area,

[0370] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g, and

[0371] - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass.

[0372] Option 6. A plastic mixture comprising at least one plastic and at least one particulate carbon material that can be prepared from renewable raw materials, wherein the particulate carbon material has:

[0373] - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g

[0374] -Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area,

[0375] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g, and

[0376] - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass.

[0377] Option 7. The plastic mixture according to Option 6, wherein the plastic mixture further comprises at least one adhesive, the adhesive preferably being in an amount of 2% to 16% by mass, more preferably 4% to 14% by mass, and particularly preferably 6% to 12% by mass, based on the mass of the plastic in the plastic mixture.

[0378] Scheme 8. A rubber compound comprising at least one rubber and at least one particulate carbon material that can be prepared from renewable raw materials, wherein the particulate carbon material has:

[0379] - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g

[0380] -Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area,

[0381] -Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g, and

[0382] - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass.

[0383] Scheme 9. The rubber mixture according to Scheme 8, wherein the rubber mixture further comprises at least one coupling agent, wherein the coupling agent is preferably present in the rubber mixture in an amount of 2% to 16% by mass, more preferably 4% to 14% by mass, and particularly preferably 6% to 12% by mass, based on the mass of the particulate carbon material in the rubber mixture.

[0384] Scheme 10. The rubber mixture according to Scheme 9, wherein the at least one coupling agent is at least one organosilane, preferably at least one organosilane selected from bis(trialkoxysilyl) oligosulfides or polysulfides, mercaptosilanes, aminosilanes, silanes having unsaturated hydrocarbon groups and silanes having large saturated hydrocarbon groups.

[0385] Scheme 11. A rubber mixture according to any one of Schemes 8 to 10, wherein the rubber mixture further comprises at least one of the following: (i) a reagent for masking the functional groups of the particulate carbon material, wherein the reagent is preferably selected from amines, glycols and organosilanes; (ii) carbon black and (iii) at least one crosslinking agent.

[0386] Scheme 12. The rubber mixture according to any one of Schemes 8 to 11, wherein the BET surface area of ​​the particulate carbon material deviates from its STSA surface area by a maximum of 20%, preferably a maximum of 15%, and more preferably a maximum of 10%.

[0387] Scheme 13. A rubber mixture according to any one of Schemes 8 to 12, wherein the particulate carbon material is prepared by hydrothermal treatment, particularly hydrothermal carbonization, of a renewable raw material.

[0388] Scheme 14. A rubber mixture according to any one of Schemes 8 to 13, wherein the particulate carbon material is non-porous or has a porosity of <0.1 cm. 3 / g pore volume.

[0389] Scheme 15. A rubber mixture according to any one of Schemes 8 to 14, wherein the rubber is selected from: natural rubber, styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene, isobutylene-isoprene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer (NBR), chloroprene, fluororubber, acrylic rubber, and mixtures thereof.

[0390] Scheme 16. A rubber mixture according to any one of Schemes 8 to 15, wherein the rubber mixture comprises at least two elastomer types as rubber, and wherein the particulate carbon material is first added separately to at least one of the elastomer types before the elastomer types are combined.

[0391] Option 17. Application of the rubber compound according to any one of Options 8 to 16, wherein the rubber compound is used to manufacture rubber products, preferably tires, particularly pneumatic tires, tire treads, tire sidewalls, cable sheaths, hoses, drive belts, conveyor belts, roller covers, shoe soles, shock absorbers, seals, profiles and damping elements, and most preferably for manufacturing pneumatic tires, tire treads and tire sidewalls.

[0392] Scheme 18. A rubber article comprising a vulcanized rubber mixture according to any one of Schemes 8 to 16, wherein the rubber article is selected from: tires, particularly pneumatic tires, tire treads, tire sidewalls, cable sheaths, hoses, drive belts, conveyor belts, roller covers, shoe soles, shock absorbers, seals, profiles and damping elements, most preferably selected from pneumatic tires, tire treads and tire sidewalls.

[0393] Option 19. The rubber product according to Option 18, wherein the rubber product is a pneumatic tire.

Claims

1. An application of a particulate carbon material prepared from renewable raw materials, said application being the use of said particulate carbon material in a polymer mixture, rubber mixture, or plastic mixture, wherein said particulate carbon material has: - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g; - Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area; - Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g; - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass. The renewable raw material mentioned above is lignin-containing biomass, and The particulate carbon material is prepared by hydrothermal treatment of renewable raw materials.

2. The application of the particulate carbon material according to claim 1, wherein the application is to use the particulate carbon material as a filler material.

3. The application of the particulate carbon material according to claim 1, wherein the application is to use the particulate carbon material as a filler material in a rubber mixture or a plastic mixture.

4. The application of the particulate carbon material according to claim 1 or 2, The particulate carbon material is prepared by hydrothermal carbonization of renewable raw materials.

5. The application of the particulate carbon material according to claim 1 or 2, The carbon content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 60% by mass and less than 75% by mass.

6. The application of the particulate carbon material according to claim 1 or 2, The oxygen content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 20% and 30% by mass.

7. A polymer mixture comprising at least one polymer and at least one particulate carbon material prepared from renewable raw materials, wherein the particulate carbon material has: - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g - Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area, - Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g. - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass. The renewable raw material mentioned above is lignin-containing biomass, and The particulate carbon material is prepared by hydrothermal treatment of renewable raw materials.

8. The polymer mixture according to claim 7, The carbon content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 60% by mass and less than 75% by mass.

9. The polymer mixture according to claim 7, The oxygen content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 20% and 30% by mass.

10. A plastic mixture comprising at least one plastic and at least one particulate carbon material prepared from renewable raw materials, wherein the particulate carbon material has: - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g - Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area, - Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g. - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass. The renewable raw material mentioned above is lignin-containing biomass, and The particulate carbon material is prepared by hydrothermal treatment of renewable raw materials.

11. The plastic mixture of claim 10, wherein the plastic mixture further comprises at least one adhesion promoter.

12. The plastic mixture of claim 11, wherein the additive is present in an amount of 2% to 16% by mass based on the mass of the plastic in the plastic mixture.

13. The plastic mixture of claim 11, wherein the additive is present in an amount of 4% to 14% by mass based on the mass of the plastic in the plastic mixture.

14. The plastic mixture of claim 11, wherein the additive is present in an amount of 6% to 12% by mass based on the mass of the plastic in the plastic mixture.

15. The plastic mixture according to claim 10, The carbon content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 60% by mass and less than 75% by mass.

16. The plastic mixture according to claim 10, The oxygen content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 20% and 30% by mass.

17. A rubber compound comprising at least one rubber and at least one particulate carbon material prepared from renewable raw materials, wherein the particulate carbon material has: - Corresponding to the renewable raw materials 14 C content 14 C content, the 14 Carbon content greater than 0.20 Bq / g and less than 0.45 Bq / g - Minimum 5m 2 / g and a maximum of 200m 2 / g STSA surface area, - Oil absorption value (OAN) between 50ml / 100g and 150ml / 100g. - The carbon content, calculated on a dry matter basis excluding ash, is between 60% and 80% by mass. The renewable raw material mentioned above is lignin-containing biomass, and The particulate carbon material is prepared by hydrothermal treatment of renewable raw materials.

18. The rubber compound of claim 17, wherein the rubber compound further comprises at least one coupling agent.

19. The rubber mixture according to claim 18, wherein the coupling agent is present in the rubber mixture in an amount of 2% to 16% by mass based on the mass of the particulate carbon material in the rubber mixture.

20. The rubber mixture according to claim 18, wherein the coupling agent is present in the rubber mixture in an amount of 4% to 14% by mass based on the mass of the particulate carbon material in the rubber mixture.

21. The rubber mixture according to claim 18, wherein the coupling agent is present in the rubber mixture in an amount of 6% to 12% by mass based on the mass of the particulate carbon material in the rubber mixture.

22. The rubber compound according to any one of claims 17 to 21, The at least one coupling agent is at least one organosilane.

23. The rubber compound according to claim 22, The at least one organosilane is selected from bis(trialkoxysilyl) oligosulfides or polysulfides, mercaptosilanes, aminosilanes, silanes having unsaturated hydrocarbon groups, and silanes having large saturated hydrocarbon groups.

24. The rubber compound according to any one of claims 17 to 21, The rubber mixture further comprises at least one of the following: (i) a reagent that masks the functional groups of the particulate carbon material.

25. The rubber compound according to claim 24, The reagents are selected from amines, glycols and organosilanes; (ii) carbon black and (iii) at least one crosslinking agent.

26. The rubber compound according to any one of claims 17 to 21, The BET surface area of ​​the granular carbon material deviates from its STSA surface area by the largest margin, by 20%.

27. The rubber compound according to any one of claims 17 to 21, The BET surface area of ​​the granular carbon material deviates from its STSA surface area by the largest margin, by 15%.

28. The rubber compound according to any one of claims 17 to 21, The BET surface area of ​​the granular carbon material deviates from its STSA surface area by the largest margin, by 10%.

29. The rubber compound according to any one of claims 17 to 21, The particulate carbon material is prepared by hydrothermal carbonization of renewable raw materials.

30. The rubber compound according to any one of claims 17 to 21, The particulate carbon material is non-porous or has a porosity of <0.1 cm. 3 / g pore volume.

31. The rubber compound according to any one of claims 17 to 21, The rubber is selected from: natural rubber, styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene, isobutylene-isoprene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer (NBR), chloroprene, fluororubber, acrylic rubber, and mixtures thereof.

32. The rubber compound according to any one of claims 17 to 21, The rubber mixture comprises at least two elastomer types as rubber, and the particulate carbon material is first added separately to at least one of the elastomer types before the elastomer types are combined.

33. The rubber compound according to any one of claims 17 to 21, The carbon content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 60% by mass and less than 75% by mass.

34. The rubber compound according to any one of claims 17 to 21, The oxygen content of the particulate carbon material, calculated on a dry matter basis excluding ash, is between 20% and 30% by mass.

35. The use of the rubber compound according to any one of claims 17 to 21, wherein the rubber compound is used to manufacture rubber products, cable sheaths, hoses, drive belts, conveyor belts, roller covers, shoe soles, shock absorbers, seals, profiles and damping elements.

36. The application of the rubber compound according to claim 35, wherein the rubber article is a tire.

37. The application of the rubber compound according to claim 36, wherein the tire is a pneumatic tire.

38. The application of the rubber compound according to claim 36, wherein the tire comprises a tire tread or a tire sidewall.

39. A rubber article comprising a vulcanized rubber mixture according to any one of claims 17 to 34, wherein the rubber article is selected from: tires, cable sheaths, hoses, drive belts, conveyor belts, roller covers, shoe soles, shock absorbers, seals, profiles, and damping elements.

40. The rubber article according to claim 39, wherein the rubber article is a pneumatic tire.

41. The rubber article according to claim 39, wherein the rubber article is a tire tread or a tire sidewall.

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