Organic filler with thioether linkages

Abstract

The present invention relates to an organic filler having a 14C content in the range of from 0.20 to 0.45 Bq / g carbon and having a 14C content in the range of from 10 to lt; at least a portion of the aliphatic hydroxyl groups present in the chemical structure of the organic filler have been substituted by covalently bonded organic residues containing one or more sulfur atoms wherein at least one sulfur atom within the organic residues is adjacent to a carbon atom, and wherein at least a portion of the aliphatic hydroxyl groups present in the chemical structure of the organic filler has been substituted by covalently bonded organic residues containing one or more sulfur atoms; such that aliphatic carbon-sulfur-carbon bonds have been formed and present in the chemical structure of the organic filler; the present invention relates to a rubber composition comprising at least one rubber and at least one filler component; relates to a vulcanizable filler, to vulcanizable rubber compositions additionally comprising a vulcanization system, to vulcanizate compositions obtainable therefrom, and to the use of the aforementioned filler for producing (vulcanizable) rubber compositions, and to the use of such rubber compositions for producing tyres and / or industrial rubber articles.

Description

[0001] The present invention relates to an organic filler which can be prepared from renewable materials, to a (vulcanizable) rubber composition which further comprises at least one rubber as a filler component, to a vulcanized rubber composition obtainable therefrom, to the use of the above organic filler for producing a (vulcanizable) rubber composition, and to the use of such a rubber composition for producing tires and / or industrial rubber articles. Background of the Invention

[0003] It is known in the prior art to use reinforcing fillers in rubber compositions. In particular, industrial carbon blacks such as furnace black are used for this purpose. Industrial carbon black still represents the largest amount of reinforcing filler. Industrial carbon black is prepared by incomplete combustion or by pyrolysis of hydrocarbons on the basis of highly aromatic petrochemical oils. However, from an environmental point of view, it is desirable to avoid or minimize the use of fossil fuels for producing fillers. From an environmental point of view, it is particularly disadvantageous that for the production of one ton of industrial carbon black, approximately one ton of carbon dioxide is released during the production process, depending on the specific surface area of the carbon black. In addition, for color reasons, industrial carbon black is usually not suitable for certain applications.

[0004] A well-known alternative to industrial carbon black as an inorganic reinforcing filler is (precipitated) silica. Chemically modified precipitated silica is particularly suitable as a reinforcing filler due to its high specific surface area.

[0005] In the tire industry, it is also advantageous to use correspondingly chemically modified and particularly silanized precipitated silica. Vehicle tires, such as pneumatic tires, have a complex structure and need to meet various requirements. On the one hand, short braking distances must be ensured on dry and wet road surfaces; on the other hand, good wear resistance and low rolling resistance must also be achieved. In addition, vehicle tires must comply with regulatory requirements. To ensure a diverse performance profile, the individual tire components are specialized and contain a variety of different materials, such as metals, polymeric fabric materials, and various rubber-based components. The tread is largely responsible for the driving characteristics. The rubber composition of the tread determines the wear behavior and dynamic driving characteristics (on dry and wet roads, in cold and hot climates, on ice and snow) under different climatic conditions. Furthermore, the design of the tread is largely responsible for the tire behavior on slippery and wet conditions as well as on snow, and also determines the noise development during driving.

[0006] In a rubber compound for a car tire tread, compared with industrial carbon black, the use of silanized precipitated silica as a reinforcing filler improves rolling resistance due to the chemical bond between the precipitated silicic acid and the elastomer of the rubber compound, and at the same time improves wet grip due to the polarity on the surface of the precipitated silica. Although tire wear is generally worse when using precipitated silica than when using industrial carbon black, this can be counteracted by an appropriate choice of the elastomer used (e.g., by using polybutadiene).

[0007] However, in a rubber compound for a truck tire tread, the use of silanized precipitated silica as a reinforcing filler does not achieve the abrasion resistance of industrial carbon black, especially because the above flexibility in the choice of elastomer as in car tires is not applicable here, and natural rubber is mainly used for truck treads.

[0008] Another disadvantage when using chemically modified and especially silanized precipitated silica in rubber compositions, especially for the production of tire treads in cars and trucks, is that the stress value at small deformations is lower than in the case of using industrial carbon black. This is particularly evident in cases where dynamic cyclic deformations can occur. To adjust the special tire properties regarding driving dynamics, industrial carbon black must therefore be additionally used, but for the reasons mentioned above, this is not desirable.

[0009] In addition, such rubber compounds are often used both in industrial rubber products and in the tire industry: in which the specific surface area of the precipitated silica used is relatively high, e.g., in the range of 100 to 250 m 2 / g (BET surface area). Although less heat is released during mechanical deformation (hysteresis) when used in car treads, which improves rolling resistance, the advantage compared to industrial carbon black, which usually has a significantly lower specific surface area in the range of BET 30 to 50 m 2 / g, is usually no longer obvious. In addition, a lower dynamic stiffness is often observed compared to rubber compounds containing industrial carbon black as a reinforcing filler.

[0010] Lignin-based bio-renewable raw materials, such as lignin in the form of hydrothermal carbonization (HTC lignin), are also used as organic fillers in rubber compositions. They represent a more environmentally friendly filler option compared to inorganic fillers and industrial carbon black.

[0011] EP 3 470 457 A1 describes a rubber blend containing HTC lignin. However, the disadvantages of using such HTC lignin in rubber compositions are generally that the compatibility between the relatively polar HTC lignin and the relatively non-polar rubber is generally too low or insufficient. Additionally, disadvantages are often observed in terms of the anti-aging properties and long-term stability of rubber compositions containing HTC lignin, especially in the vulcanized form, because due to the high proportion of free hydroxyl groups in HTC lignin, undesired reactions can occur, which have an adverse effect on the anti-aging properties and long-term stability.

[0012] In other application fields, generally in the field of producing rubber compositions for tires, WO 2017 / 085278 A1 discloses the use of particulate carbon materials, and in particular HTC lignin, as an alternative filler to industrial carbon black. Similarly, the related disadvantages described above with respect to EP 3 470 457 A1 often occur. WO 2017 / 085278 A1 also describes that the material can be in-situ modified with an organosilane as a coupling agent after being introduced into the rubber composition. However, the disadvantages of using such organosilane-modified carbon materials described in WO2017 / 085278 A1 are generally that the Si-O-C chemical bond formed between the material and the organosilane coupling agent has low thermodynamic stability, so this bond can be relatively easily hydrolyzed, and thus undesired de-coupling reactions and lower filler-rubber interactions can occur within the rubber composition, but these phenomena should be avoided because they can lead to deterioration of the properties of the rubber composition during and after vulcanization. Additionally, the coupling efficiency of the above carbon material with the organosilane coupling agent is generally too low because the proportion of the self-condensation reaction of the used organosilane is unfavorably high, and thus it can no longer be used for practical modification. Another disadvantage comes from only performing in-situ modification within the produced rubber composition because such in-situ modification generally limits the degree of freedom in producing the composition and the components contained therein to an undesired extent, especially when the above carbon material is used in combination with other fillers, such as other fillers, especially inorganic fillers, such as silica / silicon dioxide. Another disadvantage is that compared with the case of using industrial carbon black, the in-situ reaction with the organosilane requires an additional mixing stage, and for cost reasons, this additional mixing stage is generally not used in the production of industrial rubber products and most tire components (such as sidewalls, inner liners).

[0013] Finally, WO 2017 / 194346 A1 also describes the use of HTC lignin in rubber blends for pneumatic tire components, especially in combination with methylene donor compounds such as hexakis(methoxymethyl)melamine, thereby increasing the stiffness of the cured rubber components of pneumatic tires and additionally replacing phenolic resins. WO 2017 / 194346 A1 also mentions that organosilanes can be used as coupling agents for in-situ modification. However, it also has the same drawbacks as those described in WO 2017 / 085278 A1.

[0014] Therefore, there is a need for novel organic fillers suitable for introduction into rubber compositions, as well as such rubber compositions that do not have the above-mentioned drawbacks themselves.

[0015] Problem

[0016] Therefore, an object of the present invention is to provide environmentally friendly fillers that are suitable for direct introduction into rubber compositions as such, especially for tire components such as tire treads, and tire components for tire substructures (frames); and / or to provide components for industrial rubber articles, especially in view of improving the anti-aging properties and long-term stability of rubber compositions, even in vulcanized form; to improve the resistance to media and hydrolysis compared to fillers of the prior art, and to improve mechanical properties such as modulus, tensile strength, and elongation at break. Additionally, an object of the present invention is to provide corresponding rubber compositions containing these fillers.

[0017] Solution

[0018] The above object is solved by the subject matter claimed in this application and the preferred embodiments disclosed in this specification, that is, by the subject matter described herein.

[0019] The first subject matter of the present invention is an organic filler having a 14 C content in the range of 0.20 to 0.45 Bq / g carbon and a BET surface area in the range of 10 to <200 m 2 / g,

[0020] characterized in that at least a part of the hydroxyl groups present in the chemical structure of the organic filler and bonded to at least one aliphatic carbon atom have been replaced by an organic residue containing one or more sulfur atoms covalently bonded thereto, wherein at least one sulfur atom is adjacent to a carbon atom within the organic residue, such that an aliphatic carbon-sulfur-carbon bond has been formed and exists in the chemical structure of the organic filler.

[0021] The presence of an aliphatic carbon-sulfur-carbon bond, i.e., a C 脂族 -S-C- bond, in the chemical structure of the organic filler. The aliphatic carbon atoms (C 脂族) corresponding to at least one aliphatic carbon atom present in the chemical structure of the organic filler, the aliphatic carbon atom being bonded to a hydroxyl group. The sulfur atom (S) in such a bond corresponds to the sulfur atom present in the sulfur-containing organic residue and bonded to the above-mentioned aliphatic carbon atom (C 脂族 ) within the chemical structure of the organic filler of the present invention. The sulfur atom is also covalently bonded to other carbon atoms (C) of such a bond, and the other carbon atoms correspond to the carbon atoms adjacent to the sulfur atom within the sulfur-containing organic residue. Therefore, the other carbon atoms are different from the above-mentioned aliphatic carbon atoms. The C 脂族 -S-C- bond present in the chemical structure of the organic filler represents a thioether bond.

[0022] Another subject of the present invention is a rubber composition comprising at least one rubber and at least one filler component,

[0023] wherein the filler component comprises at least one organic filler as defined above and below,

[0024] and / or

[0025] wherein the filler component comprises: (i) at least one organic filler precursor FPM having a C 14 content in the range of 0.20 to 0.45 Bq / g of carbon, a BET surface area in the range of 10 to <200 m 2 / g, and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; and (ii) at least one organic modifier comprising at least one thiol group adjacent to a carbon atom within its chemical structure, via which thiol group, the hydroxyl group present in the chemical structure of the organic filler precursor FPM and bonded to at least one aliphatic carbon atom can be at least partially replaced by a covalently bonded sulfur-containing organic residue having one or more sulfur atoms, thereby forming a covalent bond connected to at least one organic filler precursor FPM, such that an aliphatic carbon-sulfur-carbon bond is formed in the chemical structure of the organic filler, wherein at least one sulfur atom present is derived from the thiol group of the organic modifier (ii), and an organic filler as defined above and below is formed.

[0026] Another subject of the present invention is a vulcanizable rubber composition comprising the rubber composition as defined above and below and a vulcanization system, the vulcanization system preferably comprising at least zinc oxide and / or at least sulfur or a sulfur donor and / or at least one peroxide, particularly preferably comprising at least sulfur.

[0027] Another subject of the present invention is a kit which comprises, in a spatially separated form, the rubber composition as defined above and below as part (A), and a vulcanization system as defined above and below as part (B).

[0028] Another subject of the present invention is a vulcanized rubber composition obtainable by vulcanizing a vulcanizable rubber composition as defined above and below, or by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (A) and (B) of a kit as defined above and below.

[0029] Another subject of the present invention is the use of an organic filler as defined above and below for the production of rubber compositions and vulcanizable rubber compositions, and the use of a rubber composition as defined above and below for the production of tires, preferably pneumatic and solid tires, in particular pneumatic tires, preferably in each case for the production of the tread, sidewall and / or inner liner of a tire, and / or for the production of industrial rubber articles, preferably profiles, seals, shock absorbers and / or hoses.

[0030] It has been found that the organic filler of the present invention is an environmentally friendly alternative to fillers known from the prior art, in particular replacing inorganic fillers such as silica and carbon black used in rubber applications.

[0031] It has also surprisingly been found that the organic filler of the present invention is suitable for direct introduction as such into rubber compositions, in particular for the production of the tread, sidewall and / or inner liner of a tire, such as pneumatic and solid tires; and / or for the production of industrial rubber articles, such as profiles, seals, shock absorbers and / or hoses.

[0032] It has furthermore surprisingly been found that the organic filler of the present invention has excellent compatibility with the rubber present in the rubber composition. In particular, it has been found that, due to the presence of covalently bonded organic residues containing one or more sulfur atoms in the chemical structure of the organic filler, including the resulting aliphatic carbon-sulfur-carbon bonds, i.e. by carrying out surface modification of the filler, the polarity of the filler can be reduced to an extent that improves the compatibility with relatively non-polar rubbers. In particular, it has been shown that, due to the presence of covalently bonded organic residues containing one or more sulfur atoms in the chemical structure of the organic filler, including the resulting aliphatic carbon-sulfur-carbon bonds, the compatibility can be further improved if the covalently bonded organic residues containing one or more sulfur atoms also contain at least one reactive functional group; when such a filler is used together with at least one rubber in a rubber composition, the reactive functional group is reactive towards at least one rubber and / or towards at least one functional group of the rubber and / or towards the vulcanization system used, in particular during the vulcanization process. In this case, at the latest moment during the vulcanization process, the filler may also bind to the rubber and / or the vulcanization system, which in addition to improving the compatibility also particularly improves the reinforcing properties (such as modulus, elongation at break, hysteresis, tear resistance and / or tensile strength) of the vulcanized composition.

[0033] Furthermore, it has surprisingly been found that if the covalently bonded organic residue containing one or more sulfur atoms comprises at least one reactive functional group which is capable of undergoing a crosslinking reaction with other identical reactive functional groups, for example in the case of alkoxysilyl groups as reactive functional groups which are reactive towards one another, and if at least two of said covalently bonded organic residues containing one or more sulfur atoms are present in the chemical structure of the organic filler, a (lateral) crosslinking reaction can be observed, which permits further modification of the surface of the organic filler. In this way, materials having the desired and / or tailor-designed properties can be produced in a targeted manner, for example by adjusting the surface porosity and / or density and / or adhesion or cohesion properties of the filler and / or its surface.

[0034] Furthermore, it has surprisingly been found that the organic fillers according to the invention are also capable of improving the aging resistance and long-term stability of the vulcanized form of the rubber composition. In this regard, it has surprisingly been found that, compared to the fillers of the prior art, the organic fillers according to the invention exhibit in particular increased resistance to media, especially to alkalis, and hydrolysis resistance. It has in particular been found that, due to the presence of covalently bonded organic residues containing one or more sulfur atoms in the chemical structure of the organic filler, including the resulting aliphatic carbon-sulfur-carbon bonds, i.e. by carrying out surface modification of the filler, not only can the abovementioned compatibility be improved, but also the proportion of aliphatic OH-groups can be reduced to an extent which prevents or at least reduces the potential occurrence of undesired reactions (with the aid of these groups) which would adversely affect the aging resistance and long-term stability. In this regard, it has in particular been found that, by carrying out surface modification, the susceptibility of the fillers according to the invention to hydrolysis can be reduced at least and the resistance to media, especially to alkalis, can be increased. This also improves the reinforcing properties of the vulcanized composition.

[0035] Furthermore, it has surprisingly been found that a suitable filler precursor (i.e. the filler FPM described below) can be covalently modified in a separate step ("off-site"), i.e. the covalently bonded organic residue containing sulfur atoms is introduced, so that in-situ incorporation in the rubber composition in the presence of rubber is not required. This has the particular advantage that: the organic fillers modified according to the invention can be used as fillers in the rubber composition in particular as such, and also in particular in combination with other fillers such as inorganic fillers, especially with (unmodified) silica; and especially if it is envisaged to modify other fillers (such as silica) with a suitable modifier (such as an organosilane) in the rubber composition and this modification must still be carried out in-situ. Thus, "off-site" modification allows the user to have greater freedom and flexibility in the preparation and formulation of the rubber composition and the components contained therein.

[0036] It has also surprisingly been found that due to the covalently bonded organic residues containing sulfur atoms, thermodynamically stable covalent C-S-C bonds are present in the chemical structure of the filler, which have a higher thermodynamic stability than, for example, the corresponding Si-O-C bonds formed when using non-functionalized silanes. This also results in improved hydrolysis resistance and can avoid or at least reduce undesired decoupling reactions and thus lower filler-rubber interactions within the rubber composition. Additionally, the advantage of using the modifier according to the invention is that a high coupling efficiency is obtained because no self-condensation reaction occurs, which can occur when, for example, using silanes containing non-thiol groups.

[0037] It has also surprisingly been found that the corresponding rubber compositions containing the organic fillers of the invention, in particular curable rubber compositions, can be used for the production of tires, such as pneumatic tires and solid tires, in particular pneumatic tires, preferably for the production of the tread, sidewall and / or inner liner of a tire in each case, and highly meet the necessary requirements for this purpose, in particular with regard to the balance between rolling resistance, abrasion resistance and wet grip performance and these performance requirements. Similarly, it has surprisingly been found that the corresponding rubber compositions containing the organic fillers of the invention, in particular curable rubber compositions, are suitable for the production of industrial rubber articles (rubber goods), in particular profiles, seals, shock absorbers and / or hoses.

[0038] It has also surprisingly been found that the vulcanized rubber compositions of the invention have improved mechanical properties, in particular with regard to tensile strength, Shore A hardness and resilience, compared to vulcanized rubber compositions containing organic fillers without sulfur-containing bonds, and sulfur-containing bonds are present in the chemical structure of the organic fillers of the invention.

[0039] It has also been particularly surprisingly found that the corresponding rubber compositions containing the organic fillers of the invention, in particular curable rubber compositions, can obtain vulcanized rubber compositions (vulcanized rubber compositions) characterized by an improved modulus at elongation up to 200%. In particular, it has been found that this is the case even when no industrial carbon black is used as an additional filler.

[0040] It has also been particularly surprisingly found that the corresponding rubber compositions containing the organic fillers of the invention, in particular curable rubber compositions, can obtain vulcanized rubber compositions which, when used as the tread of a tire in the field of passenger cars and especially trucks, can simultaneously improve rolling resistance and wet grip and at the same time have at least acceptable tire abrasion resistance compared to those vulcanized rubber compositions containing silanized precipitated silica instead of the organic fillers of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0042] When describing, for example, a rubber composition according to the present invention, a vulcanizable rubber composition according to the present invention, and process steps or stages in a method, the related term "comprising" preferably has the meaning of "consisting of". In this regard, for example, with respect to a rubber composition according to the present invention and a vulcanizable rubber composition according to the present invention, in addition to the components that must be present therein, these compositions may also contain one or more other optional components described below. All components may be present in the preferred embodiments described below. With respect to the methods according to the present invention described herein, in addition to the necessary steps and / or stages, these methods may also have optional process steps and stages.

[0043] The total amount of all components contained in the compositions described herein, such as a rubber composition according to the present invention and a vulcanizable rubber composition according to the present invention (each containing all necessary components and additionally all optional components) is 100% by weight in each case.

[0044] Organic filler with sulfur ether bond

[0045] As described above, the first subject of the present invention is an organic filler having a 14 C content in the range of 0.20 to 0.45 Bq / g carbon and having a BET surface area in the range of 10 to <200 m 2 / g,

[0046] characterized in that at least a part of the hydroxyl groups present in the chemical structure of the organic filler and bonded to at least one aliphatic carbon atom have been replaced by an organic residue containing one or more sulfur atoms covalently bonded, wherein at least one sulfur atom in the organic residue is adjacent to a carbon atom, such that an aliphatic carbon - sulfur - carbon bond has been formed and exists in the chemical structure of the organic filler.

[0047] Those skilled in the art are familiar with the term "filler", especially the term "organic filler". Preferably, the organic filler of the present invention is a reinforcing filler, i.e., an active filler. Compared with non - active (non - reinforcing) fillers, a reinforcing filler or an active filler can change the viscoelastic properties of the rubber by interacting with the rubber in the rubber composition. For example, the filler can affect the viscosity of the rubber and can improve the fracture behavior of the vulcanized rubber, such as in terms of tear propagation resistance, as well as wear resistance. On the other hand, non - active fillers dilute the rubber matrix.

[0048] Since the filler of the present invention is organic, the term does not include inorganic fillers such as precipitated silica.

[0049] The organic filler of the present invention has a 14The C content is preferably from 0.23 to 0.42 Bq / g of carbon. The C content required above is met by organic fillers obtained from further processing or conversion of biomass, preferably by fractionation, where the fractionation can be thermal, chemical, and / or biological, preferably thermal and / or chemical. Thus, fillers obtained from fossil materials, such as especially fossil fuels, are not within the definition of the fillers used according to the present invention, since they do not have the corresponding 14 C content. 14 C content.

[0050] "Biomass" is defined herein as any biomass. The term "biomass" in this text includes so-called phytomass, i.e., biomass derived from plants; biomass derived from animals; and microbial biomass, i.e., biomass derived from microorganisms, including fungi; the biomass is dry biomass or fresh biomass and is derived from dead or living organisms. Particularly preferred herein for the preparation of organic fillers is plant biomass, preferably dead plant biomass. Dead plant biomass includes, but is not limited to: dead, dead or detached plants and components. These include, for example, broken and torn leaves, cereal straws, side branches, twigs and branches, fallen leaves, fallen or pruned trees, and seeds and fruits, and components derived therefrom, as well as sawdust, and other products derived from wood processing.

[0051] Preferably, the organic filler according to the present invention has a carbon content in the range of 60% to 85% by weight, more preferably 63% to 80% by weight, very particularly preferably 65% to 75% by weight, especially 68% to 73% by weight, in each case based on the ash-free and water-free filler. The method for detecting the carbon content is described in the "Method" subsection below. The carbon content particularly distinguishes the organic filler from carbon blacks prepared from fossil raw materials and carbon blacks prepared from renewable raw materials, since these carbon blacks have a corresponding carbon content of at least 95% by weight.

[0052] Preferably, the organic filler according to the present invention has an oxygen content in the range of 15% to 30% by weight, preferably 17% to 28% by weight, particularly preferably 20% to 25% by weight, based on the ash-free and water-free filler. The oxygen content can be determined by high-temperature pyrolysis, for example, detected with the help of a EuroEA3000CHNS-O analyzer from EuroVector S.p.A.

[0053] The organic filler according to the present invention has a BET surface area (total specific surface area defined by Brunauer, Emmett, and Teller) in the range of 10 to <200 m 2 / g. The method for detecting this parameter is described in the "Method" subsection below. Particularly preferably, the organic filler according to the present invention has a BET surface area in the range of 10 to 150 m2 The BET surface area within the range of / g, most preferably within the range of 20 to 120 m 2 The BET surface area within the range of / g, even more preferably within the range of 30 to 110 m 2 The BET surface area within the range of / g, especially within the range of 40 to 100 m 2 The BET surface area within the range of / g, most preferably within the range of 40 to <100 m 2 The BET surface area within the range of / g.

[0054] The organic filler according to the present invention preferably has an STSA surface area within the range of 10 to <200 m 2 / g. The method for detecting the STSA surface area (statistical thickness surface area) is described in the "Method" section below. Preferably, the organic filler according to the present invention has an STSA surface area within the range of 10 to 150 m 2 / g, especially within the range of 20 to 120 m 2 / g, most preferably within the range of 30 to 110 m 2 / g, particularly within the range of 40 to 100 m 2 / g, most preferably within the range of 40 to <100 m 2 / g.

[0055] Preferably, the organic filler according to the present invention shows only conditional solubility in an alkaline medium, especially in 0.1 M or 0.2 M NaOH. The solubility is detected according to the method described below. Preferably, the solubility of the organic filler is less than 30%, more preferably less than 25%, most preferably less than 20%, even more preferably less than 15%, even more preferably less than 10%, further preferably less than 7.5%, even more preferably less than 5%, even more preferably less than 2.5%, especially preferably less than 1%.

[0056] Preferably, the organic filler is a lignin-based filler, more preferably a lignin-based filler obtainable by hydrothermal treatment (HTT). The lignin-based filler obtained by hydrothermal treatment is also referred to hereinafter as HTT lignin (“hydrothermally treated lignin”). In the literature, the term HTC lignin (“hydrothermally carbonized lignin”) is also often used. Fillers designated as HTC lignin are also within the scope of the term HTT lignin. The hydrothermal treatment carried out at a temperature of 150 °C to 250 °C in the presence of liquid water is also referred to hereinafter as hydrothermal treatment. Preferably, the organic filler according to the invention is a lignin-based organic filler prepared from biomass and / or biomass components. For example, before being modified according to the invention, lignin can be separated, extracted and / or dissolved from biomass for the production of lignin-based organic fillers. Suitable methods for obtaining lignin from biomass for the production of lignin-based organic fillers are, for example, hydrolysis or digestion methods, such as the Kraft cooking method. In the present invention, the term “lignin-based” preferably means that one or more lignin units and / or one or more lignin scaffolds are present in the organic filler of the present invention. Lignin is a solid biopolymer that is introduced into the plant cell wall, thus causing the lignification of plant cells. Therefore, lignin is present in biomass, especially in renewable raw materials, and thus represents an environmentally friendly filler option (especially in the form of hydrothermal treatment).

[0057] Due to its natural origin, lignin is a structurally heterogeneous phenolic biopolymer composed of different monomeric structural units and differing structurally according to its plant source. In particular, the molecular structure of lignin contains many different aliphatic OH-groups. It has now been found that they can be used to introduce organic residues containing one or more covalently bonded sulfur atoms into the aliphatic carbon atoms of such groups, in particular by substitution reactions using organic thiols as organic modifiers.

[0058] Preferably, the organic filler of the present invention is a lignin-based organic filler having a lignin content of at least 50% by weight, particularly preferably at least 60% by weight, most preferably at least 70% by weight, most preferably at least 80% by weight, in each case based on the total weight of the organic filler of the present invention. Preferably, the Klason lignin content in the organic filler of the present invention is at least 50% by weight, particularly preferably at least 60% by weight, most preferably at least 70% by weight, most preferably at least 80% by weight. The Klason lignin content is preferably determined as acid-insoluble lignin according to TAPPI T 222.

[0059] Preferably, the lignin and preferably the organic filler according to the invention itself (especially if it is a lignin-based filler) is at least partially present in the form of a hydrothermal treatment and can in each case preferably be obtained by a hydrothermal treatment. Particularly preferably, the organic filler according to the invention is based on lignin obtainable by a hydrothermal treatment. Suitable hydrothermal treatment methods, especially for lignin and lignin-containing organic fillers, can be found, for example, in WO 2017 / 085278 A1 and WO 2017 / 194346 A1 and EP 3 470 457 A1. Preferably, the hydrothermal treatment is carried out at a temperature of 150 °C to 250 °C in the presence of liquid water.

[0060] Preferably, the organic filler according to the invention has a pH in the range from 7 to 9, more preferably in the range from >7 to <9, and most preferably in the range from >7.5 to <8.5.

[0061] The organic filler according to the invention preferably has a d99 value of <25.0 μm. The method for detecting the d99 value is described in the "Method" section below and is carried out by laser diffraction according to ISO 13320:2009. The organic filler according to the invention preferably exists in particulate form. The average particle size of these particles is represented by the above-mentioned d99. Preferably, the organic filler has a d99 value of <20.0 μm, more preferably <15.0 μm, particularly preferably <10 μm, most preferably <9.0 μm, even more preferably <8.0 μm, even more preferably <7.0 μm, most preferably <6.0 μm, preferably measured in each case by laser diffraction according to ISO 13320:2009.

[0062] As described above, aliphatic carbon-sulfur-carbon bonds, i.e., C 脂族 -S-C- bonds, are present in the chemical structure of the organic filler. The aliphatic carbon atom (C 脂族 ) in this bond corresponds to at least one aliphatic carbon atom present in the chemical structure of the organic filler, and this aliphatic carbon atom is bonded to a hydroxyl group. The sulfur atom (S) in this bond corresponds to the sulfur atom present in an organic residue containing one or more sulfur atoms and is bonded to the above-mentioned aliphatic carbon atom (C 脂族) Covalent bonding. The covalently bonded organic residue containing one or more sulfur atoms contains at least one sulfur atom, but may contain one or more additional sulfur atoms present. Thus, the expression "one or more sulfur atoms" includes the presence of only one sulfur atom or the presence of more than one sulfur atom. However, at least one sulfur atom within the organic residue is adjacent to a carbon atom such that an aliphatic carbon-sulfur-carbon bond has been formed and exists in the chemical structure of the organic filler. Preferably, the at least one sulfur atom is the sulfur atom from the mercapto group of the organic modifier used. The at least one sulfur atom is also covalently bonded to other carbon atoms (C) in such a bond, which corresponds to the carbon atom adjacent to the sulfur atom within the sulfur atom-containing organic residue. Thus, the other carbon atoms are different from the above-mentioned aliphatic carbon atoms, although they can also be and preferably are aliphatic carbon atoms. The C 脂族 -S-C- bond present in the chemical structure of the organic filler represents a thioether bond.

[0063] Preferably, the (other) carbon atom is adjacent to the above-mentioned sulfur atom in the covalently bonded sulfur atom-containing organic residue, and such (other) carbon atom is not part of an unsubstituted and / or saturated hexyl group. More preferably, the (other) carbon atom is adjacent to the above-mentioned sulfur atom in the covalently bonded sulfur atom-containing organic residue, and if such (other) carbon atom is part of an unsubstituted and / or saturated straight-chain aliphatic group, it is part of such a group having at least 7 carbon atoms.

[0064] The polarity of the organic filler is advantageously changed by at least partial substitution of the hydroxyl groups that are bonded to at least one aliphatic carbon atom. Depending on the type of modifier used, a physical shielding effect may additionally occur.

[0065] Preferably, the organic filler does not contain an aliphatic carbon-sulfur-carbon bond in its chemical structure, where the latter carbon atom (i.e., the non-aliphatic carbon) is part of an unsubstituted and / or saturated hexyl group. More preferably, if the organic filler contains an aliphatic carbon-sulfur-carbon bond in its chemical structure, where the latter carbon atom (i.e., the non-aliphatic carbon) is part of an unsubstituted and / or saturated hexyl group, the minimum number of carbon atoms in such a group is at least 7. The number of at least 7 carbon atoms advantageously provides an improved physical shielding effect due to its longer-chain hydrophobic structural part.

[0066] Preferably, hydroxyl groups, more preferably primary hydroxyl groups (also referred to hereinafter as "aliphatic OH-groups") that are bonded to at least one aliphatic carbon are present on the surface of the organic filler particles (and thus are part of the chemical structure of the organic filler). Thus, in this case, such groups represent so-called surface-available groups. As a result, the formed aliphatic carbon-sulfur-carbon bonds (thioether bonds) are also preferably present on the surface of the organic filler particles.

[0067] Preferably, the hydroxyl groups of the organic filler, more preferably primary hydroxyl groups, are bonded to at least one aliphatic carbon atom and have been at least partially substituted by an organic residue containing one or more sulfur atoms covalently bonded as described above. These hydroxyl groups are attached to an aliphatic residue containing at least one aliphatic carbon atom, more preferably attached to a C 1-3 aliphatic or C 4-6 heteroaliphatic residue, even more preferably attached to a C3 aliphatic or C6 heteroalicyclic aliphatic residue, still more preferably attached to a C3 aliphatic residue, and still more preferably attached to a C3 alkyl residue.

[0068] The term "at least a portion" in relation to the expression "at least a portion of the hydroxyl groups present in the chemical structure of the organic filler and bonded to at least one aliphatic carbon atom have been substituted by (...)" means "partially" or "completely", but preferably means "partially". Further preferably, not all of the hydroxyl groups present in the chemical structure of the organic filler and bonded to at least one aliphatic carbon atom have been substituted by an organic residue containing one or more sulfur atoms covalently bonded.

[0069] Preferably, the organic residue containing one or more sulfur atoms is a divalent organic residue in which at least one sulfur atom is adjacent to an aliphatic carbon atom such that an aliphatic carbon-sulfur-aliphatic carbon bond has been formed and exists in the chemical structure of the organic filler. Preferably, the organic residue containing one or more sulfur atoms is part of an organic modifier containing at least one thiol group, and the at least one sulfur atom present in the organic residue containing a sulfur atom is derived from the thiol group of the organic modifier.

[0070] The organic residue containing one or more sulfur atoms preferably contains an organic group selected from the group consisting of aliphatic groups, cycloaliphatic groups, heteroaliphatic groups, heteroalicyclic aliphatic groups, aromatic groups, and heteroaromatic groups, more preferably selected from aliphatic groups, cycloaliphatic groups, and heteroaliphatic groups, even more preferably selected from aliphatic groups and heteroaliphatic groups, still more preferably selected from aliphatic groups, where in each case preferably an unsubstituted straight-chain group having 6 carbon atoms is excluded, especially where in each case the unsubstituted straight-chain aliphatic group has at least 7 carbon atoms.

[0071] Each of the above organic groups may be unsubstituted or substituted, especially substituted by at least one functional group. For example, the organic group may contain at least one functional group; when the filler of the present invention is used together with at least one rubber in a rubber composition, the functional group is reactive towards at least one rubber and / or towards at least one functional group of the rubber and / or towards the vulcanization system present in the rubber composition, especially during the vulcanization process, wherein the at least one functional group is preferably selected from the group consisting of: preferably non-conjugated and / or conjugated carbon-carbon double bonds, especially vinyl, and sulfur-containing groups, and mixtures thereof, particularly preferably selected from cis carbon-carbon double bonds, mercapto groups (which may optionally be blocked), disulfide and / or polysulfide groups, thioketone groups, mercaptobenzothiazole groups and carbamate groups and mixtures thereof. Additionally or alternatively, the organic group may contain at least one functional group which can increase the basicity of the filler after the formation of aliphatic carbon-sulfur-aliphatic carbon bonds in the chemical structure of the organic filler, particularly preferably an amino group, especially an amino group selected from primary and secondary amino groups. It may also be further chemically bonded to the filler via at least one other functional group FGB of the organic modifier, especially if the functional group is an amino group. Additionally or alternatively, the organic group may contain at least one alkoxysilyl group which allows crosslinking or lateral crosslinking within the organic filler via the formation of siloxane bonds.

[0072] Preferably, a hydroxyl group bonded to at least one aliphatic carbon atom remains in the chemical structure of the organic filler, i.e., an aliphatic OH-group remains, especially since only a part of such hydroxyl groups has been replaced by the covalently bonded organic residue containing a sulfur atom.

[0073] Preferably, the organic filler further contains at least one functional group selected from the following: aromatic hydroxyl groups, preferably phenolic hydroxyl groups, including phenolate groups, and carboxylic acid groups, including carboxylate groups.

[0074] Preferably, the aliphatic carbon-sulfur-carbon bonds present in the chemical structure of the organic filler have been introduced into the chemical structure by reacting at least a part of the hydroxyl groups bonded to at least one aliphatic carbon atom with at least one organic modifier containing at least one mercapto group, the organic modifier containing at least one mercapto group adjacent to a carbon atom in its chemical structure, more preferably introduced by a substitution reaction, wherein at least a part of these hydroxyl groups have been replaced by a covalently bonded organic residue containing a sulfur atom, and the sulfur atoms present are derived from the mercapto groups of the organic modifier.

[0075] The organic modifier contains at least one mercapto group adjacent to a carbon atom in its chemical structure, and at least one mercapto group in at least one of the organic modifiers may also be generated in situ via a nucleophilic ring-opening reaction of a substituted or unsubstituted thioxolane, the thioxolane being used as a mercapto precursor.

[0076] Preferably, based on the total weight of the organic filler, the sulfur content is > 1.0 wt%, more preferably in the range of > 1.0 wt% to 5.0 wt%, even more preferably 1.1 wt% to 4.5 wt%, still more preferably 1.2 wt% to 4.0 wt%, even more preferably 1.3 wt% to 3.5 wt%, still more preferably 1.3 wt% to 3.0 wt%, especially 1.4 wt% to 2.5 wt%. The sulfur content is detected according to the method disclosed in the "Method" section.

[0077] Preferably, the organic modifier used is a non-polymeric modifier, more preferably a monomer. However, as described hereinafter, as an alternative, the organic modifier may preferably be a polymeric modifier.

[0078] Preferably, the aliphatic carbon-sulfur-carbon bond in the chemical structure has been introduced by reacting at least a part of the hydroxyl groups bonded to at least one aliphatic carbon atom with at least one organic modifier, which is at least one thiol represented by the general formula (I):

[0079] R 1 -L 1 -SH

[0080] (I),

[0081] wherein L 1 is selected from C 2-30 alkylene, C 2-30 heteroalkylene, C 3-30 alkenylene, C 2-30 heteroalkenylene, C 3-30 alkynylene and C 2-30 heteroalkynylene, wherein one or more hydrogen atoms in any of these groups are optionally and / or independently replaced by at least one of a fluorine atom, a hydroxyl group and / or O-C 1-4 alkyl, and R 1 is an OH-group, O-C 1-4 alkyl, SH-group, S-C 1-4 alkyl, C(=O)OR 11 group, NR 11 R 12 group, NR 11 C(=O)NR 12 R 13 group, NR 11 C(=O)OR 12 、OC(=O)NR 11 R 12 group, S(=O)2NR 11 group, OPO3 2-a group or a salt thereof, an OC(=O)O group or a salt thereof, a C(NR 11 )R 12 group, an NR 11 CNR 12 NR 13 R 14 group, a C(=O)SR 11 or a C(=S)OR 11 group, or a halide, wherein R 11 、R 12 、R 13 and R 14 are independently selected from H, C 1-8 alkyl, C 1-8 alkenyl and C 1-8 alkynyl,

[0082] and / or

[0083] the organic modifier is at least one thiol represented by the general formula (II):

[0084] R 2 -SH

[0085] (II),

[0086] wherein R 2 is a C 1-30 hydrocarbyl group which may optionally contain one or more heteroatoms and / or heteroatom groups, wherein the heteroatoms are preferably selected from O, S and N, more preferably from O and S, even more preferably from O, and wherein the heteroatom groups are preferably selected from NH and NR, where R is a C 1-4 aliphatic residue, R 2 is preferably a C 1-30 hydrocarbyl group but does not include saturated and / or unsaturated C6 hydrocarbyl groups, more preferably does not include any C6 hydrocarbyl groups, even more preferably is a C 7-30 hydrocarbyl group, wherein in each case one or more hydrogen atoms are optionally and / or independently replaced by at least one of a fluorine atom, a hydroxyl group and / or an O-C 1-4 alkyl group,

[0087] and / or

[0088] the organic modifier is at least one thiol represented by the general formula (III):

[0089] Si(X) 3-y (Y) y -L 2 -SH

[0090] (III),

[0091] where y is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0,

[0092] where Y is a non-hydrolyzable organic residue, preferably C 1-30 alkyl, which is preferably unsubstituted; or represents the residue L 2 -SH, where L 2 has the definition described below,

[0093] wherein X independently of one another in each case represents a hydrolyzable group which is preferably reactive towards at least one of a phenolic OH-group, a phenolate group, an aliphatic OH-group, a carboxylic acid group, a carboxylate group, a silyl ether group and mixtures thereof, X preferably represents a hydrolyzable group selected from: O-C 1-4 alkyl, O(CH2) a -O(CH2) b -CH3 group, halides, and mixtures thereof, where a is an integer from 2 to 3, b is an integer from 1 to 14, and

[0094] where L 2 is a non-hydrolyzable divalent organic residue, preferably selected from C 1-30 alkylene, more preferably selected from C 1-16 alkylene, even more preferably selected from C 1-6 alkylene, most preferably selected from C 1-3 alkylene, where in each case one or more hydrogen atoms are optionally and / or independently replaced by at least one fluorine atom and O-C 1-4 alkyl, but preferably where each of the above-mentioned alkylene groups is unsubstituted,

[0095] and / or

[0096] the organic modifier is at least one thiirane of the general formula (IV) as a thiol precursor:

[0097]

[0098] where R 4 is a C 1-30 hydrocarbyl group which may optionally contain one or more heteroatoms and / or heteroatom groups, where the heteroatoms are preferably selected from O, S and N, more preferably from O and S, even more preferably from O, and where the heteroatom groups are preferably selected from NH and NR, where R is C 1-4 aliphatic residue, R 4 is preferably a C 7-30 hydrocarbyl group, where in each case one or more hydrogen atoms are optionally and / or independently replaced by at least one fluorine atom, hydroxyl group and / or O-C 1-4 alkyl,

[0099] and / or

[0100] The organic modifier is at least one polythiol polymer having at least two, or more preferably terminal, thiol groups, preferably at least one polysulfide having two, three, or more preferably terminal, thiol groups.

[0101] C as described above 2-30 heteroalkylidene, C 2-30 heteroalkenylidene and C 2-30 heteroalkynylidene, for example in relation to the definition of L 1 means an alkylidene, alkenylidene and alkynylidene which additionally contain one or more heteroatoms and / or heteroatom groups, where the heteroatoms are preferably selected from O, S and N, more preferably from O and S, even more preferably from O, and where the heteroatom groups are preferably selected from NH and NR, where R is a C 1-4 aliphatic residue. One or more heteroatoms and / or one or more heteroatom groups may be present within the respective group, i.e. may be located, for example, between two carbon atoms, as in the case of the C2H4-O-C2H4- group; or may alternatively or additionally represent the end of the respective group, as in the case of the O-C2H4-O-C2H4- group or the O-C2H4- group.

[0102] In the case where L 1 represents C 2-30 heteroalkylidene, the group is preferably selected from [(CH2) c O] d (CH2) e or [(CH2) c S] d (CH2) e , where c is an integer from 2 to 3, preferably 2; d is an integer from 1 to 6, preferably an integer from 2 to 4, more preferably d is 2; and where e is an integer from 2 to 4, preferably an integer from 2 to 3, more preferably e is 2.

[0103] C 1-30 The hydrocarbon group may optionally contain one or more heteroatoms and / or heteroatom groups in the position R of formula (II) and may be, for example, C 2 heteroalkylidene, such as [(CH2) 2-30 O] c (CH2) d or [(CH2) e S] c (CH2) d (CH2) e , where c is an integer from 2 to 3, preferably 2; d is an integer from 1 to 6, preferably an integer from 2 to 4, more preferably d is 2; and where e is an integer from 2 to 4, preferably an integer from 2 to 3, more preferably e is 2.

[0104] Examples of the thiols of the general formula (III) are mercaptoalkyltrialkoxysilanes, such as mercaptomethyltrimethoxysilane and / or mercaptopropyltrimethoxysilane. An example of the thiol of the general formula (I) is 1,2-bis(2-mercaptoethoxy)ethane.

[0105] The aliphatic carbon-sulfur-carbon bonds in the chemical structure as described above may have been optionally and / or additionally introduced by reacting at least a part of the hydroxyl groups bonded to at least one aliphatic carbon atom with at least one organic modifier, which is at least one polythiol polymer having at least two or more preferably terminal thiol groups, such as a polythiol polymer, such as a polysulfide having two, three or more preferably terminal thiol groups. Preferably, the polythiol polymer suitable for this purpose has a weight-average molecular weight (M w ) in the range of 500 to 50,000 g / mol, more preferably 500 to 25,000 g / mol, even more preferably 750 to 10,000 g / mol or 5,000 g / mol, M w which can be measured by gel permeation chromatography (GPC).

[0106] In the reaction scheme shown below, an example shows the possible reaction sequence for introducing the aliphatic carbon-sulfur-carbon bonds present in the chemical structure of the organic filler when using the thiols of the general formula (III) above. Here, HTT represents lignin having aliphatic OH-groups obtainable by hydrothermal treatment.

[0107] Reaction scheme: Possible reaction sequence:

[0108]

[0109] To prepare the organic filler of the present invention, an organic filler precursor FPM having a 14 C content in the range of 0.20 to 0.45 Bq / g carbon and a BET surface area in the range of 10 to <200 m 2 / g is suitable as a raw material, which contains at least one hydroxyl group bonded to at least one aliphatic carbon atom. At this time, no aliphatic carbon-sulfur-carbon bonds have been formed. At least in this way, the filler precursor FPM is different from the organic filler of the present invention.

[0110] Preferably, the organic filler can be obtained by performing at least one step a) and optionally one or more steps b) to d), namely:

[0111] a) Combining at least one organic modifier and at least one organic filler precursor FPM, the organic modifier containing at least one thiol group adjacent to a carbon atom in its chemical structure, the organic filler precursor FPM having a 14a C content, a BET surface area in the range from 10 to <200 m 2 / g, and having at least one hydroxyl group bonded to at least one aliphatic carbon atom,

[0112] b) Optionally heating the mixture obtained according to step a), which mixture is preferably present in a liquid or gaseous reaction medium or represents a solid phase, preferably heating the mixture to a temperature in the range from 30 °C to 190 °C, more preferably to a temperature in the range from 50 °C to 180 °C, most preferably to a temperature in the range from 70 °C to 170 °C,

[0113] c) In the case where step a) and / or the optional heating operation according to step b) have been carried out in a liquid reaction medium containing at least one organic solvent, after at least a part of the hydroxyl groups bonded to at least one aliphatic carbon atom of the organic filler precursor FPM have been replaced by organic residues containing one or more sulfur atoms which are covalently bonded, optionally extracting at least one organic solvent, wherein at least one sulfur atom present is derived from the thiol groups of the said organic modifier, and

[0114] d) Optionally, drying the organic filler obtained after carrying out step a) and optionally step b) and / or c), which is preferably carried out under vacuum and / or at a temperature in the range from 20 to 100 °C.

[0115] The combining step according to step a) and the optional heating step according to the optional step b) can be carried out in a reaction medium, which reaction medium is preferably liquid or gaseous. The organic modifier and / or the filler precursor FPM and / or the resulting mixture can each optionally be present in a liquid or gaseous reaction medium. Thus, the liquid reaction medium can preferably contain at least one organic solvent or consist of at least one organic solvent, particularly preferably at least one hydrocarbon, most preferably at least one aliphatic hydrocarbon and / or aromatic hydrocarbon. In the case of a gaseous reaction medium, the organic modifier can be covalently bonded to the filler precursor FPM by CVD (chemical vapor deposition) and / or plasma modification.

[0116] Preferably, step a) is carried out at room temperature (18 to <30 °C). Under these conditions, the organic modifier can also already be covalently bonded to the filler precursor FPM. Step b) is carried out optionally, but preferably. In this case, the organic modifier is preferably covalently bonded to the filler precursor FPM in the temperature range as described above for step b).

[0117] According to the optional step c), the extraction is preferably carried out at a temperature in the range from 20 to 150 °C and can optionally be carried out under vacuum.

[0118] Preferably, after and / or during performing step a) and optional step b), the reaction mixture is mixed for a time of from 0.01 to 30 hours, particularly preferably from 0.01 to 5 hours, which is effected, for example, by stirring, in particular to achieve complete reaction with the amounts of organic modifier used.

[0119] Preferably, the organic filler of the present invention is present in a rubber-free form and / or is prepared in a rubber-free form. This particularly means that the formation of aliphatic carbon-sulfur-carbon bonds in the chemical structure of the organic filler does not occur in situ within the rubber composition or in the presence of rubber, but rather occurs in a separate step ("off-site").

[0120] Preferably, after the formation of aliphatic carbon-sulfur-carbon bonds, the organic filler of the present invention contains from 0.1 to 30% by weight, particularly preferably from 0.5 to 25% by weight, most preferably from 1 to 15% by weight, especially from 1.5 to 12% by weight of an organic modifier, based on its total weight. Of course, it is taken into account here that during the substitution reaction between the thiol groups of the organic modifier and the aliphatic hydroxyl groups of the organic filler precursor FPM, cleavage products, such as water, can be formed, so these cleavage products do not contribute to the proportion of modifier in the filler.

[0121] Rubber composition

[0122] Another subject of the present invention is a rubber composition comprising at least one rubber and at least one filler component,

[0123] wherein the filler component comprises at least one organic filler as defined above and below,

[0124] and / or

[0125] wherein the filler component comprises: (i) at least one organic filler precursor FPM having a 14 C content in the range from 0.20 to 0.45 Bq / g carbon, a BET surface area in the range from 10 to <200 m 2 / g, and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; and (ii) at least one organic modifier comprising at least one thiol group adjacent to a carbon atom in its chemical structure, via which thiol group, at least part of the hydroxyl groups present in the chemical structure of the organic filler precursor FPM and bonded to at least one aliphatic carbon atom can be substituted by a covalently bonded organic residue containing one or more sulfur atoms, thereby forming a covalent bond to at least one organic filler precursor FPM, such that an aliphatic carbon-sulfur-carbon bond is formed in the chemical structure of the organic filler, wherein at least one of the sulfur atoms present is derived from the thiol group of the organic modifier (ii), and an organic filler as defined above and below is formed.

[0126] All preferred embodiments described above for the organic filler of the present invention are also preferred embodiments for the rubber composition of the present invention.

[0127] Preferably, the filler component comprises at least one organic filler of the present invention as described in the first subject matter of the present invention.

[0128] Any type of rubber is suitable for producing the rubber blend according to the present invention. Natural rubber (NR) and synthetic rubbers are known to those skilled in the art. Preferably, at least one rubber is selected from the following rubbers: natural rubber (NR), halogenated butyl rubber, more preferably selected from chlorobutyl rubber (CIIR; chloro-isobutene-isoprene rubber) and bromobutyl rubber (BIIR; bromo-isobutene-isoprene rubber), and mixtures thereof, butyl rubber or isobutene-isoprene rubber, isobutene-isoprene rubber (IIR; isobutene-isoprene rubber), styrene-butadiene rubber (SBR, styrene butadiene rubber), more preferably SSBR and / or ESBR, polybutadiene (BR, butadiene rubber), acrylonitrile-butadiene rubber (NBR, nitrile rubber) and / or HNBR (hydrogenated NBR), chloroprene (CR), polyisoprene (IR), ethylene-propylene-diene rubber (EPDM), and mixtures thereof.

[0129] Particularly preferred is at least one rubber selected from the following: styrene-butadiene rubber (SBR, styrene butadiene rubber), more preferably SSBR, polybutadiene (BR, butadiene rubber), EPDM, NR and acrylonitrile-butadiene rubber (NBR, nitrile rubber) and mixtures thereof. Particularly preferred is styrene-butadiene rubber (SBR, styrene butadiene rubber), more preferably SSBR and polybutadiene (BR, butadiene rubber) and mixtures thereof.

[0130] In the case of a blend of SBR and BR, the proportion of SBR is preferably higher than that of BR. The total amount of SBR rubber is preferably 60 to 100 phr, preferably 65 to 100 phr, particularly preferably 70 to 100 phr. The total amount of BR rubber is preferably 0 to 40 phr, preferably 0 to 35 phr, particularly preferably 0 to 30 phr.

[0131] The specification phr (parts per hundred parts of rubber by weight) used herein is a dosage specification commonly used in the rubber industry for compounding formulations. The weight part dosage of each component is always based on the total mass of 100 weight parts of all rubbers present in the compound.

[0132] Preferably, the rubber composition comprises from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, especially from 40 to 100 phr of at least one organic filler, and / or comprises from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, especially from 40 to 100 phr of at least one organic filler precursor FPM as described in (i) above, and from 0.1 - 30% by weight, particularly preferably from 0.5 - 25% by weight, most preferably from 1.0 - 15% by weight, especially from 1.5 - 12% by weight of at least one organic modifier as described in (ii) above, in each case based on the total weight of the organic filler precursor FPM. As explained above, any elimination products formed do not contribute to the amount of the organic modifier based on the total weight of the filler FPM.

[0133] In addition to the organic filler and / or organic filler precursor FPM according to the invention, the rubber composition may also contain other fillers different from these fillers.

[0134] In the case where the organic filler of the present invention only partially replaces conventional industrial carbon black, the rubber composition of the present invention may also contain industrial carbon black, especially furnace black, such as those for general purposes, or industrial carbon black with ASTM number N660.

[0135] Additionally or as an alternative, the rubber composition of the present invention may particularly contain inorganic fillers, for example, having different particle sizes, particle surface areas and chemical properties, and different potentials for influencing vulcanization properties. In the case of containing other fillers, these other fillers should preferably have properties as similar as possible to the organic fillers of the present invention used in the rubber composition of the present invention, especially in terms of their pH.

[0136] If other fillers are used, these other fillers are preferably phyllosilicates, such as clay minerals, such as talc; carbonates, such as calcium carbonate; silicates, such as calcium silicate, magnesium silicate and aluminum silicate; and oxides, such as magnesium oxide and silica or silicic acid.

[0137] In particular, in the case where the organic filler of the present invention only partially replaces conventional silica or silicon dioxide, the rubber composition of the present invention may also contain such inorganic fillers, such as silica or silicic acid.

[0138] However, in the present invention, zinc oxide is not counted as an inorganic filler because the role of zinc oxide is a vulcanizing agent or a vulcanization promoting additive. However, the additional fillers should be carefully selected because a higher amount of magnesium oxide, for example, can adversely affect the adhesion to adjacent tire layers, and silica tends to bind organic molecules used in some vulcanization systems, such as thiazoles, on its surface, thereby inhibiting their action.

[0139] Inorganic fillers, including preferably silica and other fillers bearing Si-OH groups on their surface, can also be surface-treated (surface-modified). In particular, it can be advantageous to use silanes for silanization, such as alkylalkoxysilanes or aminoalkylalkoxysilanes or mercaptoalkylalkoxysilanes. For example, the alkoxysilyl groups can be bonded to the surface of silicates or silica by hydrolysis and condensation, or to other suitable groups, while the amino groups and thiol groups can react, for example, with the isoprene units of certain rubbers. This can provide mechanical reinforcement to the vulcanized rubber composition of the present invention.

[0140] Fillers different from the organic fillers of the present invention can be used alone or in combination with each other.

[0141] In the case of using other fillers, their proportion is preferably less than 40 phr, more preferably 20 to 40 phr, and particularly preferably 25 to 35 phr.

[0142] The rubber composition of the present invention can contain other optional components, such as plasticizers and / or anti-degradants, resins, especially adhesion-promoting resins, and even vulcanizing agents and / or vulcanization-promoting additives, such as zinc oxide and / or fatty acids, such as stearic acid.

[0143] The use of plasticizers can particularly affect the properties of the unvulcanized rubber composition, such as processability, and the properties of the vulcanized rubber composition, such as flexibility, especially at low temperatures. Particularly suitable plasticizers in the present invention are mineral oils, which are selected from paraffinic oils (substantially saturated linear hydrocarbons) and naphthenic oils (substantially saturated cyclic hydrocarbons). Aromatic oils can also be used, and even preferably aromatic oils are used. However, with respect to the rubber composition towards other rubber-containing components in a tire, such as the carcass, a mixture of aromatic oil and paraffinic oil and / or naphthenic oil can also be advantageously used as a plasticizer. Other possible plasticizers include esters of aliphatic dicarboxylic acids, such as adipates or sebacates, kerosene waxes and polyethylene waxes. Among the plasticizers, paraffinic oils and naphthenic oils are particularly suitable for the present invention, but most preferably aromatic oils, especially aromatic mineral oils.

[0144] Preferably, the amount of plasticizer, very preferably the paraffinic oils and naphthenic oils described herein, especially aromatic processing oils, is 0 to 100 phr, preferably 10 to 70 phr, more preferably 20 to 60 phr, and especially 20 to 50 phr.

[0145] Examples of anti-degradants include quinoline, such as TMQ (2,2,4-trimethyl-1,2-dihydroquinoline), and diamines, such as 6-PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine).

[0146] To improve the adhesion of the vulcanized rubber blend of the present invention to other adjacent tire components, so-called adhesion promoting resins can be used. Particularly suitable resins are those based on phenol, preferably selected from phenolic resins, phenol-formaldehyde resins, and phenol-acetylene resins. In addition to phenolic resins, aliphatic hydrocarbon resins can also be used, such as Escorez TM 1102RM from ExxonMobil Corporation, and aromatic hydrocarbon resins. Aliphatic hydrocarbon resins particularly improve the adhesion to other rubber components in the tire. They generally have lower adhesion than phenolic resins and can be used alone or in combination with phenolic resins.

[0147] If an adhesion promoting resin is used, it is preferably selected from phenolic resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins. Preferably, the content of the resin is 0 to 15 phr or 1 to 15 phr, more preferably 2 to 10 phr, and most preferably 3 to 8 phr.

[0148] The rubber composition of the present invention can also contain additives that promote vulcanization but do not independently trigger vulcanization. Such additives include, for example, vulcanization accelerators, such as saturated fatty acids having 12-24, preferably 14-20, particularly preferably 16-18 carbon atoms, such as stearic acid, and zinc salts of the above fatty acids. These additives can also include thiazoles. However, it is also possible to use only vulcanization promoting additives in the vulcanization system, as described below.

[0149] If vulcanization promoting additives, especially the above fatty acids and / or their zinc salts, preferably stearic acid and / or zinc stearate, are used in the rubber composition of the present invention, then their proportion is 0 to 10 phr, particularly preferably 1 to 8 phr, and especially preferably 2 to 6 phr.

[0150] In addition, the rubber composition of the present invention may already contain certain vulcanizing agents, such as zinc oxide, which is preferred. However, it is also possible to use only such vulcanizing agents in the vulcanization system, as described below.

[0151] If a vulcanizing agent such as zinc oxide is used in the rubber composition of the present invention, then its proportion is preferably 0 to 10 phr, more preferably 1 to 8 phr, and especially preferably 2 to 6 phr.

[0152] Vulcanizable rubber composition

[0153] Another subject of the present invention is a vulcanizable rubber composition comprising a rubber composition and a vulcanization system as defined above and below, the vulcanization system preferably comprising at least zinc oxide and / or at least sulfur or a sulfur donor and / or at least one peroxide, particularly preferably at least comprising sulfur.

[0154] All preferred embodiments described above with respect to the organic fillers of the present invention and the rubber compositions of the present invention are also preferred embodiments with respect to the curable rubber compositions according to the present invention.

[0155] In the present invention, the term "vulcanization" means "crosslinking", and the term "vulcanization system" in the present invention means "crosslinking system". Similarly, "curable" means "crosslinkable", and "vulcanized" means "crosslinked". These definitions are known to those skilled in the art. For example, see PAC 2007, 79, pages 1801 to 1826, and see F. and F. Sommer's "Kautschuk Technologie", 3rd edition, 2013. In particular, the term "vulcanization" includes not only, for example, sulfur vulcanization, but also other types of crosslinking reactions, such as the use of peroxides.

[0156] Here, the vulcanization system is not considered as part of the rubber composition of the present invention, but as an additional system for regulating crosslinking. By adding a vulcanization system to the rubber composition of the present invention, a curable rubber composition according to the present invention is also obtained.

[0157] The rubber component in the curable rubber composition according to the present invention contains at least one rubber, and this rubber component allows the use of a variety of different vulcanization systems.

[0158] The vulcanization of the rubber composition of the present invention is preferably carried out using at least zinc oxide and / or at least sulfur and / or at least one peroxide, especially at least one organic peroxide. If zinc oxide is used, it can be added to the rubber component (A) or to the component (B). Preferably, zinc oxide is added to the component (A). If sulfur is used, it is preferably added to the component (B).

[0159] Preferably, at least zinc oxide and / or at least sulfur are combined with different organic compounds for vulcanization. Different additives can affect the vulcanization behavior and the properties of the resulting vulcanized rubber.

[0160] In a first variant where vulcanization is at least based on zinc oxide, it is preferred to add a small amount of saturated fatty acids having 12 - 24, preferably 14 - 20, particularly preferably 16 - 18 carbon atoms as vulcanization accelerators to the zinc oxide, such as stearic acid and / or zinc stearate. This allows an increase in the vulcanization rate. However, when using the said fatty acids, the final degree of vulcanization is usually reduced.

[0161] In a second variant which is vulcanized at least based on zinc oxide, a so-called thiuram, such as thiuram monosulfide and / or thiuram disulfide and / or tetrabenzylthiuram disulfide (TBzTD) and / or dithiocarbamate and / or sulfenamide, is added to zinc oxide in the absence or presence of sulfur, thereby shortening the scorch time and improving the vulcanization efficiency while forming a particularly stable network. Thiazole and sulfenamide are preferably selected from 2-mercaptobenzothiazole (MBT), mercaptobenzothiazole disulfide (MBTS), N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), 2-morpholinothiobenzothiazole (MBS) and N-tert-butyl-2-benzothiazolylsulfenamide (TBBS).

[0162] In a third variant which is vulcanized at least based on zinc oxide, alkyl dithiophenol is added to zinc oxide to adjust the scorch time, especially to accelerate them. Additionally, in a fourth variant which is vulcanized at least based on zinc oxide, a combination of zinc oxide with a polyhydroxymethylphenol resin and its halogenated derivatives is used, where preferably neither sulfur nor sulfur-containing compounds are used.

[0163] In a fifth variant which is vulcanized at least based on zinc oxide, which is the most preferred, vulcanization is carried out by a combination of zinc oxide with thiazole and / or thiuram and / or sulfenamide and preferably sulfur. Adding sulfur to these systems can simultaneously increase the vulcanization rate and degree of vulcanization, and contribute to the processability of the rubber composition during the vulcanization process. Using such a vulcanization system preferably provides a vulcanized rubber with heat resistance and fatigue resistance, which shows excellent adhesion to other components in vehicle tires, especially the rubber composition in the carcass, even when vulcanized. A particularly advantageous vulcanization system comprises zinc oxide, thiuram such as tetrabenzylthiuram disulfide (TBzTD), sulfenamide such as N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), and sulfur. Particularly preferred is the combination of the first variant and the fifth variant, i.e., the vulcanization system used comprises zinc oxide, thiuram such as tetrabenzylthiuram disulfide (TBzTD), sulfenamide such as N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), sulfur and stearic acid and / or optionally zinc stearate.

[0164] Less preferred vulcanization systems are based on pure sulfur-based vulcanization or peroxide vulcanization, the latter of which can lead to an undesired decrease in molecular weight due to molecular breakage, especially when using butyl rubber or other rubbers.

[0165] In the present invention, the vulcanization of the rubber composition of the present invention is carried out in the presence of the organic filler of the present invention, such as lignin obtained by hydrothermal treatment.

[0166] Those components in the vulcanization system that cannot trigger vulcanization by themselves can also be included in the rubber composition of the present invention as "other components of the rubber composition", that is, they can already be part of the rubber composition of the present invention, so it is not necessary to be included in the vulcanization system. Therefore, as described above, stearic acid and / or optionally zinc stearate may already be present in the rubber composition of the present invention, and a complete vulcanization system is formed in situ, for example, by mixing / adding at least zinc oxide and at least sulfur.

[0167] Kit

[0168] Due to the association between the rubber composition of the present invention and the crosslinking system (vulcanization system) selected for vulcanizing the vulcanizable rubber composition according to the present invention, the present invention also relates to a kit which contains, in a spatially separated form, the rubber composition as defined above and below as part (A), and a vulcanization system containing at least zinc oxide and / or at least sulfur as defined above and below as part (B).

[0169] In the kit, the rubber composition of the present invention and the vulcanization system are spatially separated from each other and can therefore be stored. The kit is used for preparing a vulcanizable rubber composition. For example, the rubber composition of the present invention that constitutes part of the kit can be used as part (A) in stage 1 of the following method for producing a vulcanizable rubber compound, and the second part of the kit, namely the vulcanization system, can be used as part (B) in stage 2 of the method.

[0170] The vulcanizable rubber composition already contains the components of the rubber composition of the present invention and the components of the relevant vulcanization system uniformly mixed, so that the vulcanizable rubber composition can be directly vulcanized; compared with such a vulcanizable rubber composition, in the kit of the present invention, the rubber composition of the present invention and the vulcanization system are spatially separated from each other.

[0171] All the systems described above regarding the vulcanizable rubber composition according to the present invention can be used as the vulcanization system.

[0172] All the preferred embodiments described above regarding the organic filler of the present invention and the (vulcanizable) rubber composition of the present invention are also the preferred embodiments regarding the kit of the present invention.

[0173] Preferably, the kit of the present invention comprises:

[0174] The rubber composition according to the present invention as part (A), and

[0175] A vulcanization system as part (B), the vulcanization system comprising at least zinc oxide and / or at least sulfur, wherein at least zinc oxide may optionally be present in part (A).

[0176] Particularly preferably, the kit of the present invention comprises:

[0177] The rubber composition according to the present invention as part (A), and

[0178] A vulcanization system as part (B), the vulcanization system comprising zinc oxide, sulfur and at least one thiuram, wherein at least the zinc oxide may optionally be present in part (A).

[0179] Even more preferably, the kit of the present invention comprises:

[0180] The rubber composition according to the present invention as part (A), and

[0181] A vulcanization system as part (B), the vulcanization system comprising zinc oxide, sulfur, at least one thiuram and at least one saturated fatty acid, such as stearic acid and / or optionally zinc stearate, wherein at least the zinc oxide and / or stearic acid and / or zinc stearate may optionally be present in part (A).

[0182] In particular, the kit of the present invention comprises:

[0183] The rubber composition according to the present invention as part (A), and

[0184] A vulcanization system as part (B), the vulcanization system comprising zinc oxide, sulfur, at least one thiuram, at least one sulfenamide and at least one saturated fatty acid, such as stearic acid and / or optionally zinc stearate, wherein at least the zinc oxide and / or stearic acid and / or zinc stearate may optionally be present in part (A).

[0185] The vulcanizable rubber composition according to the present invention is preferably prepared in two stages, namely stage 1 and stage 2, and preferably the rubber composition of the present invention can be obtained after the first stage of such a two-stage method.

[0186] In the first stage (stage 1), the rubber composition of the present invention is first prepared as a base mixture (masterbatch) by mixing together all the components for preparing the rubber composition of the present invention. In the second stage (stage 2), the components of the vulcanization system are added to the rubber composition of the present invention.

[0187] Stage 1

[0188] Preferably, at least one rubber contained in the rubber component of the rubber composition of the present invention is provided, and optionally a resin different from them that is available is provided, preferably to improve adhesion. However, the resin can be added together with other additives. Preferably, the rubber is at least at room temperature (23 °C), or preheated to a temperature of at most 50 °C, preferably at most 45 °C, particularly preferably at most 40 °C. Particularly preferably, the rubber is pre-kneaded for a short time before adding other components. If inhibitors are used for subsequent vulcanization control, such as magnesium oxide, it is also preferred to add these inhibitors at this time.

[0189] Subsequently, at least one organic filler of the present invention and optionally other fillers are added, preferably not including zinc oxide, because zinc oxide is used as a component of the vulcanization system in the rubber composition of the present invention and is not regarded as a filler here. The at least one organic filler of the present invention and optionally other fillers are preferably added in an incremental manner.

[0190] Advantageously but not necessarily, the plasticizer and other components, such as stearic acid and / or zinc stearate and / or zinc oxide (if used), are added only after adding at least one organic filler of the present invention or other fillers. This promotes the introduction of at least one organic filler of the present invention and other fillers if present. However, a part of the at least one organic filler of the present invention or other fillers if present can advantageously be introduced together with the plasticizer and any other components used.

[0191] The highest temperature ("pouring temperature") obtained during the production of the rubber composition in the first stage should not exceed 170 °C, because when the temperature is higher than this, the reactive rubber and / or organic filler of the present invention may undergo partial decomposition. However, temperatures > 170 °C, such as reaching < 200 °C, are also possible, especially depending on the rubber used. Preferably, the highest temperature during the production of the rubber composition in the first stage is between 80 °C and < 200 °C, particularly preferably between 90 °C and 190 °C, and most preferably between 95 °C and 170 °C.

[0192] The mixing operation of the components of the rubber composition of the present invention is generally carried out by an internal mixer equipped with a tangential rotor or an intermeshing (i.e., internal meshing) rotor. The latter generally allows better temperature control. A mixer with a tangential rotor is also called a tangential mixer. However, mixing can also be carried out, for example, using a two-roll mixer.

[0193] After the rubber composition is prepared, it is preferably cooled before the second stage. This process is also called aging. The typical aging time is 6 - 24 hours, preferably 12 - 24 hours.

[0194] Stage 2

[0195] In the second stage, the components of the vulcanization system are introduced into the rubber composition of the first stage, thereby obtaining the vulcanizable rubber composition according to the invention.

[0196] If a vulcanization system based on at least zinc oxide and at least sulfur is used as the vulcanization system, it is preferred to add at least sulfur and other optional components, such as in particular at least one thiuram and / or at least one sulfenamide, in stage 2. Zinc oxide can also be added in stage 2, and additionally optionally at least one saturated fatty acid, such as stearic acid. However, it is preferred to integrate these components into the rubber composition of the invention in stage 1.

[0197] The maximum temperature ("pouring temperature") obtained during the preparation of the mixture of the rubber composition and the vulcanization system in the second stage should preferably not exceed 130 °C, particularly preferably 125 °C. The preferred temperature range is 70 °C to 125 °C, particularly preferably 80 °C to 120 °C. Premature vulcanization can occur at temperatures higher than the maximum temperature of 105 to 120 °C for the crosslinking system.

[0198] After adding the vulcanization system in stage 2, the composition is preferably cooled.

[0199] In the above two-stage process, the rubber composition of the invention is first obtained in the first stage and added to the second stage to form a vulcanizable rubber composition.

[0200] Vulcanized rubber composition

[0201] Another subject of the invention is a vulcanized rubber composition which can be obtained by vulcanizing the vulcanizable rubber composition as defined above and below, or by vulcanizing the vulcanizable rubber composition obtained by combining and mixing the two parts (A) and (B) of the kit as defined above and below.

[0202] Before vulcanization, the obtained vulcanizable rubber composition is preferably subjected to a shaping process according to the design of the final product. The rubber composition is preferably shaped by extrusion or calendering into a suitable shape required for the vulcanization process. Vulcanization can occur in a vulcanization mold under pressure and temperature, or can occur in a temperature-controlled channel without pressure, where air or liquid material provides heat transfer.

[0203] All the preferred embodiments described above regarding the organic filler of the invention, the (vulcanizable) rubber composition of the invention and the kit of the invention are also preferred embodiments regarding the vulcanized rubber composition of the invention.

[0204] Vulcanization is generally carried out under pressure and / or heating. A suitable vulcanization temperature is preferably from 140 °C to 200 °C, particularly preferably from 150 °C to 180 °C. Optionally, vulcanization is carried out under a pressure in the range of 50 to 175 bar. However, vulcanization can also be carried out under a pressure range of 0.1 to 1 bar, for example in the case of profiles.

[0205] The vulcanized rubber composition obtained from the vulcanizable rubber composition according to the invention preferably has a Shore A hardness in the range of greater than 50 to less than 70, more preferably 53 to 65, most preferably 55 to 62, and / or a resilience in the range of greater than 60% to less than 75%, more preferably greater than 61% to less than 73%, most preferably greater than 62% to less than 72%. Methods for detecting Shore A hardness and resilience are provided in the description of the method below.

[0206] Use

[0207] Another subject of the present invention is the use of the organic filler as defined above and below for the production of rubber compositions and vulcanizable rubber compositions, and the use of the rubber composition as defined above and below for the production of tires, said tires being preferably pneumatic tires and solid tires, particularly pneumatic tires, preferably for the production of treads, sidewalls and / or inner linings of tires in each case, and / or for the production of industrial rubber articles, said industrial rubber articles being preferably profiles, seals, shock absorbers and / or hoses.

[0208] All preferred embodiments described above with respect to the organic filler of the present invention, the (vulcanizable) rubber composition of the present invention, the kit of the present invention and the vulcanized rubber composition of the present invention are also preferred embodiments with respect to the above-mentioned uses of the present invention.

[0209] For example, in order to produce a pneumatic tire, preferably including a tread, the tread can be prepared, for example, from a vulcanizable rubber composition according to the invention. The tread is usually vulcanized together with the tire carcass and / or other tire components under pressure and / or heat. A suitable vulcanization temperature is preferably from 140 °C to 200 °C, particularly preferably from 150 °C to 180 °C. This process can be carried out, for example, by molding a green tire into a closed mold by means of a closing press. For this purpose, a small pressure (<0.2 bar) can be applied to the inner bellows (heating bellows) so that the bellows also fits into the green tire. Then the press is closed, and thus the mold is also completely closed. The pressure inside the bellows increases (peak pressure, usually about 1.8 bar). This imprints the pattern onto the tread and sidewall markings. In the next step, the press is locked and a clamping force is applied. The clamping force varies depending on the type of press and the tire size and can be up to 2500 kN when using a hydraulic cylinder. After the clamping force has been applied, the actual vulcanization process is started. The mold is continuously heated from the outside with steam. A temperature between 150 and 180 °C is usually set here. Regarding the internal medium, there are very different design variants, depending on the tire type. For example, steam or hot water is used inside an airbag. The internal pressure can vary and is different depending on the tire type, such as a passenger car tire or a truck tire.

[0210] Method

[0211] 1. Detect the BET and STSA surface areas of the organic filler

[0212] The specific surface area of the filler under study was determined by the nitrogen adsorption method according to the ASTM D6556 (2019 - 01 - 01) standard for industrial carbon black. According to this standard, the BET surface area (total specific surface area defined by Brunauer, Emmett, and Teller) and the external surface area (STSA surface area; statistical thickness surface area) were also determined as follows.

[0213] Before the determination, the sample to be analyzed was dried at 105 °C to a dry matter content ≥ 97.5 wt%. Additionally, before weighing the sample, the measuring cell was dried in a drying oven at 105 °C for several hours. Then, the sample was loaded into the measuring cell using a funnel. If the upper channel of the measuring cell was contaminated during filling, it was cleaned using a suitable brush or pipe cleaner. In the case of materials that are significantly prone to flying (electrostatic), glass wool was weighed in addition to the sample. The glass wool was used to retain any flying material that could contaminate the instrument during the heating process.

[0214] The sample to be analyzed was baked at 150 °C for 2 hours, and the Al2O3 standard was baked at 350 °C for 1 hour. The subsequent N2 dosing was used for determination according to the pressure range:

[0215] p / p0 = 0 - 0.01: N2 - dosage: 5 ml / g

[0216] p / p0 = 0.01 - 0.5: N2 - dosage: 4 ml / g.

[0217] To detect BET, extrapolation is carried out in the range of p / p0 = 0.05 - 0.3, where there are at least 6 measurement points. To detect STSA, extrapolation is carried out in the range of the adsorbed N2 layer thickness t = 0.4 - 0.63 nm (corresponding to p / p0 = 0.2 - 0.5), where there are 7 measurement points.

[0218] 2. Detect the ash content of the organic filler (TGA; thermogravimetric analysis)

[0219] The anhydrous ash content of the sample is detected by thermogravimetric analysis according to the DIN 51719 standard as follows: Before weighing, the sample is crushed or ground in a mortar. Before detecting the ash, the dry matter content of the weighed material is detected. The sample material is weighed into a crucible, closest to 0.1 mg. The furnace containing the sample is heated to the target temperature of 815 °C at a heating rate of 9 °K / min, and then held at this temperature for 2 hours. Then the furnace is cooled to 300 °C before the sample is taken out. The ash content is detected. The sample is cooled to ambient temperature in a desiccator and re - weighed. The remaining ash is compared with the sample weight, and the ash content by weight is thus measured. Each sample is detected three times, and the average value is reported.

[0220] 3. Detect the pH value of the organic filler

[0221] The pH value is detected according to ASTM D 1512 as follows. If the dry sample is not obtained as a powder, it is ground or crushed into powder in a mortar. In each case, 5 g of the sample and 50 g of completely deionized water are weighed into a beaker. Using a magnetic stirrer with a heating function and a magnetic agitator, the suspension is heated to a temperature of 60 °C under constant stirring and the temperature is held at 60 °C for 30 minutes. Then, the heating function of the stirrer is stopped so that the batch can be cooled while stirring. After cooling, the evaporated water is replenished by adding completely deionized water again and stirring for another 5 minutes. The pH of the suspension is detected using a calibrated measuring instrument. The temperature of the suspension is 23 °C (±0.5 °C). Each sample is detected twice, and the average value is reported.

[0222] 4. Detection 14 C content

[0223] The 14 C content (bio - based carbon content) can be detected by the radiocarbon method according to DIN EN 16640:2017 - 08

[0224] 5. Detect the carbon content

[0225] The carbon content can be detected according to DIN 51732:2014-7 by elemental analysis.

[0226] 6. Detect the oxygen content

[0227] The oxygen content can be detected according to DIN 51732:2014-7 by elemental analysis. In this method, the CHNS content is detected by the above-mentioned analysis method, and then the oxygen content is calculated as the difference (100 - CHNS).

[0228] 7. Detect the particle size distribution

[0229] The particle size distribution can be detected by laser diffraction of materials dispersed in water according to ISO 13320:2020-01. A specified volume ratio is defined, for example, d99 in μm (the diameter of 99% of the particles in the sample volume is less than this value).

[0230] 8. Detect the solubility in alkaline medium

[0231] The detection of alkali solubility is carried out as described below:

[0232] The solubility is detected in three portions. For this purpose, 2.0 g of dry filler is weighed into 20 g of 0.1 M NaOH each. However, if the measured pH value of the sample < 10, the sample is discarded, and 2.0 g of dry filler is weighed into 20 g of 0.2 M NaOH each. Therefore, depending on the pH (< 10 or ≥ 10), 0.1 M NaOH (pH ≥ 10) or 0.2 M NaOH (pH < 10) is used. The alkaline suspension is shaken at a shaker speed of 200 / min for 2 hours at room temperature. To avoid the liquid contacting the lid during this process, the shaker speed is reduced to a level where this does not occur. Then, the alkaline suspension is centrifuged at 6000 g. The supernatant obtained by centrifugation is taken out and filtered through a Por 4 fritted glass. The solid obtained after centrifugation is washed twice with distilled water, and the above-mentioned centrifugation and filtration steps are repeated after each washing. The solid is dried in a drying oven at 105 °C for at least 24 hours until the weight is constant. The alkaline solubility of the solid is calculated as follows:

[0233] Alkaline solubility of solid [%] = mass of undissolved fraction [g] after centrifugation, filtration and drying * 100 / mass of initial product [g].

[0234] 9. 13 Solid-state C NMR

[0235] Using Bruker 9.4T (for 1 H operating at 400.34 MHz, for 13The C solid-state NMR (SSNMR) spectra were obtained on an Avance III HD 400 spectrometer operating at 100.67 MHz, equipped with a 4 mm magic angle spinning (MAS) probe. The spectra were acquired at a spinning rate of 14 kHz 13 using cross-polarization (CP) MAS detection, where the 90° pulse for 13 H was 2.4 μs and the contact time was 2 ms. 1 The C spectra were referenced internally to the chemical shift of the methoxy peak of lignin (δ = 56.1 ppm), obtained with 1486 complex points over a spectral width of 295 ppm, a relaxation delay of 2 s, and averaged up to 30000 times to ensure sufficient signal-to-noise ratio. 13

[0236] 10. Detect the sulfur content

[0237] The sulfur content can be detected by elemental analysis according to DIN 51724-1:2012-7.

[0238] Evaluate the mechanical properties 11.

[0239] The vulcanized rubber for the tensile test was cured for 30 minutes in a Wickert laboratory press in sheets of 90 x 90 x 2 mm. For the tensile test, the vulcanized sheets were cut into dumbbell-shaped specimens. The test was carried out on a Zwick Z020 Universal Tensile Tester at a crosshead speed of 500 mm / min according to ISO 37 Method A. Five samples were used to evaluate the tensile data. The average value obtained from these five samples was reported. 3

[0240] Detect the hardness of the compound 12.

[0241] The hardness of the samples was measured according to ISO 48 using a Zwick 3150 durometer, Shore A type, at 23 °C. This test was carried out for 30 minutes using cylindrical samples with a 6 mm thick base.

[0242] Examples

[0243] The following examples further illustrate the invention but are not to be construed as limiting the scope of the invention.

[0243] 1. Prepare the organic filler

[0244] 1.1 Organic filler precursor FPM1

[0245] The lignin FPM1 obtainable by hydrothermal treatment is used as a precursor material for organic fillers. The lignin FPM1 obtainable by hydrothermal treatment is prepared in a manner similar to the method for preparing lignin obtainable by hydrothermal treatment described in WO 2017 / 085278A1.

[0246] For this purpose, a liquid containing renewable raw materials is provided. First, water and lignin are mixed to obtain a lignin-containing liquid with an organic dry matter content of 15% by weight. Then, the lignin is completely dissolved in the lignin-containing liquid. For this purpose, the pH is adjusted to 9.8 by adding NaOH. The preparation of the solution is assisted by thorough mixing at 80 °C for 3 hours. Then, the lignin is dissolved in the liquid. The liquid containing renewable raw materials is subjected to hydrothermal treatment to obtain a solid. In this process, the resulting solution is heated to a reaction temperature of 220 °C at 1.4 K / min and held at this temperature for a reaction time of 7 hours. Then the solution is cooled. As a result, an aqueous solid suspension is obtained. The solid is mostly dehydrated and washed by filtration and washing. The dehydrated and washed solid is dried in a fluidized bed dryer to a residual moisture content of less than 3%. The dried solid is deflocculated on a NETZSCH steam jet mill under nitrogen to d99 < 20 μm. Subsequently, heat treatment is carried out in an oven under nitrogen, heated to a temperature of 230 °C and held at this temperature for 0.5 hours, and then cooled again.

[0247] 1.2 Organic filler precursor FPM2

[0248] Use the second lignin FPM2 obtainable by hydrothermal treatment, which is prepared according to a method similar to the method described in subsection 1.1. Hydrothermal treatment is carried out to provide a liquid containing renewable raw materials. First, water and lignin are mixed to prepare a lignin-containing liquid with an organic dry matter content of 15% by weight. Then, the lignin is completely dissolved in the lignin-containing liquid. For this purpose, the pH is adjusted to 9.8 by adding NaOH. The preparation of the solution is assisted by thorough mixing at 80 °C for 3 hours. Then, the lignin is completely dissolved in the liquid. The liquid containing renewable raw materials is subjected to hydrothermal treatment to obtain a solid. In this process, the resulting solution is heated to a reaction temperature of 220 °C at 1.4 K / min and held at this temperature for a reaction time of 7 hours. Then the solution is cooled. As a result, an aqueous solid suspension is obtained. The solid is mostly dehydrated and washed by filtration and washing. The dehydrated and washed solid is dried and heat-treated in a fluidized bed dryer under nitrogen, whereby the material is heated to 50 °C at 1.5 K / min for drying, and then further heated to 190 °C at 1.5 K / min, held at this temperature for 15 minutes, and cooled again. The dried solid is milled on the jet mill under nitrogen to de-aggregate to d99 < 10 μm. The milled solid is further processed in a ball mill under nitrogen and then sieved through a 200 μm sieve.

[0249] 1.3 Organic filler precursor FPM3

[0250] Use the third lignin FPM3 obtainable by hydrothermal treatment, which is prepared according to a method similar to the method described in subsection 1.2. However, different from the method described in subsection 1.2, the last step, i.e., de-aggregation by milling, is not carried out, and sieving is not carried out.

[0251] 1.4 The lignins FPM1, FPM2, and FPM3 obtained by hydrothermal treatment are characterized according to the above method, as shown in Table 1.1 below. All three lignins have a 14 C content in the range of 0.20 to 0.45 Bq / g carbon.

[0252] Table 1.1 - Properties of lignins FPM1, FPM2, and FPM3 obtained by hydrothermal treatment

[0253] Parameter Unit Lignin FPM1 Lignin FPM2 Lignin FPM3 Single-point BET <![CDATA[m 2 / g]]> 37 53.6 47.3 d99 volume ratio μm nd 5.08 5.74 Carbon content wt% nd 66.6 66.6 Ash content wt% nd 3.71 3.71 pH value . / . nd 8.7 8.7 Sulfur content wt% nd 0.96 0.96

[0254] nd = not detected

[0255] 1.5 Organic fillers according to the present invention

[0256] Prepare a variety of organic fillers according to the present invention, using the lignins FPM1 or FPM2 or FPM3 described in subsection 1.1 or 1.2 or 1.3 above as raw materials (precursors) in each case.

[0257] Modification of Lignin FPM1 - Example OF1

[0258] Weigh 2 g of lignin FPM1 and 8.46 mmol (50% of the molar amount of FPM1) of 3 - mercaptopropyltriethoxysilane (MPTES) and add them to a 100 mL round - bottom flask. Then, heat the resulting mixture to a temperature in the range of 160 ± 5 °C for 1 hour. Then, transfer the resulting mixture to a Soxhlet apparatus to extract the solvent, unreacted MPTES, and possible reaction by - products. The extraction is carried out using acetone for 24 hours. After extraction, the resulting product is dried in an oven under vacuum and at a temperature of 80 °C for 24 hours in each case. OF1 has a BET surface area within the required range.

[0259] Modification of Lignin FPM2 - Example OF2

[0260] Weigh 20 g of lignin FPM2 and 16 mmol of 1,2 - bis(2 - mercaptoethoxy)ethane (MEE) and add them to a 100 mL round - bottom flask which also contains 50 mL of toluene. Then, heat the resulting mixture to a temperature of 120 °C for 1 hour. Then, transfer the resulting mixture to a Soxhlet apparatus to extract the unreacted and / or physically adsorbed MEE and possible reaction by - products. The extraction is carried out using toluene for 12 hours. After extraction, the resulting product is dried in an oven under vacuum and at a temperature of 80 °C for 24 hours. The resulting organic filler OF2 is characterized by the above - mentioned method, as shown in Table 1.2 below.

[0261] Modification of Lignin FPM2 - Example OF3

[0262] Weigh 20 g of lignin FPM2 and 8 mmol of a liquid polysulfide polymer (LPST) with three terminal SH - groups and add them to a 100 mL round - bottom flask which also contains 50 mL of toluene. The liquid polysulfide polymer has a weight - average molecular weight (M w ) of 1016 g / mol. Then, heat the resulting mixture to a temperature of 120 °C for 1 hour. Then, transfer the resulting mixture to a Soxhlet apparatus to extract the solvent, unreacted and / or physically adsorbed LPST, and possible reaction by - products. The extraction is carried out using toluene for 12 hours. After extraction, the resulting product is dried in an oven under vacuum and at a temperature of 80 °C for 24 hours. The resulting organic filler OF3 is characterized by the above - mentioned method, as shown in Table 1.2 below.

[0263] Modification of Lignin FPM3 - Example OF4

[0264] 20 g of lignin FPM3 and 16 mmol of 1,2-bis(2-mercaptoethoxy)ethane (MEE) were weighed and added to a 100 mL round-bottom flask, which also contained 50 mL of toluene. Then, the resulting mixture was heated to a temperature of 120 °C for 3 hours. Then, the resulting mixture was transferred to a Soxhlet apparatus to extract unreacted and / or physically adsorbed MEE and possible reaction by-products. The extraction was carried out using toluene for 12 hours. After extraction, the resulting product was dried in an oven under vacuum and at a temperature of 80 °C for 24 hours. OF4 has a BET surface area within the required range.

[0265] Modification of Lignin FPM3 - Example OF5

[0266] 20 g of lignin FPM3 and 8 mmol of a liquid polysulfide polymer (LPST) with three terminal SH-groups were weighed and added to a 100 mL round-bottom flask, which also contained 50 mL of xylene. The liquid polysulfide polymer had a weight-average molecular weight (M w ) of 1016 g / mol. Then, the resulting mixture was heated to a temperature of 120 °C for 3 hours. Then, the resulting mixture was transferred to a Soxhlet apparatus to extract the solvent, unreacted and / or physically adsorbed LPST, and possible reaction by-products. The extraction was carried out using toluene for 12 hours. After extraction, the resulting product was dried in an oven under vacuum and at a temperature of 80 °C for 24 hours. OF5 has a BET surface area within the required range.

[0267] Table 1.2 - Properties of Lignin OF2 and OF3

[0268] Parameter Unit Lignin OF2 Lignin OF3 BET <![CDATA[m 2 / g]]> 48.7 45.6 Ash content wt% 4.69 4.85 Sulfur content wt% 1.53 1.48

[0269] The organic filler was further analyzed by 13 C NMR spectroscopy. It is clearly visible from Figure 1 that, compared with FPM1(a) in Figure 1 , additional peaks (indicated by the symbol ‘*’) in the 10 - 35 ppm region were observed for the OF1 sample (c) in Figure 1 . These peaks represent the carbon atoms of the aliphatic chains and correspond to the characteristic signals of MPTES chemically grafted onto the lignin surface. Therefore, the -S-C3H6-Si(OC2H5)3- residue of MPTES has been chemically bonded to OF1 as a sulfur-containing organic residue, bonding at least partially to the aliphatic carbon atoms of OF1 by partially replacing the OH-groups previously located on the aliphatic carbon atoms.

[0270] 1.6 Further Studies Based on Model Substances

[0271] Further studies were not based on either of the organic fillers FPM1 or FPM2, but rather on two model substances, namely VA (vanillyl alcohol) and G (guaiacol). This study, as a proof-of-concept study, showed that the sulfur atom-containing organic residues introduced into the filler chemical structure were indeed covalently bonded to the aliphatic carbon atoms previously bearing OH-groups, rather than any other positions. VA (vanillyl alcohol) and G (guaiacol) are simplified representative lignin structures in which either the phenolic hydroxyl group (G) or the combination of phenolic and aliphatic hydroxyl functional groups (VA) is modified.

[0272] For these studies, equimolar amounts (3 mmol) of VA or G and MPTES were taken in 5 ml ampoules. The vials containing the reaction mixture were immersed in an oil bath at 160 ± 5 °C and the reaction was carried out for 1 hour with continuous stirring. Then, the reaction was stopped immediately by quenching the vial in nitrogen. The resulting products were then studied in each case especially by liquid NMR 1D- and 2D-NMR, whereby different products were unambiguously confirmed from this correlation through single bond 13 C- 1 H coupling (HSQC) or multiple bond 13 C- 1 H coupling (HMBC).

[0273] It was found that when VA and MPTES reacted, the presence of aliphatic hydroxyl carbon (previously present in VA) was no longer detected by the NMR techniques used. In fact, it was found that the -S-C3H6-Si(OC2H5)3- residue of MPTES had been chemically bonded quantitatively as a sulfur atom-containing organic residue to VA, i.e., chemically bonded to the aliphatic carbon atom of VA (which aliphatic carbon atom was previously substituted by an OH-group), i.e., replacing the aliphatic OH-group. No other sulfur signals of MPTES were detected. It was also found that when G and MPTES reacted, MPTES did not react at all. Only the sulfur signal of MPTES could be detected.

[0274] 2. Prepare the vulcanizable rubber composition and the vulcanized rubber composition

[0275] A rubber composition was prepared as described below, having the components and amounts shown in Tables 2.1 and 2.2.

[0276] In particular, rubber compositions containing one of FPM2, OF2 and OF3 (Table 2.1) and containing one of FPM3, OF4 and OF5 (Table 2.2) were prepared. The units of the amounts / numbers shown in Tables 2.1 and 2.2 are phr in each case.

[0277] Table 2.1 - Rubber compositions R-FPM2, R-OF2 and R-OF3

[0278]

[0279] Table 2.2 - Rubber Compositions R - FPM3, R - OF4, and R - OF5

[0280]

[0281] SSBR - 4601 is a commercially available SSBR rubber. TDAE is a commercially available aromatic mineral oil. TBBS is N - tert - butyl - 2 - benzothiazole sulfenamide. TbzTD is tetrabenzylthiuram disulfide. ZnO is zinc oxide.

[0282] Two - stage mixing was carried out using a tangential rotor internal mixer (Brabender Plasticorder) with a chamber volume of 50 cm 3 For the mixing in Stage 1 (preparing the masterbatch), the mixer was operated at a 70% filling ratio, the rotor speed was 50 rpm, and the initial set temperature was 50 °C until compaction and ram sweep were carried out at 2:00. All the ingredients were added within 2 minutes.

[0283] Then, the rotor speed was changed to achieve the desired discharge temperature, and the compounds were mixed for 6 minutes.

[0284] Time (min:sec) Operation 0.00-2.00 Add rubber, filler, ZnO, stearic acid, TDAE 2.00-6.00 Mix and pour at a temperature between 95 °C and 170 °C

[0285] Mixing in Stage 2: The remaining ingredients were added, which was also carried out in the Brabender Plasticorder mixer, where it was operated at a 70% filling ratio, the rotor speed was 30 rpm, and the initial set temperature was 50 °C. After discharging the compound, they were processed on a two - roll mill with a gap width of 2.5 mm to form sheets.

[0286] 3. Properties of the vulcanized rubber composition

[0287] According to the above - mentioned testing methods, the properties of the vulcanized rubber compositions V - OF2, V - OF3, V - OF4, and V - OF5 of the present invention and the properties of the vulcanized rubber compositions V - FPM2 and V - FPM3 used as comparative examples were detected.

[0288] From Figure 2 It is clearly visible that, compared with the case of using the organic filler FPM2 without a thioether bond in the reference sample V - FPM2, using the organic fillers OF2 and OF3 with thioether bonds as fillers in the rubber compositions V - OF2 and V - OF3 improved the mechanical properties in terms of tensile strength. This indicates that the addition of OF2 and OF3 achieved better filler - rubber interaction than FPM2.

[0289] From Figure 3It is clearly visible that the use of organic fillers OF2 and OF3 also shows an improvement in the hardness of the vulcanized rubber composition compared to the case of using the organic filler FPM2.

[0290] Even when using the same relative proportions, for example 40 phr of fillers OF4 and OF5, in the corresponding curable rubber compositions V-OF4 and V-OF5, compared to the case of the reference sample V-FPM3 using a filler without a thioether bond ( Figure 4 ), the results obtained using the fillers of the present invention having a thioether bond show a significant improvement in mechanical properties. Moreover, in this case, compared to the comparative sample ( Figure 3 ), the use of the fillers of the present invention also shows an improvement in hardness.

Claims

1. An organic filler having a 14 C content in the range of 0.20 to 0.45 Bq / g of carbon and having a BET surface area in the range of 10 to <200 m 2 / g. It is characterized in that At least a portion of the hydroxyl groups that are present in the chemical structure of the organic filler and are bonded to at least one aliphatic carbon atom have been replaced by an organic residue containing one or more sulfur atoms that are covalently bonded, wherein at least one sulfur atom is adjacent to a carbon atom within the organic residue, such that an aliphatic carbon-sulfur-carbon bond has been formed and is present in the chemical structure of the organic filler.

2. The filler according to claim 1, characterized in that The hydroxyl group bonded to at least one aliphatic carbon atom in the organic filler is a hydroxyl group bonded to an aliphatic residue containing at least one aliphatic carbon atom, preferably such a hydroxyl group, more preferably a primary hydroxyl group: which is bonded to a C 1-3 aliphatic or C 4-6 heterocyclic aliphatic residue, more preferably bonded to a C3 aliphatic or C6 heterocyclic aliphatic residue, even more preferably bonded to a C3 aliphatic residue, still more preferably bonded to a C3 alkyl residue; and it is further characterized in that the organic residue containing one or more sulfur atoms is a divalent organic residue, within which at least one sulfur atom is adjacent to an aliphatic carbon atom, such that an aliphatic carbon-sulfur-aliphatic carbon bond has been formed and exists in the chemical structure of the organic filler.

3. The filler according to claim 1 or 2, characterized in that The aliphatic carbon-sulfur-carbon bond in the chemical structure is introduced by reacting at least a portion of the hydroxyl groups that are bonded to at least one aliphatic carbon atom with at least one organic modifier, the organic modifier containing at least one thiol group adjacent to a carbon atom within its chemical structure, preferably introduced by a substitution reaction, more preferably by a nucleophilic substitution reaction, wherein at least a portion of these hydroxyl groups have been replaced by an organic residue containing one or more sulfur atoms that are covalently bonded, and wherein at least one sulfur atom present is derived from the thiol group of the organic modifier.

4. The filler according to one or more of the preceding claims, characterized in that The carbon atom adjacent to the sulfur atom in the covalently bonded organic residue containing a sulfur atom is not part of an unsubstituted and / or saturated hexyl group.

5. The filler according to one or more of the preceding claims, characterized in that Hydroxyl groups that are bonded to at least one aliphatic carbon atom are still present in the chemical structure of the organic filler, particularly because only a portion of these hydroxyl groups have been replaced by an organic residue containing one or more sulfur atoms that are covalently bonded.

6. The filler according to one or more of the preceding claims, characterized in that The filler further comprises at least one functional group selected from: aromatic hydroxyl groups, preferably phenolic hydroxyl groups, including phenolate groups, and carboxylic acid groups, including carboxylate groups.

7. The filler according to one or more of the preceding claims, characterized in that The filler is a lignin-based filler, preferably a lignin-based filler obtainable by hydrothermal treatment.

8. The filler according to one or more of the preceding claims, characterized in that The aliphatic carbon-sulfur-carbon bond in the chemical structure is introduced by reacting at least a portion of the hydroxyl groups that are bonded to at least one aliphatic carbon atom with at least one organic modifier, the organic modifier being at least one thiol of the general formula (I): R 1 -L 1 -SH (I)， wherein L 1 is selected from C 2-30 alkylene, C 2-30 heteroalkylene, C 3-30 alkenylene, C 2-30 heteroalkenylene, C 3-30 alkynylene and C 2-30 heteroalkynylene, wherein one or more hydrogen atoms in any of these groups are optionally and / or independently replaced by at least one of a fluorine atom, a hydroxyl group and / or an O-C 1-4 alkyl group, and R 1 is an OH-group, an O-C 1-4 alkyl group, an SH-group, an S-C 1-4 alkyl group, a C(=O)OR 11 group, an NR 11 R 12 group, NR 11 C(=O)NR 12 R 13 group, NR 11 C(=O)OR 12 、OC(=O)NR 11 R 12 group Group, S(=O)2NR 11 Group, OPO3 2- Group or its salt, OC(=O)O group or its salt, C(NR 11 )R 12 Group, NR 11 CNR 12 NR 13 R 14 Group, C(=O)SR 11 or C(=S)OR 11 Group, or halide, wherein R 11 , R 12 , R 13 and R 14 are independently selected from H, C 1-8 alkyl, C 1-8 alkenyl and C 1-8 alkynyl, and / or The organic modifier is at least one thiol of the general formula (II): R 2 -SH (II), wherein R 2 is C 1-30 hydrocarbyl, which may optionally contain one or more heteroatoms and / or heteroatom groups, wherein said heteroatoms are preferably selected from O, S and N, more preferably from O and S, even more preferably from O, and wherein said heteroatom groups are preferably selected from NH and NR, where R is C 1-4 aliphatic residue, R 2 is preferably C 7-30 hydrocarbyl, wherein in each case one or more hydrogen atoms are optionally and / or independently of one another replaced by at least one of a fluorine atom, a hydroxyl group and / or an O-C 1-4 alkyl group, and / or The organic modifier is at least one thiol of the general formula (III): Si(X) 3-y (Y) y -L 2 -SH (III), where y is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0, where Y is a non-hydrolyzable organic residue, preferably C 1-30 alkyl, which is preferably unsubstituted, or represents the residue L 2 -SH, where L 2 has the definition described below, wherein X independently of one another in each case represents a hydrolysable group which is preferably reactive towards at least one of a phenolic OH-group, a phenolate group, an aliphatic OH-group, a carboxylic acid group, a carboxylate group, a silyl ether group and mixtures thereof, and X preferably represents a hydrolysable group selected from: O-C 1-4 alkyl, O(CH2) a -O(CH2) b -CH3 groups, halides, and mixtures thereof, where a is an integer from 2 to 3 and b is an integer from 1 to 14 wherein L 2 is a divalent organic residue that is non-hydrolyzable and is preferably selected from C 1-30 alkylene, more preferably selected from C 1-16 alkylene, even more preferably selected from C 1-6 alkylene, most preferably selected from C 1-3 alkylene, wherein in each case one or more hydrogen atoms are optionally and / or independently of one another replaced by fluorine atoms and / or at least one of O-C 1-4 alkyl, but preferably wherein each of the above-mentioned alkylene groups is unsubstituted, and / or The organic modifier is at least one thiirane of the general formula (IV) that is a thiol precursor: wherein R 4 is C 1-30 hydrocarbyl, which may optionally contain one or more heteroatoms and / or heteroatom groups, wherein said heteroatoms are preferably selected from O, S and N, more preferably from O and S, even more preferably from O, and wherein said heteroatom groups are preferably selected from NH and NR, where R is C 1-4 aliphatic residue, R 4 is preferably C 7-30 hydrocarbyl, wherein in each case one or more hydrogen atoms are optionally and / or independently of one another replaced by fluorine atoms, hydroxyl groups and / or at least one of O-C 1-4 alkyl and / or The organic modifier is at least one polythiol polymer having at least two or more preferably terminal thiol groups, preferably at least one polysulfide having two, three or more preferably terminal thiol groups.

9. The filler according to one or more of the preceding claims, characterized in that The filler can be obtained by performing at least one step a) and optionally one or more steps b) to d), namely: a) Combine at least one organic modifier and at least one organic filler precursor FPM, the organic modifier comprising at least one thiol group adjacent to a carbon atom within its chemical structure, the organic filler precursor FPM having a 14 C content in the range of 0.20 to 0.45 Bq / g carbon, a BET surface area in the range of 10 to <200 m 2 / g, and having at least one hydroxyl group bonded to at least one aliphatic carbon atom, b) Optionally heating the mixture obtained according to step a), which is preferably present in a liquid or gaseous reaction medium, preferably heating to a temperature in the range of 30 °C to 190 °C, more preferably heating to a temperature in the range of 50 °C to 180 °C, most preferably heating to a temperature in the range of 70 °C to 170 °C, c) Where steps a) and / or optionally the heating operation according to step b) have been carried out in a liquid reaction medium containing at least one organic solvent, after at least a part of the hydroxyl groups in the organic filler precursor FPM that are bonded to at least one fewer aliphatic carbon atom have been replaced by an organic residue containing one or more sulfur atoms that are covalently bonded, at least one organic solvent is optionally extracted, where at least one sulfur atom present is derived from the mercapto group of the organic modifier, and d) Optionally, the organic filler obtained after carrying out steps a) and optionally step b) and / or c) is dried, which is preferably carried out under vacuum and / or at a temperature in the range of 20 to 100 °C.

10. The filler according to one or more of the preceding claims, characterized in that The filler is in a rubber-free form and / or is prepared in a rubber-free form.

11. A rubber composition comprising at least one rubber and at least one filler component, where the filler component comprises at least one organic filler according to one or more of the foregoing claims, and / or wherein the filler component comprises: (i) at least one organic filler precursor FPM having a 14 C content in the range of 0.20 to 0.45 Bq / g carbon, a BET surface area in the range of 10 to <200 m 2 / g, and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; and (ii) at least one organic modifier comprising at least one thiol group adjacent to a carbon atom within its chemical structure, via which thiol group, the hydroxyl group present in the chemical structure of the organic filler precursor FPM and bonded to at least one aliphatic carbon atom can be at least partially replaced by a covalently bonded organic residue containing one or more sulfur atoms, thereby forming a covalent bond connected to at least one organic filler precursor FPM, such that an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler is generated, wherein at least one sulfur atom present is derived from the thiol group of the organic modifier, and forming the organic filler according to one or more of the preceding claims.

12. The rubber composition according to claim 11, wherein the at least one rubber is selected from the group consisting of: natural rubber (NR), halogenated butyl rubber, more preferably selected from chlorobutyl rubber (CIIR; chloro-isobutene-isoprene rubber) and bromobutyl rubber (BIIR; bromo-isobutene-isoprene rubber) and mixtures thereof, butyl rubber or isobutene-isoprene rubber, isobutene-isoprene rubber (IIR; isobutene-isoprene rubber), styrene-butadiene rubber (SBR, styrene butadiene rubber), more preferably SSBR and / or ESBR, polybutadiene (BR, butadiene rubber), acrylonitrile-butadiene rubber (NBR, nitrile rubber) and / or HNBR (hydrogenated NBR), chloroprene (CR), polyisoprene (IR), ethylene-propylene-diene rubber (EPDM), and mixtures thereof, and / or characterized in that the rubber composition comprises at least one organic filler according to any one of claims 1 to 10, in an amount of 10 to 150 phr, particularly preferably 15 to 130 phr, most preferably 20 to 120 phr, especially 40 to 100 phr; and / or comprises at least one organic filler precursor FPM as defined in (i) of claim 11, in an amount of 10 to 150 phr, particularly preferably 15 to 130 phr, most preferably 20 to 120 phr, especially 40 to 100 phr, and at least one organic modifier as defined in (ii) of claim 10, in an amount of 0.1 - 30 wt%, particularly preferably 0.5 - 25 wt%, most preferably 1.0 - 15 wt%, especially 1.5 - 12 wt%, in each case based on the total weight of the organic filler precursor FPM.

13. A vulcanizable rubber composition comprising the rubber composition according to one or more of claims 11 or 12 and a vulcanization system, the vulcanization system preferably comprising at least zinc oxide and / or at least sulfur or a sulfur donor and / or at least one peroxide, particularly preferably comprising at least sulfur.

14. A kit which contains, in a spatially separated form, a rubber composition as defined in one or more of claims 11 and 12 as part (A), and a vulcanization system as defined in claim 13 as part (B).

15. A vulcanized rubber composition which can be obtained by vulcanizing a vulcanizable rubber composition according to claim 13, or by vulcanizing a vulcanizable rubber composition obtained by combining and mixing the two parts (A) and (B) of the kit according to claim 14.

16. Use of an organic filler as defined in one or more of claims 1 to 10 for producing a rubber composition and a vulcanizable rubber composition, and use of a rubber composition as defined in one or more of claims 11 to 12 and 15 for producing a tire, which tire is preferably a pneumatic tire and a solid tire, in particular a pneumatic tire, preferably for producing a tread, a sidewall and / or an inner liner of a tire in each case, and / or for producing an industrial rubber article, which industrial rubber article is preferably a profile, a seal, a shock absorber and / or a hose.

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