Organic fillers with thioether bonds

Abstract

The present invention provides 14 C-content in the range of 0.20 to 0.45 Bq / g carbon and 10 to <200 m 2 / g(10 to 200m 2 / g), wherein at least a portion of the aliphatic hydroxyl groups present in the chemical structure of the organic filler are replaced with an organic residue comprising a covalently bonded sulfur atom, wherein at least one sulfur atom in the organic residue is adjacent to a carbon atom, thereby forming and presenting an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler; a rubber composition comprising at least one rubber and at least one filler component; a vulcanizable rubber composition further comprising a vulcanization system; a vulcanized rubber composition obtainable therefrom; and the use of the aforementioned filler for producing a (vulcanizable) rubber composition and the use of such a rubber composition for producing tires and / or technical rubber articles.

Description

[Technical Field]

[0001] The present invention relates to an organic filler (organic filler) that can be produced from renewable materials and to a (vulcanizable) rubber composition that further comprises at least one rubber as a filler component, and to the vulcanized rubber compositions obtainable therefrom, as well as to the use of said organic filler for producing a (vulcanizable) rubber composition and to the use of such a rubber composition for producing tires and / or technical rubber articles. [Background technology]

[0002] The use of reinforcing fillers in rubber compositions is well known in the art. In particular, industrial carbon black, such as furnace carbon black, is used for this purpose. Industrial carbon black still accounts for the largest amount of reinforcing fillers. Industrial carbon black is produced based on highly aromatic petrochemical oils using the incomplete combustion of hydrocarbons or by pyrolysis. However, from an environmental perspective, it is desirable to avoid or minimize the use of fossil fuels to produce fillers. In particular, from an environmental perspective, it is undesirable that the production of one ton of industrial carbon black releases approximately one ton of carbon dioxide during the production process, depending on the specific surface area of ​​the carbon black. Furthermore, industrial carbon black is often unusable for certain applications, and also due to its color.

[0003] A well-known alternative to the use of industrial carbon black as an inorganic reinforcing filler is (precipitated) silica. Chemically modified precipitated silica is particularly suitable for use as a reinforcing filler due to its high surface area.

[0004] In the tire industry, the use of corresponding chemically modified, especially silanized, precipitated silicas is also advantageous. Vehicle tires, such as pneumatic tires, have a complex structure and are subject to diverse requirements. On the one hand, short braking distances must be ensured on dry and wet road surfaces, while good wear characteristics and low rolling resistance must also be achieved. Furthermore, vehicle tires must comply with legal requirements. To ensure diverse performance characteristics, individual tire components are specialized and made of various different materials, such as metals, polymer textile materials, and various rubber-based components. The tread significantly influences the running characteristics. The rubber composition of the tread determines the wear behavior and dynamic running characteristics in various weather conditions (on wet and dry roads, in cold and warm weather, on ice and snow). Therefore, the tread design significantly influences the tire's behavior in aquaplaning and wet conditions, as well as on snow, and also determines the generation of running noise.

[0005] In passenger car tire tread rubber compounds, the use of silanized precipitated silica as a reinforcing filler compared to industrial carbon black improves rolling resistance due to the chemical bond between the precipitated silica and the elastomer of the rubber compound, while simultaneously improving wet grip due to the polar surface of the precipitated silica. Tire wear is generally worse when using precipitated silica compared to industrial carbon black, but this can be offset by appropriate selection of the elastomer used (e.g., by using polybutadiene).

[0006] However, in tire tread rubber compounds used in the truck sector, the use of silanized precipitated silica as a reinforcing filler does not provide the abrasion resistance required for industrial carbon black, especially since natural rubber is primarily used in truck treads and therefore the aforementioned flexibility in elastomer selection is not available, as is the case with passenger car tires.

[0007] Another drawback of using chemically modified, especially silanized, precipitated silica in rubber compositions, particularly for the manufacture of tire treads for both passenger cars and trucks, is that stress values ​​are lower at small deformations than when technical carbon black is used. This is particularly evident in the case of dynamic cyclic deformations that may occur. Therefore, to adjust specific tire properties for driving dynamics, the additional use of technical carbon black is necessary, which is undesirable for the reasons mentioned above.

[0008] Furthermore, both in the field of technical rubber products and in the tire industry, the precipitated silicas used have a relatively high specific surface area, e.g., between 100 and 250 m 2 / g (BET surface area) range is often used. When used in passenger car treads, less heat is released during mechanical deformation (hysteresis), which improves rolling resistance, but BET values ​​of 30 to 50 m 2 The advantages over technical carbon black, which usually has a very low specific surface area in the range of 1 / g, are therefore often no longer apparent. Furthermore, there is a lower dynamic stiffness often observed compared to rubber compounds containing technical carbon black as a reinforcing filler.

[0009] Lignin-based biologically renewable raw materials, such as hydrothermally carbonized forms of lignin (HTC lignin), are also used as organic fillers in rubber compositions. These are environmentally friendly filler alternatives compared to inorganic fillers and industrial carbon black.

[0010] EP 3470457 A1 describes rubber compounds containing HTC lignin. However, a drawback of using such HTC lignin in rubber compounds is that the compatibility between the relatively polar HTC lignin and the relatively non-polar rubber is often very low or insufficient. Further drawbacks are often observed with respect to the aging resistance and long-term stability of HTC lignin-containing rubber compositions, especially those in vulcanized form, because undesirable reactions can occur due to an excessively high proportion of free OH groups contained in the HTC lignin, which has a detrimental effect on aging resistance and long-term stability.

[0011] Among other fields of application, in the field of producing rubber compositions typically used in tires, WO 2017 / 085278 A1 also discloses the use of particulate carbon materials, in particular HTC lignin, as a replacement filler for industrial carbon black. The same frequent drawbacks as those mentioned above in connection with EP 3470457 A1 are associated with this. WO 2017 / 085278 A1 also describes that this material, after being incorporated into the rubber composition, may be subjected to in situ modification with organosilanes as coupling agents. However, as described in WO 2017 / 085278 A1, a drawback of using such organosilanes to modify carbon materials is that the chemical Si-O-C bond formed between the material and the organosilane coupling reagent often has a relatively low thermodynamic stability, which means that this bond is relatively easily hydrolyzed, resulting in undesirable decoupling reactions and therefore poor filler-rubber interactions in the rubber composition, which can lead to adverse properties of the rubber composition during and after vulcanization and are therefore avoided. Furthermore, the coupling efficiency of the aforementioned carbon materials and organosilane coupling reagents is often too low, often due to an undesirable high rate of self-condensation of the used organosilanes, which are then no longer available for actual modification. A further drawback results from the realization of modification in situ only in the rubber composition being produced, which often results in an undesirable range of freedom in the production of the composition and the components contained therein, especially when the aforementioned carbon materials are used in combination with other fillers, such as inorganic fillers, especially silica / silica. Another drawback is that the in-situ reaction with organosilanes requires an additional mixing step compared to the use of industrial carbon black, which for cost reasons is not commonly used in the manufacture of technical rubber articles and most tire components (e.g., sidewalls, innerliners).

[0012] Finally, WO 2017 / 194346 A1 also describes the use of HTC lignin, particularly together with methylene donor compounds such as hexa(methoxymethyl)melamine, in rubber compounds for pneumatic tire components to increase the stiffness of the cured rubber component of the tire and, in particular, as a replacement for phenolic resins. WO 2017 / 194346 A1 also describes possible in-situ modification with organosilanes as coupling agents. However, the same drawbacks are associated with this as those discussed above in connection with WO 2017 / 085278 A1.

[0013] Therefore, there is a need for new organic fillers suitable for incorporation into rubber compositions, as well as such rubber compositions themselves that do not suffer from the above-mentioned drawbacks. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] European Patent Application Publication No. 3470457 [Patent Document 2] International Publication No. 2017 / 085278 [Patent Document 3] International Publication No. 2017 / 194346 [Non-patent literature]

[0015] [Non-Patent Document 1] PAC2007, 79, 1801, 1826 pages [Non-patent document 2] "Kautschuk Technologie", F. Rothemeyer and F. Sommer, 3rd edition, 2013 Summary of the Invention [Problem to be solved by the invention]

[0016] The object underlying the present invention is therefore to provide environmentally friendly fillers directly in situ for incorporation into rubber compositions, in particular tire components such as tire treads and tire substructures (carcasses), and / or components of technical rubber articles, with a view to improving the aging and long-term stability of rubber compositions, especially in the vulcanized form, increasing media resistance and hydrolysis resistance compared to prior art fillers, and improving mechanical properties such as modulus, tensile strength, and elongation at break. A further object of the present invention is to provide the corresponding rubber compositions themselves, containing these fillers. [Means for solving the problem]

[0017] This object is solved by the subject matter of the claims of the present application as well as by the preferred embodiments thereof disclosed herein, i.e. by the subject matter described herein.

[0018] The first object of the present invention is to 14 C-content in the range of 0.20 to 0.45 Bq / g carbon and 10 to <200 m 2 / g(200m 2 an organic filler having a BET surface area in the range of less than 1 / g; The filler is characterized in that at least a portion of the hydroxyl groups present in the chemical structure of the organic filler that are bonded to at least one aliphatic carbon atom are replaced with a covalently bonded sulfur atom-containing organic residue (one or more sulfur atoms), where at least one sulfur atom is adjacent to a carbon atom in the organic residue, thereby forming and presenting an aliphatic carbon-sulfur-carbon bond within the chemical structure of the organic filler.

[0019] Aliphatic carbon-sulfur-carbon bonds are present in the chemical structure of the organic filler, i.e., C 脂肪族 -SC bond. The aliphatic carbon atom (C 脂肪族) corresponds to at least one aliphatic carbon atom present in the chemical structure of the organic filler to which a hydroxyl group is attached. The sulfur atom (S) of such a bond corresponds to a sulfur atom present in the sulfur atom-containing organic residue and is in accordance with the present invention with the aforementioned aliphatic carbon atom (C 脂肪族 ) covalently bonded to the other carbon atom (C) of such bond, which corresponds to the carbon atom positioned adjacent to the sulfur atom in the sulfur-containing organic residue. The other carbon atom is therefore different from the aliphatic carbon atom mentioned above. C present in the chemical structure of the organic filler 脂肪族 The -SC bond is a thioether bond.

[0020] A further object of the present invention is a rubber composition comprising at least one rubber and at least one filler component, the filler component comprises at least one organic filler as defined above and below; and / or The filler component has (i) a carbon content in the range of 0.20 to 0.45 Bq / g. 14 C content, 10 to <200m 2 / g(10m 2 / g to 200m 2and (ii) at least one organic filler precursor FPM having a BET surface area in the range of less than 1 / g and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; and (iii) at least one organic modifier comprising at least one thiol group positioned adjacent to a carbon atom in its chemical structure, wherein the organic modifier is capable of forming a covalent bond with the at least one organic filler precursor FPM through at least partial substitution of a hydroxyl group present in the chemical structure of the organic filler precursor FPM bonded to at least one aliphatic carbon atom with a covalently bonded sulfur atom-containing organic residue, 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 therein comes from the thiol group of the organic modifier, thereby forming an organic filler as defined above and below.

[0021] A further subject of the present invention is a vulcanizable rubber composition comprising the rubber composition defined above and below and a vulcanization system, which preferably comprises at least zinc oxide and / or at least sulfur or a sulfur donor and / or at least one peroxide, particularly preferably at least sulfur.

[0022] A further object of the present invention is a kit-of-parts comprising, in a spatially separate form, a rubber composition as part (A) as defined above and below, and a vulcanization system as part (B) as defined above and below.

[0023] A further subject of the present invention is a vulcanized rubber composition obtainable by vulcanizing a vulcanizable rubber composition as defined above and below, or obtainable by combining and mixing the two parts (A) and (B) of the multi-part kit as defined above and below.

[0024] Further objects of the present invention are the use of the organic fillers as defined above and below for the production of rubber compositions and vulcanized rubber compositions, as well as the use of the rubber compositions as defined above and below for the production of tires, preferably pneumatic and solid tires, in particular pneumatic tires, preferably in each case their treads, sidewalls and / or innerliners, and / or for the production of technical rubber articles, preferably profiles, seals, dampers and / or hoses.

[0025] The organic fillers according to the present invention have been found to be environmentally friendly alternatives to known fillers of the prior art, particularly inorganic fillers such as silica and carbon black for rubber applications.

[0026] It has also been surprisingly found that the organic filler according to the invention is directly suitable per se for incorporation into rubber compositions, in particular for producing treads, sidewalls and / or innerliners of tires such as pneumatic and solid tires, and / or for producing technical rubber articles, such as profiles, seals, dampers and / or hoses.

[0027] Furthermore, it has been surprisingly discovered that the organic filler according to the present invention has good compatibility with the rubber present in the rubber composition. In particular, it has been discovered that due to the presence of covalently bonded sulfur atom(s)-containing organic residues containing an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler, i.e., due to the surface modification of the filler, the polarity of the filler can be reduced to such an extent that its compatibility with relatively non-polar rubber is improved. In particular, it has been shown that compatibility can be further improved due to the presence of covalently bonded sulfur atom-containing organic residues containing an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler when the filler is used together with at least one rubber in the rubber composition, when the covalently bonded sulfur atom-containing organic residue further contains at least one reactive functional group that is reactive with at least one rubber and / or with at least one functional group of this rubber and / or with the vulcanization system used, especially during vulcanization. In this case, binding of the filler to the rubber and / or vulcanization system is possible at the latest during vulcanization, which, in addition to improved compatibility, further improves in particular the reinforcement properties of the vulcanized composition (e.g., modulus, elongation at break, hysteresis, tear resistance, and / or tensile strength).

[0028] Furthermore, it has been surprisingly discovered that when the covalently bonded sulfur-containing organic residue contains at least one reactive functional group that can undergo a crosslinking reaction with another identical reactive functional group that is reactive with each other, for example, when the reactive functional group is an alkoxysilyl group, and when at least two such covalently bonded sulfur-containing organic residues are present in the chemical structure of the organic filler, a (lateral) crosslinking reaction can be observed, which allows further modification of the surface of the organic filler. In this way, materials with desired and / or tailored properties can be produced in a targeted manner, for example, by adjusting the surface porosity and / or density and / or adhesive or cohesive properties of the filler and / or its surface.

[0029] Furthermore, it has been surprisingly found that the organic fillers according to the invention enable the aging resistance and long-term stability of rubber compositions, even in the vulcanized form, to be improved. In this regard, it has been surprisingly found that the organic fillers according to the invention exhibit increased media resistance, particularly to bases, and hydrolysis resistance, compared with fillers of the prior art. In particular, it has been found that due to the presence of covalently bonded sulfur-containing organic residues containing aliphatic carbon-sulfur-carbon bonds in the chemical structure of the organic filler, i.e., due to surface modification of the filler, not only has this compatibility been improved, but the proportion of aliphatic OH groups has also been reduced to such an extent that potentially undesirable reactions that adversely affect aging resistance and long-term stability can be prevented or at least reduced with the help of these groups. In this regard, it has been found that the susceptibility of the fillers according to the invention to hydrolysis can be at least reduced due to the surface modification carried out, and media resistance, particularly to bases, can be increased. This further improves the reinforcing properties of the vulcanized composition.

[0030] Furthermore, it has been surprisingly discovered that the covalent modification, i.e., the introduction of an organic residue containing a covalently bonded sulfur atom into a suitable filler precursor (i.e., the filler FPM described below), can be carried out in a separate step ("ex situ") and therefore does not necessarily require in situ bonding in the rubber composition in the presence of the rubber. This has the particular advantage that the already modified organic filler according to the invention can be used as is in the rubber composition, in particular in combination with other fillers, such as inorganic fillers, and in particular (unmodified) silica, as fillers; in particular, if modification of other fillers, such as silica, with suitable modifiers, such as organosilanes, is considered in the rubber composition, such modification must still be carried out in situ. Therefore, the "ex situ" modification allows the user greater freedom and flexibility in the preparation and formulation of the rubber composition and the components contained therein.

[0031] Furthermore, it was unexpectedly discovered that due to the presence of an organic residue containing a covalently bonded sulfur atom, a thermodynamically stable covalent C-C bond exists in the chemical structure of the filler, which has a higher thermodynamic stability than the corresponding Si-O-C bond formed, for example, when a non-functional organosilanes is used. This also results in increased hydrolysis resistance, and can avoid or at least reduce undesirable decoupling reactions, thus lowering filler-rubber interactions in the rubber composition. Furthermore, the use of the modifier according to the present invention has the advantage that high coupling efficiency is achieved because self-condensation reactions, which can occur, for example, when a non-thiol-containing organosilanes is used, do not occur.

[0032] It has been surprisingly found that corresponding rubber compositions, in particular vulcanizable rubber compositions containing the organic filler according to the invention, can be used for the manufacture of tires, for example pneumatic and solid tires, in particular pneumatic tires, preferably in the case of the tread, sidewall, and / or innerliner, respectively, and meet the requirements necessary for this purpose to a very high degree, in particular with regard to rolling resistance, wear, and wet slippage, and balance these requirements.It has also been surprisingly found that corresponding rubber compositions, in particular vulcanizable rubber compositions containing the organic filler according to the invention, are suitable for use in the manufacture of technical rubber products (rubber articles), in particular profiles, seals, dampers, and / or hoses.

[0033] It has also been surprisingly discovered that the vulcanized rubber compositions according to the invention have improved mechanical properties, in particular with respect to tensile strength, Shore A hardness, and rebound, compared to vulcanized rubber compositions containing organic fillers that do not have sulfur-containing bonds present in the chemical structure of the organic filler according to the invention.

[0034] It has also been particularly surprising to discover that rubber compositions according to the invention, and in particular vulcanizable rubber compositions containing organic fillers according to the invention, result in vulcanized rubber compositions characterized by an increased modulus in the range of up to 200% elongation, even when no technical carbon black is used as additional filler.

[0035] It has also been particularly surprisingly discovered that rubber compositions according to the invention, in particular vulcanizable rubber compositions containing an organic filler according to the invention, result in vulcanized rubber compositions for use in tire treads in passenger cars, and in particular in the truck sector, that provide at least acceptable tire wear with improved rolling resistance and wet grip compared to vulcanized rubber compositions which contain silanated precipitated silica instead of the organic filler according to the invention. [Brief explanation of the drawings]

[0036] [Figure 1] Figure 1 shows the 13C NMR spectrum of the organic filler. [Figure 2] FIG. 2 shows stress-strain curves of the vulcanized rubber compositions V-OF2 and V-OF3, and the vulcanized rubber composition V-FPM2 used as a comparative example. [Figure 3] FIG. 3 shows the hardness of vulcanized rubber compositions V-OF2, V-OF3, V-OF4, and V-OF5, as well as vulcanized rubber compositions V-FPM2 and V-FPM3 used as comparative examples. [Figure 4] FIG. 4 shows stress-strain curves of the vulcanized rubber compositions V-OF4 and V-OF5, and the vulcanized rubber composition V-FPM3 used as a comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0037] The term "comprising" as used herein, for example in connection with the rubber composition according to the invention, the vulcanizable rubber composition according to the invention, and the process steps or stages in the context of the methods described herein, preferably has the meaning "consisting of." In this context, for example with respect to the rubber composition according to the invention and the vulcanizable rubber composition according to the invention, in addition to the components that are necessarily present therein, one or more of the following optional further components may be contained therein. All components may be present in their respective preferred embodiments described below. With respect to the methods according to the invention and described herein, these may further comprise optional process steps and stages in addition to the mandatory steps and / or stages.

[0038] The amounts of all components contained in the compositions described herein, such as the rubber composition according to the invention and the vulcanizable rubber composition according to the invention (in each case including all essential components and optionally including all optional components), in each case add up to 100% by mass.

[0039] Organic fillers with thioether bonds As outlined above, the primary focus of the present invention is to detect carbon in the range of 0.20 to 0.45 Bq / g. 14 C content and 10 to <200m 2 / g(10m 2 / g to 200m 2 an organic filler having a BET surface area in the range of less than 1 / g; A filler characterized in that at least a portion of the hydroxyl groups present in the chemical structure of the organic filler, which are bonded to at least one aliphatic carbon atom, are replaced with an organic residue containing covalently bonded sulfur atom(s), wherein at least one sulfur atom in the organic residue is positioned adjacent to a carbon atom, thereby forming and presenting an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler.

[0040] Those skilled in the art are familiar with the term filler, especially organic filler. Preferably, the organic filler according to the present invention is a reinforcing filler, i.e., an active filler. Reinforcing or active fillers, in contrast to inert (non-reinforcing) fillers, can change the viscoelastic properties of rubber by interacting with the rubber in the rubber composition. For example, they can affect the viscosity of the rubber and improve the fracture behavior of the vulcanizate, for example, in terms of tear propagation resistance and abrasion. On the other hand, inert fillers dilute the rubber matrix.

[0041] Since the fillers according to the present invention are organic, inorganic fillers such as precipitated silica are not encompassed by this term.

[0042] The organic filler according to the present invention has a carbon content in the range of 0.20 to 0.45 Bq / g, preferably 0.23 to 0.42 Bq / g. 14 The required C content is as defined here. 14 The C content is filled by organic fillers obtained from biomass by further processing or conversion, preferably by fractionation thereof, where fractionation may be thermal, chemical and / or biological, preferably thermal and / or chemical. Thus, fillers obtained from fossil materials, in particular fossil fuels, can be filled by the corresponding 14 Since it does not have a C content, it is not included in the definition of the fillers used in accordance with the present invention.

[0043] "Biomass" is defined herein as any biomass, and the term "biomass" as used herein encompasses so-called phytomass, i.e., biomass of plant origin, biomass of animal origin, and microbial biomass, i.e., biomass of microorganisms, including fungi. Biomass can be dry or fresh biomass and can be biomass of dead or living organisms. A particularly preferred biomass for the production of organic fillers herein is phytomass, preferably dead phytomass. Dead phytomass includes, but is not limited to, dead, dead, or detached plants and components. These include, for example, broken and torn leaves, cereal stalks, leaves attached to stalks, twigs and branches, leaf litter, felled or pruned trees, as well as seeds and fruits and components derived therefrom, as well as sawdust, and other products derived from wood processing.

[0044] Preferably, the organic fillers according to the invention have 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, and in particular 68% to 73% by weight, based in each case on the ashless and anhydrous filler. Methods for determining the carbon content are given in the methods section below. This distinguishes organic fillers from both carbon blacks produced from fossil raw materials and carbon blacks produced from renewable raw materials, since the carbon blacks have a corresponding carbon content of at least 95% by weight.

[0045] Preferably, the organic fillers according to the invention have 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 ashless and anhydrous filler. The oxygen content can be determined by high-temperature pyrolysis, for example with the aid of a EuroEA3000 CHNS-O analyzer from EuroVector SpA.

[0046] The organic fillers according to the present invention are from 10 to <200 m2 / g(10m 2 / g to 200m 2 / g). The method for determining this parameter is described in the Methods section below. Particularly preferably, the organic fillers according to the present invention have a BET surface area (total specific surface area according to Brunauer, Emmett, and Teller) in the range of 10 to 150 m 2 BET surface area in the range of 20 to 120 m / g, most preferably 2 / g, and even more preferably 30 to 110 m 2 / g, especially between 40 and 100 m 2 BET surface area in the range of 40 to <100 m / g, most preferably 2 / g(40m 2 / g to 100m 2 / g).

[0047] The organic fillers according to the invention preferably have a viscosity of 10 to <200 m 2 / g(10m 2 / g to 200m 2 / g). A method for determining the STSA surface area (Statistical Thickness Surface Area) is given in the Methods section below. Preferably, the organic fillers according to the present invention have an STSA surface area in the range of 10 to 150 m 2 / g range, especially from 20 to 120 m 2 / g, most preferably in the range of 30 to 110 m 2 / g range, especially from 40 to 100 m 2 / g, most preferably in the range of 40 to <100m 2 / g(40m 2 / g to 100m 2 / g).

[0048] Preferably, the organic filler according to the present invention only exhibits conditional solubility in alkaline medium, in particular in 0.1 M or 0.2 M NaOH. The solubility is determined 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%, even more preferably less than 7.5%, even more preferably less than 5%, even more preferably less than 2.5%, and particularly preferably less than 1%.

[0049] Preferably, the organic filler is a lignin-based filler, more preferably a lignin-based filler obtainable by hydrothermal treatment (HTT). A lignin-based filler obtained by hydrothermal treatment is hereinafter also referred to as HTT lignin ("hydrothermally treated lignin"). The term HTC lignin ("hydrothermally carbonized lignin") is also frequently used in the literature. Fillers designated as HTC lignin are also encompassed under the term HTT lignin. Hydrothermal treatment at temperatures between 150°C and 250°C in the presence of liquid water is also hereinafter referred to as hydrothermal treatment. Preferably, the organic filler according to the present invention is a lignin-based organic filler produced from biomass and / or biomass components. For example, lignin for the production of lignin-based organic fillers can be isolated, extracted, and / or dissolved from biomass before its modification according to the present invention. Suitable methods for obtaining lignin for producing lignin-based organic fillers from biomass are, for example, hydrolysis processes or digestion processes, such as the Kraft digestion process. In the context of 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 according to the present invention. Lignins are solid biopolymers incorporated into plant cell walls, thus causing the ligninization of plant cells. They are therefore present in biomass, especially biologically renewable raw materials, and therefore, are an environmentally friendly filler alternative, especially in hydrothermally treated form.

[0050] Due to their natural origin, lignins are structurally heterogeneous phenolic biopolymers composed of various monomer building blocks that vary structurally depending on their plant source. In particular, the molecular structure of lignin contains, among other things, several different aliphatic OH groups. It has been discovered that these can then be used to introduce organic residues containing sulfur atoms by covalently bonding them to the aliphatic carbon atoms of such groups, in particular by substitution reactions using organic thiols as organic modifiers.

[0051] Preferably, the organic filler according to the 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, and most preferably at least 80% by weight, in each case based on the total weight of the organic filler according to the invention. Preferably, the Klason lignin content in the organic filler according to the invention is at least 50% by weight, particularly preferably at least 60% by weight, most preferably at least 70% by weight, and most preferably at least 80% by weight. The Klason lignin content is preferably determined as acid-insoluble lignin according to TAPPI T 222.

[0052] Preferably, the lignin and preferably the organic filler according to the present invention itself, especially if it is a lignin-based filler, is at least partially present in a hydrothermally treated form and is particularly preferably obtainable in each case using hydrothermal treatment. Particularly preferably, the organic filler according to the present invention is based on lignin obtainable using hydrothermal treatment. Suitable methods for hydrothermal treatment, especially for the hydrothermal treatment of lignin and lignin-containing organic fillers, are described, for example, in WO 2017 / 085278 A1, WO 2017 / 194346 A1, and EP 3470457 A1. Preferably, the hydrothermal treatment is carried out in the presence of liquid water at a temperature between 150 ° C and 250 ° C.

[0053] Preferably, the organic filler according to the present invention has a pH in the range of 7 to 9, more preferably in the range of >7 to <9 (greater than 7 and less than 9), and most preferably in the range of >7.5 to <8.5 (greater than 7.5 and less than 8.5).

[0054] The organic filler according to the present invention preferably has a d99 value of <25.0 μm (less than 25.0 μm). The method for determining 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 present invention is preferably present in the form of particles. The average particle size of these particles is described by the aforementioned d99. Preferably, the organic filler has a d99 value, preferably determined in each case by laser diffraction in accordance with ISO 13320:2009, of <20.0 μm (less than 20.0 μm), more preferably <15.0 μm (less than 15.0 μm), particularly preferably <10 μm (less than 10 μm), most preferably <9.0 μm (less than 9.0 μm), even more preferably <8.0 μm (less than 8.0 μm), even more preferably <7.0 μm (less than 7.0 μm), most preferably <6.0 μm (less than 6.0 μm).

[0055] As outlined above, aliphatic carbon-sulfur-carbon bonds are present in the chemical structure of organic fillers, i.e., C 脂肪族 -SC bond. The aliphatic carbon atom (C 脂肪族 ) corresponds to at least one aliphatic carbon atom present in the chemical structure of the organic filler to which a hydroxyl group is bonded. The sulfur atom (S) of such a bond corresponds to a sulfur atom present in an organic residue containing sulfur atom(s) and corresponds to the aliphatic carbon atom (C) described above in the chemical structure of the organic filler according to the present invention. 脂肪族) covalently bonded to the organic residue containing a sulfur atom. The covalently bonded sulfur atom-containing organic residue contains at least one sulfur atom, but may contain one or more additional sulfur atoms. Thus, the expression "sulfur atom" includes the presence of exactly one sulfur atom or multiple sulfur atoms. However, at least one sulfur atom in the organic residue is located next to a carbon atom, thus forming and presenting an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler. Preferably, the at least one sulfur atom is a sulfur atom derived from the thiol group of the organic modification used. The at least one sulfur atom is also covalently bonded to the other carbon atom (C) of such bond, which carbon atom corresponds to the carbon atom located adjacent to the sulfur atom in the organic residue containing a sulfur atom. Thus, the other carbon atom is different from the aliphatic carbon atom mentioned above, but may also be an aliphatic carbon, preferably an aliphatic carbon. The C present in the chemical structure of the organic filler 脂肪族 The -SC bond is a thioether bond.

[0056] Preferably, the (other) carbon atom adjacent to said sulfur atom of the covalently bonded sulfur atom-containing organic residue is not part of an unsubstituted and / or saturated hexyl group. More preferably, if the (other) carbon atom adjacent to said sulfur atom of the covalently bonded sulfur atom-containing organic residue is part of an unsubstituted and / or saturated straight-chain aliphatic group, it is part of such a group having a number of carbon atoms of at least 7.

[0057] The polarity of the organic filler is advantageously altered by at least partial substitution of the hydroxyl group attached to at least one aliphatic carbon atom. Depending on the type of modifier used, a physical shielding effect may also occur.

[0058] Preferably, the organic filler does not contain an aliphatic carbon-sulfur-carbon bond in its chemical structure, and the carbon atoms (i.e., the non-aliphatic carbon atoms) are 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, the carbon atoms (i.e., the non-aliphatic carbon atoms) are part of an unsubstituted and / or saturated straight-chain aliphatic group, and such group has a minimum number of carbon atoms of at least seven. A minimum number of seven carbon atoms advantageously provides improved physical shielding effect due to its relatively long chain hydrophobic portion.

[0059] Preferably, hydroxyl groups, more preferably primary hydroxyl groups bonded to at least one aliphatic carbon (hereinafter also referred to as "aliphatic OH groups"), are present on the surface of the organic filler particles (and therefore are part of the organic filler's chemical structure). In such cases, these groups therefore represent so-called surface-available groups. As a result, the formed aliphatic carbon-sulfur-carbon bonds (thioether bonds) are preferably also present on the surface of the organic filler particles.

[0060] Preferably, the hydroxyl groups of the organic filler, more preferably primary hydroxyl groups, which are bonded to at least one aliphatic carbon atom and which are at least partially substituted by an organic residue containing a covalently bonded sulfur atom as described above, are bonded to an aliphatic residue containing at least one aliphatic carbon atom, more preferably C 1~3 Aliphatic or C 4~6 A hydroxyl group bonded to a heteroaliphatic residue, even more preferably bonded to a C3 aliphatic or C6 heterocycloaliphatic residue, even more preferably bonded to a C3 aliphatic residue, and even more preferably bonded to a C3 alkyl residue.

[0061] The expression "at least partially" in connection with the phrase "at least a portion of the hydroxyl groups present in the chemical structure of the organic filler that are bonded to at least one aliphatic carbon atom are substituted with (...)" means "partially" or "completely," but preferably means "partially." Thus, preferably, not all of the hydroxyl groups bonded to at least one aliphatic carbon atom in the chemical structure of the organic filler are substituted with an organic residue that includes a covalently bonded sulfur atom.

[0062] Preferably, the sulfur-containing organic residue is a divalent organic residue in which at least one sulfur atom is located adjacent to an aliphatic carbon atom such that an aliphatic carbon-sulfur-aliphatic carbon bond is formed and present within the chemical structure of the organic filler. Preferably, the sulfur-containing organic residue is part of an organic modifier containing at least one thiol group, where the at least one sulfur atom present in the sulfur-containing organic residue is derived from the thiol group of the organic modifier.

[0063] The organic residue containing a sulfur atom preferably comprises an organic group selected from aliphatic, alicyclic, heteroaliphatic, heterocycloaliphatic, aromatic, and heteroaromatic groups, more preferably selected from aliphatic, alicyclic, and heteroaliphatic groups, even more preferably selected from aliphatic and heteroaliphatic groups, and even more preferably selected from aliphatic groups, in each case preferably excluding straight-chain unsubstituted groups having 6 carbon atoms, and in particular in each case the above-mentioned straight-chain unsubstituted aliphatic groups have at least 7 carbon atoms.

[0064] Each of the aforementioned organic groups may be unsubstituted, but may alternatively be substituted, in particular with at least one functional group. For example, the organic group may have at least one functional group that is reactive with at least one rubber and / or with at least one functional group of this rubber and / or with the vulcanization system present in the rubber composition, especially during vulcanization, when the filler according to the present invention is used in a rubber composition together with at least one rubber, and the at least one functional group is preferably selected from the group consisting of non-conjugated and / or conjugated carbon-carbon double bonds, in particular vinyl groups, sulfur-containing groups, and mixtures thereof, and particularly preferably cis carbon-carbon double bonds, optionally blocked mercapto groups, and di- and / or polysulfide groups, thioketone groups, mercaptobenzothiazole groups, dithiocarbamate groups, and mixtures thereof. Additionally or alternatively, the organic group may contain at least one functional group that increases the basicity of the filler after the formation of an aliphatic carbon-sulfur-aliphatic carbon bond within the chemical structure of the organic filler, particularly preferably an amino group, in particular an amino group selected from the group consisting of primary and secondary amino groups. Further chemical bonding with the filler can also occur via at least one additional functional group FGB of the organic modifier, especially when this is an amino group. Additionally or alternatively, the organic group may contain at least one alkoxysilyl group that allows crosslinking or lateral crosslinking within the organic filler through the formation of a siloxane bond.

[0065] Preferably, hydroxyl groups are still present in the chemical structure of the organic filler, in particular only a portion of these hydroxyl groups are replaced with an organic residue containing a covalently bonded sulfur atom, so that they are bound to at least one aliphatic carbon atom, i.e., the aliphatic OH group is still present.

[0066] Preferably, the organic filler further comprises at least one functional group selected from aromatic hydroxyl groups, preferably selected from phenolic hydroxyl groups, including phenolate groups, and carboxylic acid groups, including carboxylate groups.

[0067] Preferably, the aliphatic carbon-sulfur-carbon bonds present in the chemical structure of the organic filler are introduced by reaction, more preferably by substitution reaction, of at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom with at least one organic modifier comprising at least one thiol group located adjacent to a carbon atom in the chemical structure, such that at least a portion of these hydroxyl groups are replaced with an organic residue comprising a covalently bonded sulfur atom, the sulfur atom present therein originating from the thiol group of the organic modifier.

[0068] The at least one thiol group of the at least one organic modifier comprising at least one thiol group located adjacent to a carbon atom in its chemical structure can also be generated in situ via nucleophilic ring opening of a substituted or unsubstituted thiirane that serves as a thiol precursor.

[0069] Preferably, the sulfur content, based on the total weight of the organic filler, is >1.0% by weight (greater than 1.0%), more preferably in the range of >1.0% to 5.0% by weight (greater than 1.0% to 5.0% by weight), even more preferably 1.1 to 4.5%, even more preferably 1.2 to 4.0%, even more preferably 1.3 to 3.5%, even more preferably 1.3 to 3.0%, and especially 1.4 to 2.5% by weight. The sulfur content is determined according to the method disclosed in the "Method" section.

[0070] Preferably, the organic modifier used is a non-polymeric modifier, more preferably a monomer, however, as outlined below, preferably the organic modifier is instead a polymeric modifier.

[0071] Preferably, the aliphatic carbon-sulfur-carbon bond in the chemical structure is introduced by reacting at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom with at least one organic modifier, the at least one organic modifier having the following general formula (I): R 1 -L 1 -SH (I) (In the formula, L 1 is C 2~30 Alkylene group, C 2~30 Heteroalkylene group, C 3~30 Alkenylene group, C 2~30 Heteroalkenylene group, C 3~30 Alkynylene group, and C 2~30 heteroalkynylene groups, one or more hydrogen atoms of which may optionally and / or independently of one another be fluorine, a hydroxyl group, and / or an OC 1~4 substituted with at least one alkyl group, R 1 is an OH group, OC 1~4 Alkyl group, SH group, SC 1~4 Alkyl group, 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 base, OPO3 2- group or a salt thereof, an OC(=O)O group or a salt thereof, a 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, provided that R 11 , R 12 , R 13 , and R 14 are independently H, C 1~8 Alkyl, C 1~8 Alkenyl, and C 1~8 alkynyl) and at least one thiol of and / or The following general formula (II): R 2 -SH (II) (In the formula, R 2 C optionally contains one or more heteroatoms and / or heteroatom groups 1~30 is a hydrocarbon group, the heteroatoms are preferably selected from O, S, and N, more preferably selected from O and S, even more preferably selected from O, the heteroatom groups are preferably selected from NH and NR, and R is C 1~4 Aliphatic residues, preferably C 1~30 Hydrocarbon groups, excluding saturated and / or unsaturated C6 hydrocarbon groups, more preferably excluding C6 hydrocarbon groups, even more preferably C 7~30 a hydrocarbon group, in each case one or more hydrogen atoms may optionally and / or independently of one another be fluorine, a hydroxyl group, and / or OC 1~4 substituted with at least one alkyl group) and at least one thiol of and / or The following general formula (III): Si(X) 3-y (Y) y -L 2 -SH (III) (wherein y is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0; Y is a non-hydrolyzable organic residue, preferably unsubstituted C 1-30 is an alkyl group or a residue L 2 -SH represents L 2 has the meaning defined below: X, in each case independently of one another, represent a hydrolyzable group, which is preferably reactive with at least one of phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups, silyl ether groups, and mixtures thereof, preferably OC 1~4 Alkyl group, O(CH2) a -O(CH2) brepresents a hydrolyzable group selected from a -CH group (wherein a is an integer from 2 to 3 and b is an integer from 1 to 14), a halide, and mixtures thereof; L 2 is a divalent non-hydrolyzable organic residue, preferably C 1~30 alkylene groups, more preferably C 1~16 alkylene groups, and even more preferably C 1~6 alkylene groups, most preferably C 1~3 alkylene groups, in each case one or more hydrogen atoms are optionally and / or independently of one another selected from fluorine and OC 1~4 and each of said alkylene groups is substituted with at least one of said alkylene groups, however preferably each of said alkylene groups is unsubstituted. and at least one thiol of and / or As the thiol precursor, a compound represented by the following general formula (IV): [ka] (In the formula, R 4 C optionally containing one or more heteroatoms and / or heteroatom groups 1~30 is a hydrocarbon group, the heteroatoms are preferably selected from O, S, and N, more preferably selected from O and S, even more preferably selected from O, the heteroatom groups are preferably selected from NH and NR, and R is C 1~4 an aliphatic residue, preferably C 7~30 a hydrocarbon group, in which in each case one or more hydrogen atoms are optionally optionally and / or independently of one another fluorine, a hydroxyl group, and / or OC 1~4 substituted with at least one alkyl group) and at least one thiirane of and / or At least one polymeric polythiol having at least two or more, preferably terminal thiol groups, and preferably at least one polysulfide having two, three, or more, preferably terminal thiol groups.

[0072] For example, L 1 C as mentioned above in relation to the definition of 2~30 Heteroalkylene group, C 2~30 Heteroalkenylene groups, and C 2~30 Heteroalkynylene groups are alkylene, alkenylene, and alkynylene groups that additionally contain one or more heteroatoms and / or heteroatomic groups, where the heteroatoms are preferably selected from O, S, and N, more preferably O and S, and even more preferably O, and the heteroatomic groups are preferably selected from NH and NR, where R is C 1~4 The heteroatom(s) and / or heteroatom group(s) can be present within the respective group, i.e., can be located between two carbon atoms, such as in the case of a C2H4-O-C2H4 group, or alternatively or additionally can be at the end of the respective group, such as in the case of an O-C2H4-O-C2H4 group or an O-C2H4 group.

[0073] L 1 C 2~30 When representing a heteroalkylene group, said group preferably is [(CH2) c O] d (CH2) e or [(CH2) c S] d (CH2) e wherein c is an integer from 2 to 3, preferably 2; d is an integer from 1 to 6, preferably 2 to 4, more preferably d is 2; and e is an integer from 2 to 4, preferably 2 to 3, more preferably e is 2.

[0074] R in formula (II) 2C optionally containing one or more heteroatoms and / or heteroatom groups at positions 1~30 The hydrocarbon group may be, for example, C 2~30 Heteroalkylene groups, such as [(CH2) c O] d (CH2) e or [(CH2) c S] d (CH2) e wherein c is an integer from 2 to 3, preferably 2; d is an integer from 1 to 6, preferably 2 to 4, more preferably d is 2; and e is an integer from 2 to 4, preferably 2 to 3, more preferably e is 2.

[0075] Examples of thiols of general formula (III) are mercaptoalkyltrialkoxysilanes, such as mercaptomethyltrimethoxysilane and / or mercaptopropyltrimethoxysilane. An example of a thiol of general formula (I) is 1,2-bis(2-mercaptoethoxy)ethane.

[0076] As mentioned above, the aliphatic carbon-sulfur-carbon bonds in the chemical structure can alternatively and / or additionally be introduced by reacting at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom with at least one organic modifier, e.g., a polymeric polythiol, e.g., at least one polymeric polythiol having at least two or more, preferably terminal, thiol groups, e.g., polysulfides having two, three, or more, preferably terminal thiol groups. Preferably, polymeric polythiols suitable for this purpose have a weight average molecular weight (M), as determinable by gel permeation chromatography (GPC), in the range of 500 to 50,000 g / mol, more preferably 500 to 25,000 g / mol, and even more preferably 750 to 10,000 g / mol, or 5,000 g / mol. w )

[0077] In the scheme below, possible reaction sequences for introducing the above-mentioned aliphatic carbon-sulfur-carbon bonds present in the chemical structure of organic fillers are exemplarily shown when thiols of the above-mentioned general formula (III) are used, where HTT stands for lignin having aliphatic OH groups and obtainable by hydrothermal treatment.

[0078] Scheme: Possible reaction sequence: [ka]

[0079] For the preparation of the organic filler according to the invention, 14 C content ranges from 0.20 to 0.45 Bq / g carbon and BET surface area ranges from 10 to <200 m 2 / g(10 to 200m 2 Organic filler precursor FPMs in the range of % by mass (wt. or less than 1 / g) are suitable as starting materials, which contain at least one hydroxyl group bonded to at least one aliphatic carbon atom. Formation of any aliphatic carbon-sulfur-carbon bonds has not yet occurred at this point. At least in this respect, the filler precursor FPMs differ from the organic fillers of the present invention.

[0080] Preferably, the organic filler can be obtained by carrying out at least one step a) and optionally one or more of steps b) to d), wherein steps a) to d) are as follows: a) at least one organic modifier containing at least one thiol group located adjacent to a carbon atom in its chemical structure and a concentration in the range of 0.20 to 0.45 Bq / g carbon; 14 C content, 10 to <200m 2 / g(10-200m 2 and at least one organic filler precursor FPM having a BET surface area in the range of 0.1 to 1.0 MPa (less than 1 / g) and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; b) optionally and optionally heating the mixture obtained according to step a), preferably in a liquid or gaseous reaction medium or in solid phase, preferably to a temperature in the range of from 30° C. to 190° C., more preferably to a temperature in the range of from 50° C. to 180° C., most preferably to a temperature in the range of from 70° C. to 170° C., c) optionally, if the optional heating according to step a) and / or step b) has been carried out in a liquid reaction medium containing at least one organic solvent, extracting at least one organic solvent after at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom of the organic filler precursor FPM has been replaced with an organic residue containing a covalently bonded sulfur atom, in which at least one sulfur atom is derived from a thiol group of the organic modifier; and d) Optionally, if necessary, after carrying out step a) and optionally step b) and / or c), drying the organic filler obtained, preferably in vacuum and / or at a temperature in the range of from 20 to 100°C.

[0081] The combining step in step a) and, optionally, the optional heating step in step b) can be carried out in a reaction medium that is preferably in a liquid or gaseous state. The organic modifier and / or the filler precursor FPM used and / or the resulting mixture can be present in a liquid or gaseous reaction medium, as appropriate in each case. A liquid reaction medium therefore preferably comprises or consists exclusively of at least one organic solvent, particularly preferably at least one hydrocarbon, most preferably at least one aliphatic and / or aromatic hydrocarbon. In the case of a gaseous reaction medium, the covalent bonding of the organic modifier to the filler precursor FPM can be achieved by CVD (chemical vapor deposition) and / or plasma modification.

[0082] Preferably, step a) is carried out at room temperature (18 to <30°C). Covalent bonding of the organic modifier to the filler precursor FPM can already occur under these conditions. However, optionally and preferably, step b) is carried out. In this case, covalent bonding of the organic modifier to the filler precursor FPM preferably occurs in the temperature range already mentioned in connection with step b).

[0083] The extraction according to optional step c) is preferably carried out at a temperature ranging from 20 to 150° C., and may optionally be carried out in vacuum.

[0084] Preferably, after and / or during step a) and optionally step b), the reaction mixture is mixed, for example by stirring, for a period of 0.01 to 30 hours, particularly preferably 0.01 to 5 hours, in order to achieve complete reaction, in particular with the organic modifier used in the amounts used above.

[0085] Preferably, the organic filler according to the invention is present in rubber-free form and / or is produced in rubber-free form, which means in particular that the formation of the aliphatic carbon-sulfur-carbon bonds present in the chemical structure of the organic filler does not occur in situ in the rubber composition or in the presence of the rubber, but has already occurred in a separate step (ex situ).

[0086] Preferably, after the aliphatic carbon-sulfur-carbon bond has been formed, the organic filler according to the invention contains, based on its total weight, from 0.1 to 30% by weight of the organic modifier, particularly preferably from 0.5 to 25% by weight, most preferably from 1 to 15% by weight, and in particular from 1.5 to 12% by weight. Of course, it is taken into account herein that during the substitution reaction involving the thiol group of the organic modifier and the aliphatic hydroxyl group of the organic filler precursor FPM, cleavage products such as water may be formed, which therefore do not contribute to the proportion of modifier in the filler.

[0087] rubber composition A further object of the present invention is a rubber composition comprising at least one rubber and at least one filler component, the filler component comprises at least one organic filler as defined above and below; and / or The filler component comprises: (i) a carbon content in the range of 0.20 to 0.45 Bq / g; 14 C content, 10 to <200m 2 / g(10 to 200m 2 and (ii) at least one organic filler precursor FPM having a BET surface area in the range of less than 1 / g and having at least one hydroxyl group bonded to at least one aliphatic carbon atom; and (iii) at least one organic modifier comprising at least one thiol group located adjacent to a carbon atom in its chemical structure, with which a covalent bond to the at least one organic filler precursor FPM can be formed through at least partial substitution of a hydroxyl group present in the chemical structure of the organic filler precursor FPM bonded to at least one aliphatic carbon atom with an organic residue comprising a covalently bonded sulfur atom, such that an aliphatic carbon-sulfur-carbon bond occurs in the chemical structure of the organic filler, wherein at least one sulfur atom present therein comes from the thiol group of the organic modifier, to form an organic filler as defined above and below.

[0088] All preferred embodiments already described in connection with the organic filler according to the invention are also preferred embodiments for the rubber composition according to the invention.

[0089] Preferably, the filler component comprises at least one organic filler according to the invention as described in relation to the first subject of the invention.

[0090] Any type of rubber is suitable for preparing the rubber compounds according to the invention. Natural rubber (NR) and synthetic rubbers are known to those skilled in the art. Preferably, the at least one rubber is selected from the group consisting of natural rubber (NR), halobutyl rubber, and likewise preferably chlorobutyl rubber (CIIR; chloro-isobutene-isoprene rubber) and bromobutyl rubber (BIIR; bromo-isobutene-isoprene rubber), and mixtures thereof, butyl rubber or isobutylene-isoprene rubber, respectively, isobutylene-isoprene rubber (IIR; isobutene-isoprene rubber), styrene-butadiene rubber (SBR, styrene-butadiene rubber), also 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.

[0091] Particularly preferred is styrene-butadiene rubber (SBR), and likewise preferred is at least one rubber selected from the group consisting of SSBR, polybutadiene (BR), EPDM, NR, and acrylonitrile-butadiene rubber (NBR), and mixtures thereof. Particularly preferred is styrene-butadiene rubber (SBR), and likewise preferred are SSBR and polybutadiene (BR), and mixtures thereof.

[0092] In the case of a blend of SBR and BR, the proportion of SBR is preferably higher than the proportion 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.

[0093] The designation phr (parts by weight per hundred parts by weight rubber) used herein is the designation of amounts commonly used in the rubber industry for compounding compounds. The amount of an individual component used in parts by weight is always relative to 100 parts by weight, which is the total weight of all rubbers present in the compound.

[0094] Preferably, the rubber composition comprises at least one organic filler in an amount ranging from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, in particular from 40 to 100 phr, and / or at least one organic filler precursor FPM as defined under (i) above in an amount ranging from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, in particular from 40 to 100 phr, and at least one organic modifier as defined under (ii) above in an amount ranging from 0.1 to 30% by mass, particularly preferably from 0.5 to 25% by mass, most preferably from 1.0 to 15% by mass, in particular from 1.5 to 12% by mass, in each case based on the total mass of the organic filler precursor FPM. As explained above, the formed reject product does not contribute to the amount of organic modifier relative to the total mass of the filler FPM.

[0095] In addition to the organic fillers and / or organic filler precursors FPM according to the invention, the rubber composition may contain other fillers different from these fillers.

[0096] If the organic filler according to the present invention serves only as a partial replacement for common industrial carbon black, the rubber composition according to the present invention may also contain industrial carbon black, in particular furnace carbon black, such as general-purpose or industrial carbon black classified under ASTM code N660.

[0097] Additionally or alternatively, the rubber composition according to the invention may contain inorganic fillers, which have different potential to influence the vulcanization behavior, for example, of different particle sizes, particle surface areas, and chemical nature. If further fillers are included, they should preferably have properties as similar as possible to the properties of the organic fillers of the invention used in the rubber composition according to the invention, in particular with respect to their pH.

[0098] If further fillers are used, these are preferably phyllosilicates, such as clay minerals, e.g. talc; carbonates such as calcium carbonate; silicates, such as calcium, magnesium, and aluminum silicates; and oxides, such as magnesium oxide, silica, or silicic acid.

[0099] In particular, when the organic filler according to the invention serves only as a partial replacement for conventional silica(s), the rubber composition according to the invention may contain such inorganic filler as silica or silicic acid.

[0100] However, in the context of this invention, zinc oxide is not counted as an inorganic filler because its function is as a vulcanizing agent or vulcanization accelerator additive. However, additional fillers should be carefully selected because, for example, higher amounts of magnesium oxide can adversely affect adhesion to adjacent tire layers, and silica tends to bind organic molecules, such as thiazoles used in some vulcanization systems, to its surface, thus inhibiting their action.

[0101] Preferably, inorganic fillers, including silica and other fillers having Si-OH groups on their surfaces, can also be surface-treated (surface-modified). In particular, silanization with an organic silane, such as an alkylalkoxysilane, an aminoalkylalkoxysilane, or a mercaptoalkylalkoxysilane, can be advantageous. For example, alkoxysilane groups can be bonded to the surface of silicate or silica or other suitable groups by hydrolytic condensation, while amino and thiol groups, for example, can react with the isoprene units of certain rubbers. This can provide mechanical reinforcement for the vulcanized rubber composition of the present invention.

[0102] Fillers other than the organic fillers according to the invention can be used individually or in combination with one another.

[0103] If further fillers are used, their proportion is preferably less than 40 phr, more preferably from 20 to 40 phr, particularly preferably from 25 to 35 phr.

[0104] The rubber composition according to the present invention may contain further optional components, such as plasticizers and / or anti-aging agents, resins, especially adhesion-enhancing resins, and also the previously mentioned vulcanizing and / or vulcanization-accelerating additives, for example zinc oxide and / or fatty acids such as stearic acid.

[0105] The use of plasticizers can affect the properties of unvulcanized rubber compositions, such as their processability, but can also affect the properties of vulcanized rubber compositions, such as their flexibility, especially at low temperatures. Particularly suitable plasticizers in the context of the present invention are mineral oils from the groups of paraffin oils (especially saturated chain-form hydrocarbons) and naphthenic oils (substantially saturated cyclic hydrocarbons). The use of aromatic hydrocarbon oils is also possible and preferred. However, mixtures of paraffinic and / or naphthenic oils with aromatic oils can also be advantageous as plasticizers in terms of adhesion of the rubber composition to other rubber-containing components of the tire, such as the carcass. Other possible plasticizers include esters of aliphatic dicarboxylic acids, such as adipic or sebacic acid, kerosene wax, and polyethylene wax. Among the plasticizers, paraffinic and naphthenic oils are particularly suitable in the context of the present invention, but aromatic oils, especially aromatic mineral oils, are most preferred.

[0106] Preferably, plasticizers, hereinafter very preferably paraffinic and / or naphthenic, especially aromatic processing oils, are used in an amount of 0 to 100 phr, preferably 10 to 70 phr, more preferably 20 to 60 phr, especially 20 to 50 phr.

[0107] Examples of the deterioration inhibitor include quinolines such as TMQ (2,2,4-trimethyl-1,2-dihydroquinoline) and diamines such as 6-PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine).

[0108] To improve the adhesion of the vulcanized rubber compound of the present invention to other adjacent tire components, so-called adhesion-enhancing resins can be used. Particularly suitable resins are phenol-based, preferably from the group consisting of phenolic resins, phenol-formaldehyde resins, and phenol-acetylene resins. In addition to phenolic resins, aliphatic hydrocarbon resins, such as Escorez® 1102 RM from ExxonMobil, as well as aromatic hydrocarbon resins can also be used. Aliphatic hydrocarbon resins, in particular, improve adhesion to other rubber components of the tire. They generally have lower adhesion than phenolic resins and can be used alone or mixed with phenolic resins.

[0109] When an adhesion-enhancing resin is used, it is preferably selected from the group consisting of phenolic resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins, and its content is preferably 0 to 15 phr, or 1 to 15 phr, more preferably 2 to 10 phr, and most preferably 3 to 8 phr.

[0110] The rubber composition according to the present invention may contain additives that accelerate vulcanization but cannot independently cause it. Such additives include, for example, saturated fatty acids having 12 to 24, preferably 14 to 20, and particularly preferably 16 to 18 carbon atoms, such as stearic acid, and vulcanization accelerators such as zinc salts of the aforementioned fatty acids. Thiazoles may also be included among these additives. However, vulcanization accelerator additives can only be used in the vulcanization system described below.

[0111] If vulcanization accelerator additives, in particular the above-mentioned fatty acids and / or zinc salts, preferably stearic acid and / or zinc stearate, are used in the rubber composition according to the invention, their proportion is from 0 to 10 phr, particularly preferably from 1 to 8 phr, particularly preferably from 2 to 6 phr.

[0112] Furthermore, the rubber composition according to the present invention may already contain certain vulcanizing agents, such as zinc oxide, which is preferred, but it is also possible to use such vulcanizing agents only in the vulcanization system described below.

[0113] If vulcanizing agents such as zinc oxide are used in the rubber composition according to the invention, their proportion is preferably 0 to 10 phr, more preferably 1 to 8 phr, particularly preferably 2 to 6 phr.

[0114] Vulcanizable rubber composition A further subject of the present invention is a vulcanizable rubber composition comprising the rubber composition 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 at least sulfur.

[0115] All preferred embodiments mentioned above in relation to the organic filler and rubber composition according to the invention are also preferred embodiments for the vulcanizable rubber composition according to the invention.

[0116] The term "vulcanization" in the sense of the present invention means "crosslinking", and the term "vulcanization system" in the sense of the present invention means "crosslinking system". Similarly, "vulcanizable" means "crosslinkable", and "vulcanized" means "crosslinked". These definitions are known to those skilled in the art, for example from PAC 2007, 79, 1801, 1826, and from "Kautschuk Technologie", F. Rothemeyer and F. Sommer, 3rd Edition, 2013. In particular, not only sulfur vulcanization is included in the term "vulcanization", but also other types of crosslinking reactions, for example crosslinking reactions with peroxides.

[0117] The vulcanization system is not counted here as part of the rubber composition according to the invention, but is treated as an additional system for adjusting crosslinking. By adding the vulcanization system to the rubber composition according to the invention, a vulcanizable rubber composition also according to the invention is obtained.

[0118] The rubber component of the vulcanizable rubber composition according to the present invention, which contains at least one rubber, allows for the use of a wide variety of vulcanization systems.

[0119] 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, for example, particularly at least one organic peroxide. When zinc oxide is used, it may be added to the rubber component (A) or to the component (B). Preferably, zinc oxide is added to the component (A). When sulfur is used, it is preferably added to the component (B).

[0120] Preferably, at least zinc oxide and / or at least sulfur are used in combination with various organic compounds for vulcanization, which various additives can affect the vulcanization behavior and the properties of the resulting vulcanized rubber.

[0121] In at least the first variant of vulcanization based on zinc oxide, a small amount of saturated fatty acid having 12 to 24, preferably 14 to 20, particularly preferably 16 to 18 carbon atoms, such as stearic acid and / or zinc stearate, is preferably added to zinc oxide as a vulcanization accelerator. This allows the vulcanization rate to increase. However, the final degree of vulcanization usually decreases when the aforementioned fatty acid is used.

[0122] In a second variant of vulcanization based at least on zinc oxide, so-called thiurams, such as thiuram monosulfide and / or thiuram disulfide and / or tetrabenzylthiuram disulfide (TBzTD) and / or dithiocarbamates and / or sulfenamides, are added to zinc oxide in the absence or presence of sulfur in order to shorten the scorch time and improve the efficiency of the vulcanization by forming a particularly stable network. The thiazoles and sulfenamides are preferably selected from the group consisting of 2-mercaptobenzothiazole (MBT), mercaptobenzothiazyl disulfide (MBTS), N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), 2-morpholinothiobenzothiazole (MBS), and N-tert-butyl-2-benzothiazyl sulfenamide (TBBS).

[0123] In at least a third variant of vulcanization based on zinc oxide, alkylphenol disulfides are added to zinc oxide in order to adjust, and in particular accelerate, its scorch time. Furthermore, at least a fourth variant of vulcanization based on zinc oxide uses a combination of zinc oxide with polymethylolphenolic resins and their halogenated derivatives, in which case preferably no sulfur or sulfur-containing compounds are used.

[0124] In a most preferred fifth variant of vulcanization based at least on zinc oxide, vulcanization is carried out using a combination of zinc oxide with thiazoles and / or thiurams and / or sulfenamides, and preferably sulfur. The addition of sulfur to such a system increases both the rate and extent of vulcanization, contributing to the processability of the rubber composition during the vulcanization process. The use of this vulcanization system preferably results in a heat- and fatigue-resistant vulcanizate that exhibits good adhesion to other components of vehicle tires, particularly the rubber composition of the carcass, even after vulcanization. A particularly advantageous vulcanization system comprises zinc oxide, a thiuram, such as tetrabenzyl thiuram disulfide (TBzTD), a sulfenamide, such as N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), and sulfur. Particularly preferred is the combination of the first and fifth variants, i.e. the use of a vulcanization system comprising zinc oxide, a thiuram such as tetrabenzylthiuram disulfide (TBzTD), a sulfenamide such as N-tert-butyl-2-benzothiazylsulfenamide (TBBS), sulfur, and stearic acid, and / or optionally zinc stearate.

[0125] Less preferred vulcanization systems are those based on pure sulfur vulcanization or peroxide vulcanization, the latter of which can lead to undesirable reduction in molecular weight due to molecular scission, especially when butyl or other rubbers are used.

[0126] In the context of the present invention, the vulcanization of the rubber composition according to the invention is carried out in the presence of the organic fillers according to the invention, for example lignins obtainable by hydrothermal treatment.

[0127] Components of the vulcanization system that cannot themselves cause vulcanization can also be included in the rubber composition of the present invention as "further components of the rubber composition", i.e. they can already be part of the rubber composition according to the present invention and therefore do not necessarily have to be included in the vulcanization system. Thus, as already mentioned above, it is in particular possible that stearic acid and / or optionally zinc stearate are already present in the rubber composition according to the present invention and that the complete vulcanization system is formed in situ, for example by mixing / adding at least zinc oxide and at least sulfur.

[0128] Multi-part kits (kit-of-parts) For the combination between the rubber composition according to the invention and the crosslinking system (vulcanization system) to be selected for its vulcanization, for the preparation of the vulcanizable rubber composition according to the invention, the present invention also relates to a kit of parts, which comprises, in spatially separated form, the rubber composition as part (A) as defined above and below, and a vulcanization system as part (B) as defined above and below, preferably a vulcanization system comprising at least zinc oxide and / or at least sulfur.

[0129] In a multi-part kit (kit of parts), the rubber composition according to the invention and the vulcanization system are spatially separated from one another and can therefore be stored. This kit of parts is used to prepare vulcanizable rubber compositions. For example, the rubber composition according to the invention, which is part of the kit of parts, can be used as part (A) in step 1 of the method described below to produce a vulcanizable rubber compound, and the second part of the kit of parts, i.e., the vulcanization system, can be used as part (B) in step 2 of the method.

[0130] In contrast to a vulcanizable rubber composition which already contains a homogeneous mixture of both the components of the rubber composition according to the invention and the accompanying vulcanization system described above, and which can therefore be vulcanized directly, in the kit-of-parts according to the invention the rubber composition according to the invention and the vulcanization system are spatially separated from each other.

[0131] All systems already mentioned above in connection with the vulcanizable rubber composition according to the invention can be used as vulcanization systems.

[0132] All of the preferred embodiments already mentioned herein in relation to the inventive organic filler and the inventive (vulcanizable) rubber composition are also preferred embodiments in relation to the inventive kit-of-parts.

[0133] Preferably, the kit of parts according to the invention comprises: as part (A) a rubber composition according to the invention, and as part (B) a vulcanization system comprising at least zinc oxide and / or at least sulfur, Here, at least the zinc oxide may instead (alternatively) be present in part (A).

[0134] Particularly preferably, the kit of parts according to the invention comprises: as part (A) a rubber composition according to the invention, and as part (B) a vulcanization system comprising zinc oxide, sulfur, and at least one thiuram; Here, at least the zinc oxide may instead (alternatively) be present in part (A).

[0135] Even more preferably, the kit-of-parts according to the invention comprises: as part (A) a rubber composition according to the invention, and as part (B) a 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; Here, at least zinc oxide and / or stearic acid and / or zinc stearate may instead (alternatively) be present in part (A).

[0136] In particular, the kit of parts according to the invention comprises: as part (A) a rubber composition according to the invention, and as part (B) a 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; Here, at least zinc oxide and / or stearic acid and / or zinc stearate may instead (alternatively) be present in part (A).

[0137] The vulcanizable rubber composition according to the present invention is preferably prepared in two stages, stages 1 and 2, and the rubber composition according to the present invention is preferably obtainable after passing through the first stage of this two-stage process.

[0138] In a first step (step 1), the rubber composition according to the invention is first prepared as a base mixture (masterbatch) by mixing together all the components used to prepare the rubber composition according to the invention. In a second step (step 2), the components of the vulcanization system are added to the rubber composition according to the invention.

[0139] <Level 1> Preferably, at least one rubber contained in the rubber component of the rubber composition according to the invention is prepared together with a different, preferably adhesion-improving, optional resin. However, the latter may also be added together with further additives. Preferably, the rubber is at least at room temperature (23°C) or is preheated to a temperature of preferably up to 50°C, preferably up to 45°C, particularly preferably up to 40°C. Particularly preferably, the rubber is premixed for a short time before the other components are added. If inhibitors are used to control the subsequent vulcanization (e.g., magnesium oxide), they are also preferably added at this point.

[0140] Thereafter, at least one organic filler according to the present invention and optionally further fillers are added, preferably excluding zinc oxide, since this is used in the rubber composition according to the present invention as a component of the vulcanization system and is therefore not considered a filler here. The addition of the at least one organic filler according to the present invention and optionally other fillers is preferably done in increasing amounts.

[0141] Advantageously, but not necessarily, the plasticizer and other components, such as stearic acid and / or zinc stearate and / or zinc oxide, are added only after the addition of at least one organic filler according to the present invention or other fillers, if used. This facilitates the incorporation of at least one organic filler according to the present invention and other fillers, if present. However, it may be advantageous to incorporate a portion of the at least one organic filler according to the present invention or a portion of other fillers, if present, together with the plasticizer and any other components used.

[0142] In the first stage, the maximum temperature attained during the preparation of the rubber composition ("dump temperature") should not exceed 170°C, since temperatures higher than these temperatures allow partial decomposition of the reactive rubber and / or the organic filler of the present invention. However, temperatures >170°C (higher than 170°C), for example up to <200°C (lower than 200°C), are also possible, depending in particular on the rubber used. Preferably, the maximum temperature during the preparation of the rubber composition in the first stage is between 80°C and <200°C (less than 200°C), particularly preferably between 90°C and 190°C, and most preferably between 95°C and 170°C.

[0143] The mixing of the components of the rubber composition according to the invention is usually carried out using an internal mixer with tangential or meshing (i.e., intermeshing) rotors. The latter usually allows for better temperature control. Mixers with tangential rotors are also called tangential mixers. However, mixing can also be carried out using, for example, a two-roller mixer.

[0144] After the rubber composition is prepared, it is preferably cooled before the second step is carried out. Such a process is also called aging. Typical aging periods are 6 to 24 hours, preferably 12 to 24 hours.

[0145] <Stage 2> In a second stage, the components of the vulcanization system are incorporated into the rubber composition of the first stage, thereby obtaining a vulcanizable rubber composition according to the present invention.

[0146] If a vulcanization system based on at least zinc oxide and at least sulfur is used as the vulcanization system, at least sulfur and other optional components, such as in particular at least one thiuram and / or at least one sulfenamide, are preferably added in stage 2. It is also possible to add zinc oxide in stage 2 and, optionally, at least one saturated fatty acid, such as stearic acid. However, these components are preferably already integrated into the rubber composition according to the invention in stage 1.

[0147] The maximum temperature ("dump temperature") attained during the preparation of the mixture of the vulcanization system to the rubber composition in the second stage should preferably not exceed 130°C, particularly preferably 125°C. The preferred temperature range is between 70°C and 125°C, particularly preferably 80°C to 120°C. For crosslinked systems, premature vulcanization may occur at temperatures higher than the maximum of 105 to 120°C.

[0148] After the vulcanization system is added in stage 2, the composition is preferably cooled.

[0149] In the two-stage procedure described above, the rubber composition according to the invention is thus initially obtained in a first stage, and in a second stage the auxiliary ingredients are added to form the vulcanizable rubber composition.

[0150] vulcanized rubber composition A further 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 the kit-of-parts as defined above and below.

[0151] Prior to vulcanization, the vulcanizable rubber composition produced, preferably subjected to a molding process, is fabricated into a final article. The rubber composition is preferably formed into the appropriate shape required for the vulcanization process by extrusion or calendering. Vulcanization can be carried out in a vulcanization mold using pressure and temperature, or vulcanization can be carried out without pressure in a temperature-controlled channel where air or liquid material provides heat transfer.

[0152] All preferred embodiments described above in relation to the organic filler according to the invention, the (vulcanizable) rubber composition according to the invention and the kit-of-parts according to the invention are also preferred embodiments for the vulcanized rubber composition according to the invention.

[0153] Vulcanization is usually carried out under pressure and / or heat. Suitable vulcanization temperatures are preferably 140°C to 200°C, particularly preferably 150°C to 180°C. Optionally, vulcanization is carried out at a pressure in the range of 50 to 175 bar. However, for example, in the case of profiles, vulcanization can also be carried out at a pressure in the range of 0.1 to 1 bar.

[0154] The vulcanized rubber compositions obtained from the vulcanizable rubber composition according to the present invention preferably have a Shore A hardness in the range of from greater than 50 to less than 70, more preferably from 53 to 65, and most preferably from 55 to 62, and / or a rebound resilience in the range of from greater than 60% to less than 75%, more preferably from greater than 61% to less than 73%, and most preferably from greater than 62% to less than 72% at 70° C. Methods for determining Shore A hardness and rebound resilience are given in the method description below.

[0155] use Further objects of the present invention are the use of the organic fillers as defined above and below for producing rubber compositions and vulcanizable rubber compositions, and the use of the rubber compositions as defined above and below for producing tires, preferably pneumatic and solid tires, in particular pneumatic tires, preferably in each case for producing their treads, sidewalls and / or innerliners, and / or for producing technical rubber articles, preferably profiles, seals, dampers and / or hoses.

[0156] All preferred embodiments mentioned above in relation to the organic filler according to the invention, the (vulcanizable) rubber composition according to the invention, the kit-of-parts according to the invention and the vulcanized rubber composition according to the invention are also preferred embodiments in relation to the aforementioned uses according to the invention.

[0157] For example, the vulcanizable rubber composition according to the present invention can be used to manufacture pneumatic tires, preferably pneumatic tires comprising a tread made from the vulcanizable rubber composition. The tread is typically vulcanized under pressure and / or heat together with the tire carcass and / or other tire components. Suitable vulcanization temperatures are preferably 140°C to 200°C, particularly preferably 150°C to 180°C. This process can be carried out, for example, by closing a press to form a tire blank in a closed mold. For this purpose, a low pressure (<0.2 bar) can be applied to an internal bellows (heated bellows) so that the bellows also fits into the tire blank. The press, and thus the mold, is then completely closed. The pressure in the bellows increases (peak pressure, typically about 1.8 bar). This imprints the profile into the tread and the sidewall labeling. 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 size of the tire and can be up to 2500 kN using a hydraulic cylinder. After applying the clamping force, the actual vulcanization process begins. The mold is continuously heated with steam from the outside. A temperature between 150 and 180°C is generally set. As for the internal medium, there are many different designs depending on the type of tire. For example, steam or hot water is used inside the bladder. The internal pressure can vary and be different depending on the type of tire, for example, car and truck tires.

[0158] <Method> 1. Determination of BET and STSA surface areas of organic fillers. The specific surface area of ​​the fillers investigated was determined by nitrogen adsorption in accordance with ASTM D 6556 (2019-01-01) standard for industrial carbon black, in accordance with which the BET surface area (total specific surface area according to Brunauer, Emmett, and Teller) and external surface area (STSA surface area; statistical thickness surface area) were also determined as follows:

[0159] The samples to be analyzed were dried to a dry matter content of ≥ 97.5 (97.5 or greater) by weight at 105 °C before measurement. Furthermore, the measuring cell was dried for several hours in a drying oven at 105 °C before the sample was weighed in. The sample was then placed in the measuring cell using a funnel. If the upper measuring cell shaft became contaminated during filling, it was cleaned using a suitable brush or pipe cleaner. For strongly spattering (electrostatic) materials, glass wool was weighed in addition to the sample. The glass wool served to retain any spattering material that could contaminate the instrument during the heating process.

[0160] The samples to be analyzed were baked for 2 hours at 150° C., and the Al2O3 standard sample was baked for 1 hour at 350° C. The following N2 feed rates were used for the measurements, depending on the pressure range: p / p0=0-0.01:N2 supply amount:5ml / g p / p0=0.01-0.5:N2 supply amount: 4ml / g.

[0161] To determine the BET, extrapolations were performed over at least six measurement points in the range of p / p0 = 0.05-0.3. To determine the STSA, extrapolations were performed over at least seven measurement points in the range of adsorbed N2 layer thicknesses of t = 0.4-0.63 nm (corresponding to p / p0 = 0.2-0.5).

[0162] 2. Determination of ash content of organic fillers (TGA; thermogravimetric analysis) The anhydrous ash content of the samples was determined by thermogravimetric analysis in accordance with the DIN 51719 standard as follows: the samples were crushed or ground before weighing. The dry matter content of the weighed material was determined before determining the ash content. The sample was weighed into a crucible to the nearest 0.1 mg. The furnace containing the sample was heated to a target temperature of 815°C at a heating rate of 9°K / min and then held at this temperature for 2 hours. The furnace was then cooled to 300°C, after which the sample was removed. The ash content was determined. The sample was cooled to ambient temperature in a desiccator and reweighed. The remaining ash was related to the mass of the sample to determine the ash content by mass. Triplicate determinations were made for each sample, and the average value was reported.

[0163] 3. Determining the pH value of organic fillers The pH values ​​were determined according to ASTM D 1512 as follows: The dried samples, if not already available as powders, were ground or crushed to a powder. In each case, 5 g of sample and 50 g of fully deionized water were weighed into a beaker. The suspension was heated to a temperature of 60°C using a magnetic stirrer with heating function and magnetic stirring, while constantly stirring, and the temperature was maintained at 60°C for 30 minutes. The heating function of the stirrer was then turned off to allow the batch to cool while stirring. After cooling, the evaporated water was replaced by adding fully deionized water again, and stirring was again carried out for 5 minutes. The pH of the suspension was determined using a calibrated balance. The temperature of the suspension was brought to 23°C (±0.5°C). Duplicate determinations were made for each sample, and the average value was reported.

[0164] 4. 14 Determination of C content 14 Determination of the C content (biobased carbon content) can be carried out using the radiocarbon method in accordance with DIN EN 16640:2017-08.

[0165] 5. Carbon content determination The carbon content can be determined by elemental analysis according to DIN 51732:2014-7.

[0166] 6. Oxygen content determination The oxygen content can be determined by elemental analysis in accordance with DIN 51732:2014-7. In this process, the CHNS content is determined using the aforementioned analysis and the oxygen is then calculated as the difference (100-CHNS).

[0167] 7. Determination of particle size distribution The particle size distribution can be determined by laser diffraction of the material dispersed in water according to ISO 13320:2020-01. The volume fraction is specified as d99 (the diameter of 99% of the particles in the sample volume is below this value), e.g. in μm.

[0168] 8. Determination of solubility in alkaline media The determination of alkaline solubility is carried out as follows:

[0169] The solubility is determined in triplicate. For this purpose, 2.0 g of dry filler is weighed into 20 g of 0.1 M NaOH, respectively. However, if the pH of the determined sample is <10 (less than 10), this sample is discarded, and instead 2.0 g of dry filler is weighed into 20 g of 0.2 M NaOH, respectively. Therefore, depending on the pH (<10 or ≥10 (less than 10 or ≥10)), 0.1 M NaOH is used (pH ≥10) or 0.2 M NaOH (pH <10) is used. The alkaline suspension is shaken at room temperature for 2 hours at a shaker speed of 200 revolutions per minute. To avoid contact of the liquid with the lid during this process, the shaker speed is reduced to a level where this contact does not occur. The alkaline suspension is then centrifuged at 6000 g. The supernatant from the centrifugation is removed and filtered through a Por 4 frit. The centrifuged solid is washed twice with distilled water, and the above centrifugation and filtration steps are repeated after each wash. The solid is dried to constant weight in a drying oven at 105°C for at least 24 hours. The alkali solubility of the solid is calculated as follows:

[0170] Alkali-soluble solids [%] = mass of undissolved fraction after centrifugation, filtration, and drying [g] × 100 / mass of starting material [g].

[0171] 9. 13 C solid-state NMR 13 C solid-state NMR (SSNMR) spectra were obtained on a Bruker 9.4T ( 1Operates at 400.34 MHz for H, and 13 The spectra were obtained on an Avance III HD 400 spectrometer (operating at 100.67 MHz for C). 13 C cross-polarization (CP) MAS measurements were performed at a spin rate of 14 kHz with a 90° pulse. 1 For H, the contact time was 2.4 μs and 2 ms. 13 C spectra were internally referenced by the chemical shift of the methoxy peak of lignin (δ = 56.1 ppm) and acquired with 1486 complex points, a spectral wavewidth of 295 ppm, a relaxation delay of 2 s, and up to 30000 averages to ensure a sufficient signal-to-noise ratio.

[0172] 10. Sulfur content determination The sulfur content can be determined by elemental analysis in accordance with DIN 51724-1:2012-7.

[0173] 11. Mechanical property evaluation The vulcanizates for tensile testing were pressed into a 90 x 90 x 2 mm Wickert laboratory press for 30 minutes. 3 The vulcanized sheets were then die-cut into dumbbell-shaped specimens for tensile testing. Testing was performed on a Zwick Z020 universal tensile testing machine according to ISO 37, Method A, at a crosshead speed of 500 mm / min. Five specimens were used for evaluation of the tensile data. The average values ​​obtained from these five specimens are reported.

[0174] 12. Determination of compound hardness The hardness of the samples was measured at 23°C on a Zwick 3150 hardness tester, Shore A, according to ISO 48. The test was carried out using cylindrical specimens 6 mm thick, prepared for 30 minutes. [Example]

[0175] The following examples further illustrate the present invention but should not be construed as limiting its scope.

[0176] 1. Preparation of organic fillers 1.1 Organic filler precursor FPM1 The hydrothermally obtainable lignin FPM1 was used as the organic filler precursor material. The hydrothermally obtainable lignin FPM1 was prepared in a manner similar to that described in WO 2017 / 085278 A1 for the preparation of hydrothermally obtainable lignin.

[0177] For this purpose, a liquid containing renewable raw materials is prepared. First, water and lignin are mixed to prepare a lignin-containing liquid with an organic dry matter content of 15% by mass. The lignin is then completely dissolved in the lignin-containing liquid. For this purpose, the pH is adjusted to 9.8 by adding NaOH. The solution is prepared with the aid of vigorous mixing at 80°C for 3 hours. The lignin is then dissolved in the liquid. The liquid containing renewable raw materials is subjected to hydrothermal treatment to obtain a solid. In this process, the prepared solution is heated at 1.4 K / min to a reaction temperature of 220°C and maintained for a reaction period of 7 hours. The solution is then cooled. As a result, an aqueous solid suspension is obtained. The solid is extensively dehydrated and cleaned 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 deagglomerated and deagglomerated in a NETZSCH steam jet mill under nitrogen to a d99 < 20 μm. The subsequent heat treatment is carried out in a furnace under nitrogen, heated to a temperature of 230° C., held for 0.5 hours and cooled again.

[0178] 1.2 Organic filler precursor FPM2 A second lignin, FPM2, was used, which was prepared similarly to the process described in section 1.1 and was obtainable by hydrothermal treatment. The hydrothermal treatment was carried out in such a way that a liquid containing renewable raw materials was obtained. First, water and lignin were mixed to prepare a lignin-containing liquid with an organic dry matter content of 15% by mass. The lignin was then completely dissolved in the lignin-containing liquid. For this purpose, the pH was adjusted to 9.8 by adding NaOH. The solution was prepared with the aid of vigorous mixing at 80°C for 3 hours. The lignin was then dissolved in the liquid. The liquid containing renewable raw materials was subjected to hydrothermal treatment to obtain a solid. In this process, the prepared solution was heated at 1.4 K / min to a reaction temperature of 220°C, which was maintained for a reaction period of 7 hours. The solution was then cooled. As a result, an aqueous solid suspension was obtained. The solid was extensively dehydrated and purified by filtration and washing. The dewatered and washed solid is dried and heat-treated under nitrogen in a fluidized bed dryer, whereby the material is heated to 50°C at 1.5 K / min and dried, then further heated to 190°C at 1.5 K / min, held for a period of 15 minutes, and cooled again. The dried solid is deagglomerated by grinding under nitrogen in an opposed jet mill to d99<10 μm. The milled solid is further processed in a ball mill under nitrogen and then sieved using a 200 μm sieve.

[0179] 1.3 Organic filler precursor FPM3 A third lignin, FPM3, obtainable by hydrothermal treatment, was used, prepared similarly to the process described in section 1.2, except that the final step of deagglomeration by grinding and sieving was not carried out.

[0180] 1.4 Lignins FPM1, FPM2 and FPM3 obtained by hydrothermal treatment were characterized by the above-mentioned methods as shown in Table 1.1 below. All three lignins had values ​​ranging from 0.20 to 0.45 Bq / g carbon. 14 It had a C content.

[0181] [Table 1]

[0182] 1.5 Organic fillers according to the invention Several organic fillers according to the invention were prepared, in each case using either the lignins FPM1 or FPM2 or FPM3 described above in sections 1.1 or 1.2 or 1.3 as starting material (precursor).

[0183] <Modification of Lignin FPM1 - Example OF1> 2 g of lignin FPM1 and 8.46 mmol (50% of the molar amount of FPM1) of 3-mercaptopropyltriethoxysilane (MPTES) were weighed into a 100 mL round-bottom flask. The resulting mixture was then heated to a temperature in the range of 160±5°C for 1 hour. The resulting mixture was then transferred to a Soxhlet apparatus to extract the solvent, unreacted MPTES, and possible reaction by-products. Extraction was carried out using acetone for 24 hours. After extraction, the products obtained in each case were dried in an oven under vacuum at a temperature of 80°C for 24 hours. OF1 had a BET surface area within the claimed range.

[0184] <Modification of Lignin FPM2 - Example OF2> 20 g of lignin FPM2 and 16 mmol of 1,2-bis(2-mercaptoethoxy)ethane (MEE) were weighed into a 100 mL round-bottom flask containing 50 mL of toluene. The resulting mixture was then heated to a temperature of 120°C for 1 hour. The resulting mixture was then transferred to a Soxhlet apparatus to extract unreacted and / or physically adsorbed MEE and possible reaction by-products. Extraction was carried out using toluene for 12 hours. After extraction, the resulting product was dried in an oven under vacuum at a temperature of 80°C for 24 hours. The resulting organic filler OF2 thus obtained was characterized by the methods described above, as shown in Table 1.2 below.

[0185] <Modification of Lignin FPM2 - Example OF3> 20 g of lignin FPM2 and weight average molecular weight (M w 8 mmol of a liquid polysulfide polymer (LPST) with three terminal SH groups and a molecular weight of 1016 g / mol was weighed into a 100 mL round-bottom flask containing 50 mL of toluene. The resulting mixture was then heated to a temperature in the range of 120°C for 1 hour. The resulting mixture was then transferred to a Soxhlet apparatus to extract the solvent, unreacted and / or physically adsorbed LPST, and possible reaction by-products. This extraction was carried out using toluene for 12 hours. After extraction, the resulting product was dried under vacuum at a temperature of 80°C for 24 hours. The resulting product, organic filler OF3, was characterized using the methods described above, as shown in Table 1.2 below.

[0186] <Modification of Lignin FPM3 - Example OF4> 20 g of lignin FPM3 and 16 mmol of 1,2-bis(2-mercaptoethoxy)ethane (MEE) were weighed into a 100 mL round-bottom flask containing 50 mL of xylene. The resulting mixture was then heated to a temperature of 120°C for 3 hours. The resulting mixture was then transferred to a Soxhlet apparatus to extract unreacted and / or physically adsorbed MEE and possible reaction by-products. This extraction was carried out using toluene for 12 hours. After extraction, the resulting product was dried in an oven under vacuum at a temperature of 80°C for 24 hours. OF4 had a BET surface area within the claimed range.

[0187] <Modification of Lignin FPM3 - Example OF5> 20 g of lignin FPM3 and weight average molecular weight (M w8 mmol of a liquid polysulfide polymer (LPST) with three terminal SH groups and a molecular weight of 1016 g / mol was weighed into a 100 mL round-bottom flask containing 50 mL of xylene. The resulting mixture was then heated to a temperature in the range of 120°C for 3 hours. The resulting mixture was then 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 at a temperature of 80°C for 24 hours. OF5 had a BET surface area within the claimed range.

[0188] [Table 2]

[0189] The organic filler 13 Further investigation was performed using C NMR spectroscopy. Compared to FPM1 (a) in Figure 1, it is clear from Figure 1 that additional peaks (indicated by the symbol "*") are observed for OF1 sample (c) in the region between 10 and 35 ppm. These represent aliphatic chain carbons, corresponding to the characteristic signals of MPTES chemically grafted onto the lignin surface. Thus, the -S-C3H6-Si(OC2H5)3 residue of MPTES is chemically bonded to OF1 as a sulfur-containing organic residue, at least in part by partial substitution of the OH groups previously present on these carbon atoms for the aliphatic carbon atoms of OF1.

[0190] 1.6 Further investigations based on model materials Further studies, not based on either the organic fillers FPM1 or FPM2, but on two model substances, namely VA (vanillyl alcohol) and G (guaiacol), were carried out as proof-of-concept studies, demonstrating that the sulfur-containing organic residues to be introduced into the filler's chemical structure are indeed covalently bonded to the aliphatic carbon atom that previously bore the OH group, and not to any other position. VA (vanillyl alcohol) and G (guaiacol) are simplified representative structures of lignin, bearing either phenolic (G) or a combination of phenolic and aliphatic hydroxyl functional groups (VA), both of which are generally amenable to modification.

[0191] For these studies, equimolar amounts (3 mmol) of VA or G and MPTES were taken in 5 ml ampoules. The vials containing the reaction mixtures were immersed in an oil bath at 160 ± 5 °C, and the reaction was carried out for 1 hour under continuous stirring. The reaction was then immediately stopped by quenching the vials in liquid nitrogen. The products obtained in each case were then investigated, inter alia, by liquid-state NMR 1D- and 2D-NMR, through which the various products could be identified using correlations as single bond units. 13 C- 1 H coupling (HSQC) or multiple bonds 13 C- 1 It was clearly identified by H coupling (HMBC).

[0192] Upon reaction of VA and MPTES, it was discovered that the presence of the aliphatic hydroxy carbon (previously present in VA) could no longer be detected by the NMR method used. Instead, it was discovered that the -S-C3H6-Si(OC2H5)3 residue of MPTES was quantitatively chemically bonded to VA as a sulfur-atom-containing organic residue, i.e., by substitution of the aliphatic OH group for the aliphatic carbon atom of VA previously substituted with an OH group. The remaining sulfur signals of MPTES were completely undetectable. It was further discovered that when G and MPTES reacted, no reaction with MPTES occurred at all. Only the sulfur signals of MPTES could be detected.

[0193] 2. Preparation of vulcanizable and vulcanized rubber compositions Rubber compositions having the ingredients and amounts shown in Tables 2.1 and 2.2 were prepared as follows. In particular, rubber compositions containing one of FPM2, OF2, and OF3 (Table 2.1) and FPM3, OF4, and OF5 (Table 2.2) were prepared. The amounts / numbers shown in Tables 2.1 and 2.2 are in phr (parts per 100 parts by mass of resin) in each case.

[0194] [Table 3]

[0195] [Table 4]

[0196] 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 tetrabenzyl thiuram disulfide. ZnO is zinc oxide.

[0197] Two-stage mixing is performed with a chamber volume of 50 cm 3 Mixing was performed using a tangential rotor internal mixer (Brabender Plasticorder). For Stage 1 mixing (masterbatch preparation), the mixer was run at 70% fill, rotor speed of 50 rpm, and initial temperature of 50°C until the ram sweep occurred at 2:00. All ingredients were added within 2 minutes. The compound was then mixed for 6 minutes, with rotor speeds varied to achieve the desired discharge temperature.

[0198] [Table 5]

[0199] Stage 2 Mixing: The addition of the remaining ingredients was also carried out in a Brabender Plasticorder operating at 70% fill, a rotor speed of 30 rpm, and an initial temperature of 50° C. After the compound was discharged, it was sheeted on a two-roll mill operating at a gap width of 2.5 mm.

[0200] 3. Properties of vulcanized rubber compositions The properties of the vulcanized rubber compositions V-OF2, V-OF3, V-OF4, and V-OF5 according to the present invention, and the vulcanized rubber compositions V-FPM2 and V-FPM3 used as comparative examples, were determined according to the test methods described above.

[0201] As is clear from Figure 2, the use of organic fillers OF2 and OF3 with thioether bonds as fillers in rubber compositions V-OF2 and V-OF3 improved the mechanical properties in terms of tensile strength compared to the use of organic filler FPM2 without thioether bonds in reference sample V-FPM2, indicating that the addition of OF2 and OF3 results in better filler-rubber interaction than FPM2.

[0202] As is evident from Figure 3, the use of organic fillers OF2 and OF3 also showed improved hardness of the vulcanized rubber composition compared to using organic filler FPM2.

[0203] Even when using the same relative proportions, for example 40 phr of fillers OF4 and OF5 in the respective vulcanizable rubber compositions V-OF4 and V-OF5, the results obtained with the fillers with thioether bonds according to the invention show a clear improvement in the mechanical properties compared to the reference sample V-FPM3, in which no filler with thioether bonds is used at all (Figure 4).In this case, the use of the fillers according to the invention also shows an improved hardness compared to the comparative sample (Figure 3).

Claims

1. １４ C-content in the range of 0.20 to 0.45 Bq / g carbon and 10 to 200 m ２ / g, 1. An organic filler characterized in that at least a portion of the hydroxyl groups present in the chemical structure of the organic filler, which are bonded to at least one aliphatic carbon atom, are replaced with an organic residue containing covalently bonded sulfur atom(s), wherein at least one sulfur atom is adjacent to a carbon atom in the organic residue, such that an aliphatic carbon-sulfur-carbon bond is formed and present in the chemical structure of the organic filler.

2. The hydroxyl group of the organic filler bonded to the at least one aliphatic carbon atom is a hydroxyl group bonded to an aliphatic residue containing the at least one aliphatic carbon atom, preferably a hydroxyl group, more preferably a C １～３ Aliphatic or C ４～６ is attached to a heterocycloaliphatic residue, more preferably C ３ Aliphatic or C ６ Even more preferably C ３ attached to an aliphatic residue, even more preferably C ３ characterized by a primary hydroxyl group attached to an alkyl residue; and 10. The filler of claim 1, further characterized in that the organic residue containing the sulfur atom(s) is a divalent organic residue in which at least one sulfur atom is located adjacent to an aliphatic carbon atom, such that an aliphatic carbon-sulfur-aliphatic carbon bond is formed and present in the chemical structure of the organic filler.

3. 3. The filler of claim 1 or 2, characterized in that the aliphatic carbon-sulfur-carbon bonds in the chemical structure have been introduced by reaction, preferably by a substitution reaction, more preferably by a nucleophilic substitution reaction, of at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom with at least one organic modifier comprising at least one thiol group located adjacent to a carbon atom in the chemical structure, wherein at least a portion of the hydroxyl groups have been replaced with an organic residue comprising covalently bonded sulfur atom(s), wherein at least one sulfur atom present therein originates from the thiol group of the organic modifier.

4. 4. The filler according to claim 1, wherein the carbon atom located next to the sulfur atom of the organic residue containing the covalently bonded sulfur atom is not part of an unsubstituted and / or saturated hexyl group.

5. 5. A filler according to any one of claims 1 to 4, characterized in that hydroxyl groups are still present in the chemical structure of the organic filler, the hydroxyl groups being attached to at least one aliphatic carbon atom, in particular because only a portion of these hydroxyl groups have been replaced with organic residues comprising the covalently bonded sulfur atom(s).

6. 6. The filler according to any one of claims 1 to 5, characterized in that it further comprises at least one functional group selected from aromatic hydroxyl groups, preferably selected from phenolic hydroxyl groups, including phenolate groups, and carboxylic acid groups, including carboxylate groups.

7. 7. Filler according to any one of claims 1 to 6, characterized in that it is a lignin-based filler, preferably a lignin-based filler obtainable by hydrothermal treatment.

8. 8. The filler according to claim 1, wherein the aliphatic carbon-sulfur-carbon bond in the chemical structure is introduced by reacting at least a portion of the hydroxyl groups bonded to at least one aliphatic carbon atom with at least one organic modifier, the at least one organic modifier being represented by the following general formula (I): R １ -L １ -SH (I)、 (In the formula, L １ is C ２～３０ Alkylene group, C ２～３０ Heteroalkylene group, C ３～３０ Alkenylene group, C ２～３０ Heteroalkenylene group, C ３～３０ Alkynylene groups, and C ２～３０ heteroalkynylene groups, in which one or more hydrogen atoms of any of these groups may optionally and / or independently of one another be fluorine, a hydroxyl group, and / or an O—C １～４ substituted with at least one alkyl group; R １ is an OH group, O-C １～４ Alkyl group, SH group, S—C １～４ Alkyl group, 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) ２ NR １１ Group, OPO ３ ２－ group or a salt thereof, an OC(=O)O group or a salt thereof, a 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, where R １１ , R １２ , R １３ , and R １４ are independently H, C １～８ Alkyl, C １～８ Alkenyl, and C １～８ alkynyl) and at least one thiol of and / or The following general formula (II): ( ２ ) (().) (In the formula, R ２ C optionally containing one or more heteroatoms and / or heteroatom groups １～３０ is a hydrocarbon group, wherein the heteroatoms are preferably selected from O, S, and N, more preferably selected from O and S, and even more preferably selected from O, and the heteroatom groups are preferably selected from NH and NR, where R is C １～４ an aliphatic residue, preferably C ７～３０ a hydrocarbon group, in which in each case one or more hydrogen atoms are optionally optionally and / or independently of one another fluorine, a hydroxyl group, and / or an O—C １～４ and at least one alkyl group is substituted. and at least one thiol of and / or The following general formula (III): ()() ３－ｙ ( ) ｙ fi ２ ). (wherein y is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0; Y is a non-hydrolyzable organic residue, preferably unsubstituted C １～３０ is an alkyl group or a residue L ２ represents —SH, and L ２ has the meaning defined below: X in each case independently of one another represents a hydrolyzable group, which is preferably reactive with at least one of phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups, silyl ether groups and mixtures thereof, preferably O—C １～４ Alkyl groups, O(CH ２ ) ａ -O(CH ２ ) ｂ -CH ３ represents a hydrolyzable group selected from the group consisting of: a) a group in which a is an integer from 2 to 3 and b is an integer from 1 to 14; halide; and mixtures thereof; L ２ is a divalent non-hydrolyzable organic residue, preferably C １～３０ alkylene groups, more preferably C １～１６ alkylene groups, and even more preferably C １～６ alkylene groups, most preferably C １～３ alkylene groups, in each case one or more hydrogen atoms are optionally optionally and / or independently of one another selected from fluorine and O—C １～４ and each of said alkylene groups is substituted with at least one of said alkylene groups; however, preferably, each of said alkylene groups is unsubstituted. and at least one thiol of and / or As the thiol precursor, a compound represented by the following general formula (IV): 【Chemistry 1】 (In the formula, R ４ C optionally containing one or more heteroatoms and / or heteroatom groups １～３０ is a hydrocarbon group, wherein the heteroatoms are preferably selected from O, S, and N, more preferably selected from O and S, and even more preferably selected from O, and the heteroatom groups are preferably selected from NH and NR, wherein R is C １～４ an aliphatic residue, preferably C ７～３０ a hydrocarbon group, in which in each case one or more hydrogen atoms are optionally optionally and / or independently of one another fluorine, a hydroxyl group, and / or an O—C １～４ and at least one alkyl group is substituted. and at least one thiirane of the formula: and / or at least one polymeric polythiol having at least two or more, preferably terminal thiol groups; preferably at least one polysulfide having two, three, or more, preferably terminal thiol groups; 8. The filler according to claim 1, wherein the filler is a hydroxypropyl methylcellulose.

9. The filler according to any one of claims 1 to 8, which can be obtained by carrying out at least one step a) and optionally one or more of steps b) to d), wherein steps a) to d) are as follows: a) at least one organic modifier containing at least one thiol group located adjacent to a carbon atom in its chemical structure; and １４ C content, 10 to <200 m ２ / g (10-200m ２ and at least one organic filler precursor FPM having a BET surface area in the range of 0.15 wt. ft. / g or less 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), preferably present in a liquid or gaseous reaction medium, preferably to a temperature in the range of from 30° C. to 190° C., more preferably to a temperature in the range of from 50° C. to 180° C., most preferably to a temperature in the range of from 70° C. to 170° C., c) optionally, if the optional heating according to step a) and / or step b) has been carried out in a liquid reaction medium containing at least one organic solvent, extracting at least one organic solvent after at least a portion of the hydroxyl groups attached to at least one aliphatic carbon atom of said organic filler precursor FPM have been replaced with an organic residue comprising a covalently bonded sulfur atom, in which at least one sulfur atom is derived from the thiol group of said organic modifier; and d) optionally, after carrying out step a) and optionally step b) and / or c), drying the organic filler obtained, preferably in vacuum and / or at a temperature in the range of from 20 to 100° C.; A filler characterized in that it can be obtained by carrying out the steps of:

10. 10. Filler according to any one of claims 1 to 9, characterized in that it is and / or has been prepared in rubber-free form.

11. A rubber composition comprising at least one rubber and at least one filler component, The filler component comprises at least one organic filler according to any one of claims 1 to 10; and / or The filler component comprises: (i) a carbon content in the range of 0.20 to 0.45 Bq / g carbon; １４ C content, 10 to <200 m ２ / g (10 to 200 m ２ 11. The organic filler of claim 1, wherein the filler is a polymer having a BET surface area in the range of 0.05 wt. ft. / g (less than 0.05 wt. ft. / g) and 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 located adjacent to a carbon atom in its chemical structure, whereby a covalent bond to the at least one organic filler precursor FPM is formed through at least partial substitution of a hydroxyl group bonded to at least one aliphatic carbon atom present in the chemical structure of the organic filler precursor FPM with an organic residue comprising covalently bonded sulfur atom(s), thereby resulting in an aliphatic carbon-sulfur-carbon bond in the chemical structure of the organic filler, wherein at least one sulfur atom present in the organic filler comes from a thiol group of the organic modifier, to form the organic filler of claim 1. Rubber composition.

12. The rubber composition according to claim 11, the at least one rubber is selected from the group consisting of natural rubber (NR), halobutyl rubber, and also preferably chlorobutyl rubber (CIIR; chloro-isobutene-isoprene rubber) and bromobutyl rubber (BIIR; bromo-isobutene-isoprene rubber), and mixtures thereof, butyl rubber or isobutylene-isoprene rubber, respectively, isobutylene-isoprene rubber (IIR; isobutene-isoprene rubber), styrene-butadiene rubber (SBR), also 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 The rubber composition comprises at least one organic filler according to any one of claims 1 to 10 in an amount ranging from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, in particular from 40 to 100 phr, and / or the at least one organic filler precursor FPM as defined in item (i) of claim 11 in an amount ranging from 10 to 150 phr, particularly preferably from 15 to 130 phr, most preferably from 20 to 120 phr, in particular from 40 to 100 phr, and the at least one organic modifier as defined in item (ii) of claim 10 in an amount ranging from 0.1 to 30% by weight, particularly preferably from 0.5 to 25% by weight, most preferably from 1.0 to 15% by weight, in particular from 1.5 to 12% by weight, in each case the amount being based on the total weight of the organic filler precursor FPM. A rubber composition characterized by:

13. 13. A vulcanizable rubber composition comprising the rubber composition according to claim 11 or 12 and a 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 a vulcanization system comprising at least sulfur.

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

15. 15. A vulcanized rubber composition obtainable by vulcanizing the vulcanizable rubber composition according to claim 13 or by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (A) and (B) of the multi-part kit according to claim 14.

16. Use of an organic filler according to any one of claims 1 to 10 for the production of rubber compositions and vulcanizable rubber compositions, and use of a rubber composition according to any one of claims 11 to 12 and 15 for the production of tires, preferably pneumatic tires and solid tires, in particular pneumatic tires, preferably in each case their treads, sidewalls and / or inner liners and / or for the production of technical rubber articles, preferably profiles, seals, dampers and / or hoses.

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