EP4341342A1 - Charges organiques à surface modifiée et compositions de caoutchouc les contenant - Google Patents

Charges organiques à surface modifiée et compositions de caoutchouc les contenant

Info

Publication number
EP4341342A1
EP4341342A1 EP22730165.2A EP22730165A EP4341342A1 EP 4341342 A1 EP4341342 A1 EP 4341342A1 EP 22730165 A EP22730165 A EP 22730165A EP 4341342 A1 EP4341342 A1 EP 4341342A1
Authority
EP
European Patent Office
Prior art keywords
groups
filler
rubber
organic
functional group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22730165.2A
Other languages
German (de)
English (en)
Inventor
Jacob Podschun
Gerd Schmaucks
Alexander STÜCKER
Tobias Wittmann
Priyanka SEKAR
Rafal Anyszka
Anke Blume
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suncoal Industries GmbH
Original Assignee
Suncoal Industries GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suncoal Industries GmbH filed Critical Suncoal Industries GmbH
Publication of EP4341342A1 publication Critical patent/EP4341342A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to an organic filler, in which (i) at least one functional group of the filler, selected from phenolic OFI groups, phenolate groups, aliphatic OFI groups, carboxylic acid groups, carboxylate groups, has at least part of the oxygen atoms and mixtures thereof and/or (ii) at least one organic modifier has been covalently bonded to the organic filler via at least some of the carbon atoms ortho to phenolic OFI groups and/or phenolate groups of the filler, comprising a rubber composition at least one rubber and at least this aforementioned filler, a vulcanizable rubber composition additionally comprising a vulcanization system, a vulcanized rubber composition obtainable therefrom, and a use of the aforementioned filler for the production of (vulcanizable) rubber composition ments for use in the fixing of tires, preferably pneumatic tires and solid rubber tires, preferably for their tread, side wall and/or inner liner, and/or for use in the fixing of technical rubber articles, preferably profiles
  • carbon blacks can often not be used for certain applications, also for reasons of color.
  • a known alternative to the use of carbon blacks as inorganic reinforcing fillers are precipitated silicic acids or silica.
  • the chemically modified precipitated silicas are particularly suitable for use as reinforcing fillers due to their high specific surface area.
  • the use of corresponding chemically modified and in particular silanized precipitated silicas is also advantageous.
  • Vehicle tires such as pneumatic vehicle tires have a complex structure. The requirements for these are correspondingly diverse. On the one hand, short braking distances must be ensured on dry and wet roads, and on the other hand, they must have good abrasion properties and low rolling resistance. In addition, the vehicle tires must comply with the legal requirements.
  • the individual tire components are specialized and consist of a variety of different materials, such as metals, polymeric textile materials and various rubber-based components.
  • the tread is largely responsible for the driving characteristics.
  • the rubber composition of the tread determines the abrasion behavior and the dynamic driving characteristics in different weather conditions (on wet and dry roads, in cold and warm weather, on ice and snow).
  • the profile design is in turn largely responsible for the behavior of the tire in aquaplaning and in the wet, as well as on snow, and also determines the noise behavior.
  • silanized precipitated silicas as reinforcing fillers improves the rolling resistance compared to industrial carbon blacks due to a chemical bond between the precipitated silica and the elastomer of the rubber mixture, and at the same time wet grip is improved by the polarity on the surface of the precipitated silica.
  • Tire abrasion is fundamental when using precipitated silica compared to carbon black deteriorated, but this can be counteracted by a suitable choice of the elastomers used (e.g. by using polybutadiene).
  • rubber mixtures are often used in which the specific surface areas of the precipitated silicas used are comparatively high, for example in a BET range of 100 to 250 m 2 /g.
  • BET range 100 to 250 m 2 /g.
  • industrial carbon blacks which usually have a significantly lower specific surface area in the BET range of 30 to 50 m 2 /g. then often no more.
  • HTC lignin biologically renewable raw materials based on lignin, such as lignins in hydrothermally carbonized form (HTC lignin), can be used as organic fillers in rubber compositions. These places an environmentally friendly filler alternative compared to inorganic fillers and carbon blacks.
  • HTC lignin hydrothermally carbonized form
  • EP 3470 457 A1 describes rubber mixtures which contain FITC lignin.
  • the disadvantage of using such HTC lignins in rubber compositions is often that the compatibility between the comparatively polar HTC lignins and the comparatively nonpolar rubbers is often too low or insufficient.
  • disadvantages in relation to the aging resistance and long-term stability of the HTC lignin-containing rubber compositions can also and especially be observed in vulcanized form, since the HTC lignins contain too high a proportion of free OH groups, and undesirable reactions can take place that reduce the aging resistance and adversely affect long-term stability.
  • WO 2017/085278 A1 discloses the use of particulate carbon material, in particular also of HTC lignin, as a substitute filler for carbon blacks. This is associated with the same frequently occurring disadvantages mentioned above in connection with EP 3 470 457 A1. WO 2017/085278 A1 also describes that this material, after incorporation into a rubber composition, can be subjected to in situ modification with organosilanes as coupling reagents.
  • the disadvantage of using such organosilanes to modify carbon materials as described in WO 2017/085278 A1 is often that the thermodynamic stability of the chemical Si-OC bond formed between materials and organosilane coupling reagents is comparatively low, this bond is therefore optionally comparatively easily hydrolyzable, and undesirable decoupling reactions and thus less filler-rubber interaction can occur within the rubber composition, which is to be avoided since this can lead to impaired properties of the rubber composition during and after vulcanization.
  • the efficiency of the coupling of the aforementioned carbon materials and organosilane coupling agents is often too low, since there is often an undesirably high proportion of Self-condensation reactions of the organosilanes used come, which are then no longer available for the actual modification.
  • Another disadvantage results from carrying out the modification in situ only within the rubber composition produced, since this often undesirably restricts the degrees of freedom in the production of the composition and the components contained in it, especially when the aforementioned carbon materials are used in combination with other fillers such as, in particular, inorganic fillers such as silicic acids/silica.
  • Another disadvantage is that the in situ reaction with organosilanes requires an additional mixing stage compared to the use of carbon black, which is not usually used in the production of technical rubber articles and most tire components (e.g. sidewall, inner liner) for cost reasons.
  • WO 2017/194346 A1 also describes the use of HTC lignins in rubber mixtures for tire components, in particular together with a methylene donor compound such as hexa(methoxymethyl)melamine, in order to increase the stiffness of a cured rubber component of a tire, and under other things to replace phenolic resins.
  • a possible in situ modification with organosilanes as coupling reagents is also mentioned in WO 2017/194346 A1. However, this is associated with the same disadvantages mentioned above in connection with WO 2017/085278 A1.
  • One object of the present invention is therefore to provide environmentally friendly fillers which are suitable directly as such for incorporation into rubber compositions, in particular to provide tire components such as tire treads and tire components for the tire substructure (carcass) and/or to provide components for technical rubber goods.
  • tire components such as tire treads and tire components for the tire substructure (carcass)
  • components for technical rubber goods in particular with regard to an improvement in the aging resistance and long-term stability of the rubber compositions in vulcanized form, increased media resistance and hydrolysis resistance compared to the fillers of the prior art and improved mechanical properties such as moduli, tensile strength and elongation at break.
  • a first object of the present invention is therefore an organic filler with a 14 C content in a range from 0.20 to 0.45 Bq/g carbon, characterized in that (i) at least one functional group over at least part of the oxygen atoms of the filler, which is selected from phenolic OH groups, phenolate groups, aliphatic OH groups,
  • Carboxylic acid groups, carboxylate groups and mixtures thereof and/or (ii) at least some of the carbon atoms of the filler ortho to phenolic OH groups and/or phenolate groups covalently bond at least one organic modifier to the organic Filler is carried out, wherein the used at least one organic modifier contains at least one organic residue which, prior to attachment to the filler, has at least one opposite (i) the at least one functional group of the filler and/or opposite (ii) to phenolic OH groups and /or phenolate groups in ortho-position carbon atoms reactive functional group RFG, by means of which the attachment to the filler has taken place, and wherein the at least one reactive functional group RFG of the organic modifier contains no silicon atoms, preferably the organic modifier as such contains no silicon atoms, and the at least one reactive functional group RFG is preferably selected from the group consisting of acid groups and salts, anhydrides, halides and esters of these acid groups, epoxide groups, thiirane groups,
  • the organic filler according to the invention is preferably present in a rubber-free form and/or has been produced in a rubber-free form.
  • the at least one organic modifier is attached to the filler used for this purpose (i.e. the FPM filler before the modification, which is described below) does not take place in situ within a rubber composition, but rather the attachment takes place in a separate upstream step ( "ex situ"). In other words, no rubber is then present during the modification using the at least one modifier used according to the invention.
  • Another subject of the present invention is a rubber composition
  • a rubber composition comprising at least one rubber component, which contains at least one rubber, and a filler component, wherein the filler component contains at least one organic filler according to the invention as described in connection with the first subject of the present invention, and / or wherein the Filler component (i) contains at least one organic filler FPM with a 14 C content in a range from 0.20 to 0.45 Bq/g carbon, which has at least one functional group selected from phenolic OH groups, phenolate Groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof, wherein the organic filler FPM preferably has a BET surface area in a range from 10 to ⁇ 200 m 2 / g, and (ii) comprises at least one organic modifier which contains at least one organic radical which has at least one compared to (i) the at least one functional Group of the filler FPM and / or compared to (ii) to phenolic OFI groups and
  • Another object of the present invention is a vulcanizable rubber composition
  • a vulcanizable rubber composition comprising the rubber composition according to the invention and a vulcanization system, preferably comprising at least zinc oxide and/or at least sulfur and/or at least one preferably organic peroxide, particularly preferably comprising at least sulfur.
  • kits of parts comprising, in spatially separated form, a rubber composition according to the invention as part (A) and a vulcanization system as part (B) as is contained in the vulcanizable rubber composition according to the invention.
  • Another object of the present invention is a vulcanized rubber composition which is obtainable by vulcanizing the vulcanizable rubber composition according to the invention or by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (A) and (B) of the kit-of-parts according to the invention.
  • Another subject of the present invention is the use of at least one organic filler according to the invention for the production of rubber compositions and vulcanizable rubber compositions for use in the production of tires, preferably pneumatic tires and solid rubber tires, in particular pneumatic tires, preferably for their tread, side wall and/or inner liner , and/or to manufacture technical rubber articles, preferably to manufacture profiles, seals, dampers and/or hoses.
  • the organic filler according to the invention is an environmentally friendly alternative both to known, in particular inorganic, fillers and to carbon blacks for rubber applications.
  • the organic filler according to the invention is suitable directly as such for incorporation into rubber compositions, in particular to produce treads, side walls and / or inner liners of tires such as pneumatic tires and solid rubber tires and / or to produce technical rubber articles such as profiles, seals, dampers and /or manufacture hoses.
  • the organic filler according to the invention has good compatibility with the rubbers contained in rubber compositions.
  • the compatibility can be further improved if the at least one organic modifier used has at least one other functional group FGK, which is different from the at least one reactive functional group RFG, and - if the filler together with at least a rubber is used within a rubber composition, - a reactivity towards the at least one rubber and/or towards at least one functional group of this rubber and/or compared to the vulcanization system used, in particular during vulcanization.
  • the filler can also be attached to the rubber and/or the vulcanization system at the latest during vulcanization, which, in addition to improved compatibility, in particular improves the reinforcing properties (such as moduli, elongation at break, flysteresis, tear propagation resistance and/or tensile strength) of the vulcanized composition be further improved.
  • the reinforcing properties such as moduli, elongation at break, flysteresis, tear propagation resistance and/or tensile strength
  • the organic filler according to the invention makes it possible to improve the aging resistance and long-term stability of the rubber compositions, even in vulcanized form.
  • the organic filler according to the invention has increased media resistance, in particular to bases, and hydrolysis resistance in particular compared to the fillers of the prior art.
  • the at least one organic modifier to the filler, i.e.
  • the at least one organic modifier can be attached to the filler used (i.e. the FPM filler described below) in a separate upstream step (“ex situ”) and thus not necessarily in situ attachment must occur within the rubber composition in the presence of a rubber.
  • the organic filler according to the invention and already modified can be used as such in rubber compositions as a filler, especially in combination with other fillers such as inorganic fillers, especially with (unmodified) silica, especially when a Modification of the other fillers such as silica with suitable modifiers such as organosilanes within the rubber compositions is envisaged and such modification therefore still has to take place in situ.
  • the "ex situ” modification thus allows the user more degrees of freedom and flexibility in the preparation and formulation of rubber compositions and the components contained therein.
  • the use of the modifier used according to the invention whose reactive groups RFG are Si-free, and which is preferably Si-free as such, and in this case cannot carry any Si-containing groups as in the case of organosilanes covalent attachment to the filler leads to thermodynamically stable C-O-C bonds, or to C-O-C bonds which have a higher thermodynamic stability than corresponding Si-O-C bonds formed, for example, when using organosilanes.
  • This also achieves increased resistance to flydrolysis and undesired decoupling reactions and thus lower filler-rubber interactions within the rubber composition can be avoided or at least reduced.
  • the use of the modifier used according to the invention has the advantage that a high coupling efficiency is achieved, since self-condensation reactions such as when organosilanes are used may not occur.
  • corresponding, in particular vulcanizable, rubber compositions which contain the organic filler according to the invention can be used in the manufacture of tires such as pneumatic tires and solid rubber tires, in particular pneumatic tires, preferably for their tread, side walls and/or inner liner. and meet the necessary requirements to a very high degree, especially in With regard to rolling resistance, abrasion and wet slipping and a balance of these requirements.
  • corresponding, in particular vulcanizable, rubber compositions which contain the organic filler according to the invention are suitable for use in the production of technical rubber goods (rubber articles), in particular profiles, seals, dampers and/or hoses.
  • the vulcanized rubber compositions of the invention improved mechanical properties, especially in terms of tensile strength, Shore A hardness and
  • rubber compositions according to the invention in particular vulcanizable rubber compositions which contain the organic filler according to the invention, lead to vulcanized rubber compositions which are characterized by increased moduli in the range of up to 200% of elongation. This was also found in particular when no carbon blacks are used as additional fillers.
  • inventive, in particular vulcanizable, rubber compositions which contain the organic filler according to the invention lead to vulcanized rubber compositions for use as tire treads in passenger cars and in particular in the truck sector which, compared to vulcanized rubber compositions, which instead of the organic filler according to the invention have silanized precipitated silica, lead to an improvement in rolling resistance and wet grip while at the same time at least acceptable tire wear.
  • compositions described herein such as the rubber compositions according to the invention and the vulcanizable rubber compositions according to the invention (in each case comprising all mandatory and also all optional components) add up to a total of 100% by weight in each case.
  • the organic filler according to the invention is an organic filler with a 14 C-content in a range from 0.20 to 0.45 Bq/g carbon, wherein (i) at least over part of the oxygen atoms at least one functional group of the filler, which is selected of phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof and/or (ii) at least part of the phenolic OH groups and/or phenolate groups in ortho- Position located carbon atoms of the filler is a covalent attachment of at least one organic modifier to the organic filler.
  • the phrase "at least in part” means partially or fully, preferably partially.
  • the phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof are preferably located on the surface of the FPM filler used for modification (so-called surface-available groups).
  • surface-available OH groups can be determined qualitatively and quantitatively colorimetrically according to Sipponen. The Sipponen method is based on the adsorption of the basic dye Azure B onto the acidic hydroxyl groups accessible on the filler surface. If a corresponding adsorption takes place under the conditions that are specified in the article cited below under point 2.9 (p. 82), then surface-available groups are present within the meaning of the present invention.
  • the amount of surface-available groups for the purposes of the present invention is given in mmol/g of filler.
  • the amount of surface available groups is in the range from 0.05 mmol/g to 40 mmol/g, more preferably 0.1 mmol/g to 30 mmol/g and most preferably 0.15 to 30 mmol/g.
  • the filler according to the invention is organic, inorganic fillers such as precipitated silicas do not come under this term.
  • the term filler and in particular organic filler is known to the person skilled in the art.
  • the organic filler according to the invention is preferably a reinforcing filler, ie an active filler. Reinforcing or active fillers, in contrast to inactive (non-reinforcing) fillers, can change the viscoelastic properties of the rubber through an interaction with a rubber within a rubber composition. For example, they can influence the viscosity of the rubbers and can improve the fracture behavior of the vulcanizates, for example with regard to tear propagation strength, tear propagation resistance and abrasion.
  • Inactive fillers dilute the rubber matrix.
  • the organic filler of the present invention has a 14 C content ranging from 0.20 to 0.45 Bq/g, preferably from 0.23 to 0.42 Bq/g carbon.
  • the required 14 C content specified above is met by organic fillers which are obtained from biomass by further treatment or conversion, preferably fractionation, of the same, where the fractionation can take place thermally, chemically and/or biologically, preferably thermally and chemically.
  • Fillers obtained from fossil materials, such as in particular fossil fuels therefore do not fall under the definition of the filler to be used according to the present invention, since they do not have a corresponding 14 C content.
  • biomass any biomass is referred to as biomass here, the term “biomass” herein so-called phytomass, i.e. biomass originating from plants, zoomass, i.e. biomass originating from animals, and microbial biomass, i.e. biomass originating from microorganisms including fungi, encompasses it the biomass is dry biomass or fresh biomass and originates from dead or living organisms.
  • the most preferred biomass herein for preparing the fillers is phytomass, preferably dead phytomass. Dead phytomass includes, but is not limited to, dead, shed, or severed plants and components.
  • the organic filler according to the invention preferably has a carbon content in the range from 60% by weight to 85% by weight, particularly preferably from 63% by weight to 80% by weight and very particularly preferably from 65% by weight to 75% by weight %, in particular from 68% by weight to 73% by weight, based in each case on the ashless and anhydrous filler.
  • a method for determining the carbon content is given below in the Methods section. This distinguishes the organic filler from both carbon blacks made from fossil raw materials and carbon blacks made from renewable ones Raw materials are produced because carbon blacks have a corresponding carbon content of at least 95% by weight.
  • the fillers according to the invention preferably have an oxygen content in the range from 15% by weight to 30% by weight, preferably 17% by weight to 28% by weight and particularly preferably 20% by weight to 25% by weight to the ashless and anhydrous filler.
  • the oxygen content can be determined by means of floch temperature pyrolysis, for example using the EuroEA3000 CHNS-0 analyzer from EuroVector S.p.A.
  • the organic filler according to the invention preferably has a BET surface area (specific total surface area according to Brunauer, Emmett and Teller) in a range from 10 to ⁇ 200 m 2 /g. A method for determining this parameter is described below in the Methods section.
  • the organic filler according to the invention particularly preferably has a BET surface area in a range from 10 to 150 m 2 /g, very particularly preferably a BET surface area in a range from 20 to 120 m 2 /g, even more preferably a BET surface area in one range from 30 to 110 m 2 /g, in particular a BET surface area in a range from 40 to 100 m 2 /g, most preferably a BET surface area in a range from 40 to ⁇ 100 m 2 /g.
  • the organic filler according to the invention preferably has an STSA surface area in a range from 10 to ⁇ 200 m 2 /g.
  • a method for determining the STSA is given below in the Methods section.
  • the organic filler according to the invention preferably has an STSA surface area in a range from 10 to 150 m 2 /g, particularly in a range from 20 to 120 m 2 /g, very particularly preferably in a range from 30 to 110 m 2 /g , in particular one in a range from 40 to 100 m 2 /g, most preferably in a range from 40 to ⁇ 100 m 2 /g.
  • the organic filler according to the invention preferably has only limited solubility in alkaline media, in particular in 0.1 M or 0.2 M NaOH.
  • the solubility is determined according to the method described below.
  • the solubility of the organic filler is preferably less than 30%, particularly preferably less than 25%, very particularly preferably less than 20%, even more preferably less than 15%, even more preferably less than 10%, further preferably less than 7.5%, even more preferably less than 5% , more preferably less than 2.5%, most preferably less than 1%.
  • the organic filler according to the invention is preferably a lignin-based organic filler which is produced from biomass and/or biomass components.
  • the lignin for the production of the lignin-based organic filler can be isolated, extracted and/or dissolved from biomass before it is modified according to the invention.
  • Suitable methods for obtaining the lignin for the production of the lignin-based organic filler from biomass are, for example, hydrolysis methods or digestion methods such as the Kraft digestion method.
  • the expression “based on lignin” in the context of the present invention preferably means that one or more lignin units and/or one or more lignin frameworks are present in the organic filler according to the invention.
  • Lignins are solid biopolymers that are stored in plant cell walls and thus cause lignification of plant cells. They are therefore contained in biomass and in particular in biologically renewable raw materials and therefore represent an environmentally friendly filler alternative - especially in hydrothermally treated form.
  • the organic filler according to the invention is preferably a lignin-based organic filler with a lignin content of at least 50% by weight, particularly preferably at least 60% by weight, very particularly preferably at least 70% by weight, most preferably at least 80% by weight. %, each based on that
  • the content of Klason lignin in the organic filler according to the invention is preferably at least 50% by weight, particularly preferably at least 60% by weight, very particularly preferably at least 70% by weight, most preferably at least 80% by weight.
  • the Klason lignin content is preferably determined as acid-insoluble lignin according to TAPPI T 222.
  • the lignin and preferably the organic filler according to the invention as such, if it is a lignin-based filler, at least partially in hydrothermally treated form and is particularly preferably obtainable by means of hydrothermal treatment.
  • the organic filler according to the invention is particularly preferably based on lignin obtainable by means of hydrothermal treatment. Suitable methods of hydrothermal treatment, in particular of lignins and lignin-containing organic fillers, are described, for example, in WO 2017/085278 A1 and WO 2017/194346 A1 and in EP 3470457 A1.
  • the hydrothermal treatment is preferably carried out at temperatures between 150° C. and 250° C. in the presence of liquid water.
  • the organic filler according to the invention preferably has a pH in a range from 7 to 9, particularly preferably in a range from >7 to ⁇ 9, very particularly preferably in a range from >7.5 to ⁇ 8.5.
  • the at least one organic modifier used for the covalent attachment contains an organic residue and preferably consists of this organic residue, the residue before attachment to the filler having at least one opposite (i) the at least one functional group of the filler and/or opposite (ii ) to the phenolic OH groups and / or phenolate groups located in the ortho-position carbon atoms reactive functional group RFG, by means of which the connection to the filler has taken place.
  • the covalent and thus chemical binding of the at least one organic modifier to the organic filler used for this purpose, preferably to the lignin contained in the filler, takes place by a chemical reaction via at least some of the oxygen atoms of the at least one functional group of the filler, which is selected from phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof and/or (ii) at least part of the phenolic OH groups and/or phenolate groups in the ortho position Carbon atoms of the filler each having at least one functional group RFG of the organic modifier that is reactive toward these groups.
  • the at least partial, preferably partial, reaction advantageously changes the polarity of the filler.
  • Modifiers can also have a physical shielding effect (eg in the case of 1,2-epoxy-9-decene (ED) due to its comparatively long-chain hydrophobic residue). Is only over part of the oxygen atoms of the phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof and/or only over part of the phenolic OH groups and/or phenolate groups If the at least one organic modifying agent is covalently bonded to the carbon atoms of the filler in the ortho-position of the carbon atoms in the filler, the organic filler according to the invention can still have free phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups after bonding. groups, carboxylate groups and mixtures thereof. Preferably this is the case.
  • the organic filler according to the invention has no free phenolic OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures more of that.
  • the filler can still have one or more types of its functional group, for example aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof, whereas all the phenolic OH groups previously present Groups and phenolate groups have been implemented.
  • the organic filler according to the invention is preferably present in a rubber-free form and/or has been produced in a rubber-free form.
  • An organic filler FPM with a 14 C content in the range from 0.20 to 0.45 Bq/g carbon is suitable as the starting material or precursor for the production of the organic filler according to the invention and contains at least one functional group selected from phenolic ones OH groups, phenolate groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups and mixtures thereof.
  • the FPM filler used according to the invention differs from the organic filler according to the invention at least in this way.
  • the organic filler FPM preferably has a BET surface area in a range from 10 to ⁇ 200 m 2 /g.
  • the organic filler according to the invention can preferably be obtained by carrying out at least one step a) and optionally one or more of steps b) to d), namely a) bringing together the at least one organic modifier used according to the invention and at least one organic filler FPM, which has a 14 C -has a content in a range from 0.20 to 0.45 Bq/g carbon and which has at least one functional group selected from phenolic OH groups, phenolate-
  • step a) optional heating of the mixture obtained according to step a), which is preferably present within a liquid or gaseous reaction medium, preferably to a temperature in the range of 30 ° C to
  • the bringing together according to step a) and optionally also the heating according to optional step b) can be carried out in a reaction medium which is preferably liquid or gaseous.
  • the modifier used and/or the FPM filler and/or the resulting mixture can optionally be present in a liquid or gaseous reaction medium.
  • the liquid reaction medium can preferably contain or consist of at least one organic solvent, particularly preferably at least one hydrocarbon, very particularly preferably at least one aliphatic and/or aromatic hydrocarbon.
  • the modifier can be covalently bonded to the FPM filler by CVD (chemical vapor deposition).
  • step a) preferably takes place at room temperature (18 to ⁇ 30° C.).
  • the covalent attachment of the modifier to the filler FPM can already take place under these conditions.
  • step b) is carried out.
  • the covalent attachment of the modifier to the FPM filler preferably takes place in the temperature ranges mentioned above in connection with step b).
  • the extraction according to optional step c) is preferably carried out at a temperature in a range from 20 to 150° C. and can optionally be carried out under reduced pressure.
  • reaction mixture is preferably mixed for a period of 0.01 to 30 h, particularly preferably 0.01 to 5 h, for example by stirring, in particular by one to achieve full implementation with the modifier used in the amount used
  • the organic filler according to the invention preferably contains the organic filler, based on its total weight, after the covalent attachment has taken place
  • the organic modifier used according to the invention as such does not bind to the filler FPM via silicon atoms and preferably contains no silicon atoms.
  • the organic filler according to the invention as such is preferably free of Si atoms which are introduced into it via the modifier.
  • the at least one organic modifier used for the covalent attachment contains an organic residue and preferably consists of this organic residue, the residue before attachment to the filler having at least one opposite (i) the at least one functional group of the filler and/or opposite (ii) to phenolic OH groups and / or phenolate groups in the ortho-position carbon atoms reactive functional group RFG, by means of which the connection to the filler takes place.
  • the at least one reactive functional group RFG of the organic modifier used is preferably selected from the group consisting of acid groups and salts, anhydrides, halides and esters of these acid groups, epoxide groups, thiirane groups, alcohol groups, thiol groups , Thioester groups, aldehyde groups, isocyanate groups and mixtures thereof, particularly preferably selected from the group consisting of acid groups and salts, anhydrides, halides and esters of these acid groups, epoxide groups, thiirane groups, alcohol Groups, thiol groups, thioester groups, isocyanate groups and mixtures thereof, most preferably selected from the group consisting of acid groups and salts, anhydrides, halides and esters of these acid groups, epoxide groups, thiol groups and mixtures of them.
  • acid groups are carboxylic acid groups, sulfonic acid groups, phosphonic acid groups and phosphoric acid groups.
  • Carboxylic acid groups and phosphoric acid groups and their respective salts, anhydrides, halides and esters, and epoxide groups are particularly preferred. Most preferred are carboxylic acid groups and epoxide groups and thiol groups.
  • the at least one organic modifier used preferably has at least one further functional group FGK, which is different from the at least one reactive functional group RFG, and which—if the filler according to the invention is used together with at least one rubber within a rubber composition—reacts towards it the at least one rubber and/or towards at least one functional group of this rubber and/or a vulcanization system present in the rubber composition, in particular during vulcanization, the at least one further functional group FGK preferably being selected from the group consisting of preferably not -conjugated and / or conjugated carbon-carbon double bonds, in particular vinyl groups, and sulfur-containing groups and mixtures thereof, is particularly preferably selected from the group consisting of cis-position Carbon-carbon double bonds, mercapto groups, which may be blocked, and di- and/or polysulfide groups, thioketone groups, mercaptobenzothiazole groups and dithiocarbamate groups, and mixtures thereof.
  • the at least one organic modifying agent used preferably has at least one further functional group FGB, which is different from the at least one reactive functional group RFG, and which is preferably also different from the optionally present further functional group FGK.
  • the at least one further functional group FGB is preferably a functional group which increases the basicity of the filler after attachment of the organic modifier used, particularly preferably an amino group, in particular an amino group selected from the group consisting of primary and secondary amino groups . It is also possible that there is a further chemical bond to the filler via the at least one further functional group FGB of the organic modifier, in particular if this is an amino group.
  • the organic radical of the organic modifier is preferably selected from the group consisting of aliphatic, cycloaliphatic, heteroaliphatic, heterocycloaliphatic and aromatic, heteroaromatic radicals, and also from mixed forms of at least two of the aforementioned organic radicals.
  • each of these organic radicals can preferably have at least one further functional group FGB defined above and/or at least one further functional group FGK defined above.
  • the at least one organic modifier is selected from the group consisting of aliphatic epoxides, aromatic epoxides, aliphatic carboxylic acids and/or carboxylic anhydrides, aromatic and heteroaromatic carboxylic acids and/or carboxylic anhydrides, cycloaliphatic and heterocycloaliphatic carboxylic acids and/or carboxylic anhydrides, aliphatic thiols, and mixtures thereof .
  • each of these compounds can preferably have at least one further functional group defined above Group FGB and/or at least one further functional group FGK defined above.
  • At least monounsaturated aliphatic epoxides at least monounsaturated aliphatic carboxylic acids and/or carboxylic anhydrides, and at least monounsaturated cycloaliphatic and heterocycloaliphatic carboxylic acids and/or carboxylic anhydrides are preferred.
  • each of these compounds can preferably have at least one further functional group FGB defined above and/or at least one further functional group FGK defined above.
  • Examples of specific preferred organic modifiers are cystine, especially L-cystine, 1,2-epoxy-9-decene, ethylene sulfide, thiobutyrolactone, flexanethiol, polymeric diphenylmethane diisocyanate, and dodecen-1yl-succinic anhydride, as well as 3-mercaptopropionic acid, linoleic acid, 3-mercaptopyridine-3 -carboxylic acid and 5-norborene-2-carboxylic acid.
  • organic modifiers examples include L-cystine-1,2-epoxy-9-decene, thiobutyrolactone, hexanethiol and dodecen-1yl-succinic anhydride. Most preferred are L-cystine and 1,2-epoxy-9-decene and hexanethiol.
  • Rubber composition according to the invention Another subject of the present invention is a rubber composition comprising at least one rubber component, which contains at least one rubber, and a filler component, wherein the filler component contains at least one organic filler according to the invention as described in connection with the first subject of the present invention, and/or , preferably or, wherein the filler component (i) contains at least one organic filler FPM with a 14 C content in a range from 0.20 to 0.45 Bq/g carbon, which has at least one functional group selected from phenolic OFI groups, phenolate groups, aliphatic OFI groups, carboxylic acid groups, carboxylate groups and mixtures thereof, wherein the organic filler FPM preferably has a BET surface area in a range from 10 to ⁇ 200 m 2 /g, and (ii) at least one comprises an organic modifier which contains an organic radical which contains at least one carbon atom of the Filler FPM has reactive functional group RFG, by means of which a covalent connection can be made to the at least one organic filler
  • the filler component preferably contains at least one organic filler according to the invention, as described in connection with the first subject matter of the present invention.
  • the rubber composition comprises the at least one organic filler of the invention in an amount ranging from 10 to 150, more preferably 15 to 130, most preferably 20 to 120, especially 40 to 100 phr and/or the at least one organic filler FPM as defined above under (i) in an amount ranging from 10 to 150, particularly preferably 15 to 130, very particularly preferably 20 to 120, in particular 40 to 100 phr, and the at least one organic modifier as defined above under (ii) in an amount ranging from 0.1 to 30% by weight, particularly preferably from 0.5 to 25% by weight, very particularly preferably from 1.0 to 15% by weight, in particular from 1.5 to 12% by weight, based in each case on the total weight of the filler FPM.
  • any cleavage products formed do not contribute to the amount of modifier based on the total weight of the filler FPM.
  • the rubber composition according to the invention comprises at least one rubber component which contains at least one rubber.
  • NR Natural rubber
  • synthetic rubbers are known to those skilled in the art.
  • the at least one rubber is preferably selected from the group consisting of natural rubber (NR), halobutyl rubbers, in turn preferably selected from the group consisting of chlorobutyl rubbers (CIIR; chloro-isobutene-isoprene rubber) and bromobutyl rubbers ( BIIR; bromo-isobutene-isoprene rubber), butyl rubber or isobutylene-isoprene rubber (IIR; isobutene isoprene rubber), styrene-butadiene rubber (SBR, styrene butadiene rubber), in turn preferably SSBR (solution-polymerized SBR and/or ESBR (emulsion-polymerized SBR), polybutadiene (BR, butadiene rubber), acrylonitrile-butadiene rubber
  • CIIR chlorobutyl rubbers
  • the at least one rubber is particularly preferably selected from the group consisting of styrene-butadiene rubber (SBR, styrene butadiene rubber), in turn preferably SSBR, polybutadiene (BR, butadiene rubber), EPDM, NR and acrylonitrile-butadiene rubber (NBR, nitrile rubber) and mixtures thereof.
  • SBR styrene-butadiene rubber
  • SBR styrene butadiene rubber
  • BR styrene butadiene rubber
  • BR polybutadiene
  • BR polybutadiene
  • BR butadiene rubber
  • the proportion of SBR is preferably higher than the proportion of BR.
  • the total amount of SBR rubber is preferably 60 to 100 phr, more preferably 65 to 100 phr, more preferably 70 to 100 phr.
  • the total amount of BR rubber is preferably 0 to 40 phr, more preferably 0 to 35 phr, more preferably 0 to 30 phr.
  • the specification phr (parts per hundred parts of rubber by weight) used here is the quantity specification for compound formulations customary in the rubber industry.
  • the dosage of the parts by weight of the individual components is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • Filler component of the rubber composition is the quantity specification for compound formulations customary in the rubber industry.
  • the rubber composition according to the invention comprises at least one filler component, the filler component containing at least one organic filler according to the invention and/or the filler component (i) comprising at least one organic filler FPM having a 14 C content in a range from 0.20 to 0.45 Bq/ g contains carbon which has at least one functional group selected from phenolic OFI groups, phenolate groups, aliphatic OFI groups,
  • carbon atoms of the filler FPM has reactive functional group RFG, by means of which a covalent connection to the at least one organic filler FPM can take place, the at least one functional group RFG of the organic modifier containing no silicon atoms, preferably the organic modifier as such contains no silicon atoms.
  • the at least one organic filler FPM corresponds to the starting material used in connection with the preparation of the organic filler according to the invention, ie a precursor of the organic filler according to the invention which has not yet been modified by means of the at least one organic modifier.
  • this modification only takes place in situ, i.e. it does not take place in advance in a separate step as in the case of the filler according to the invention.
  • the filler component of the rubber composition according to the invention preferably contains at least one organic filler according to the invention, ie such a filler to which the at least one organic modifier has already been attached beforehand in a separate step.
  • the rubber compositions can contain other fillers that are different from these fillers.
  • the rubber compositions according to the invention can also contain industrial carbon blacks, in particular furnace blacks, such as are classified as general-purpose carbon blacks under ASTM Code N660.
  • the rubber compositions according to the invention can contain, in particular, inorganic fillers, for example of different particle size, particle surface area and chemical nature with different potential for influencing the vulcanization behavior. If other fillers are present, they should preferably have properties that are as similar as possible to those in the filler according to the invention Rubber composition used organic fillers according to the invention, in particular with regard to their pH.
  • fillers are preferably phyllosilicates such as clay minerals, for example talc; carbonates like
  • the rubber compositions according to the invention can also contain inorganic fillers such as silica or silicic acid.
  • inorganic fillers such as silica or silicic acid.
  • zinc oxide is not one of the inorganic fillers, since zinc oxide has the task of a vulcanizer or a vulcanization-promoting additive.
  • magnesium oxide can have a negative effect on adhesion to neighboring tire layers and silica tends to bind organic molecules such as the thiazoles used in some vulcanization systems to its surface and thus reduce their effectiveness to inhibit.
  • Inorganic fillers including preferably silica and other fillers that carry Si—OH groups on their surface, can also be surface-treated
  • silanization with organosilanes such as, for example, alkylalkoxysilanes or aminoalkylalkoxysilanes or mercaptoalkylalkoxysilanes can be advantageous.
  • the alkoxysilane groups can bond, for example, by hydrolytic condensation to the surfaces of silicates or silica, or to other suitable groups, while, for example, the amino groups and thiol groups can react with isoprene moieties of certain rubbers. This can provide mechanical reinforcement for the vulcanized rubber compositions of the present invention.
  • the fillers other than the organic fillers according to the invention can be used individually or in combination with one another.
  • fillers are used, their proportion is preferably less than 40 phr, particularly preferably 20 to 40 phr and particularly preferably 25 to 35 phr.
  • the rubber composition according to the invention can contain further optional components such as plasticizers and/or antidegradation agents, resins, in particular resins which increase adhesion and even already vulcanizers and/or vulcanization-promoting additives such as zinc oxide and/or fatty acids such as stearic acid.
  • plasticizers and/or antidegradation agents resins, in particular resins which increase adhesion and even already vulcanizers and/or vulcanization-promoting additives such as zinc oxide and/or fatty acids such as stearic acid.
  • plasticizers makes it possible in particular to influence properties of the unvulcanized rubber composition, such as processability, but also properties of the vulcanized rubber composition, such as its flexibility, especially at low temperatures.
  • particularly suitable plasticizers are mineral oils from the group of paraffinic oils (essentially saturated chain-like hydrocarbons) and naphthenic oils (essentially saturated cyclic hydrocarbons).
  • paraffinic oils essentially saturated chain-like hydrocarbons
  • naphthenic oils essentially saturated cyclic hydrocarbons
  • aromatic hydrocarbon oils is also possible and even preferred.
  • a mixture of paraffinic and/or naphthenic oils with aromatic oils can also be advantageous as plasticizers with regard to the flattening of the rubber composition to other rubber-containing components in tires, such as the carcass, for example.
  • plasticizers are, for example, esters of aliphatic dicarboxylic acids such as adipic acid or sebacic acid, paraffin waxes and polyethylene waxes.
  • the paraffinic oils and naphthenic oils are particularly suitable in the context of the present invention, but aromatic oils, in particular aromatic mineral oils, are most preferred.
  • Plasticizers and very particularly preferably the paraffinic and/or naphthenic and in particular aromatic process oils are preferably used in an amount of 0 to 100 phr, preferably 10 to 70 phr, particularly preferably 20 to 60 phr, in particular 20 to 50 phr.
  • antidegradants examples 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).
  • adhesion-promoting resins can be used to improve adhesion of the vulcanized rubber composition of the present invention to other adjacent tire components.
  • Particularly suitable resins are those based on phenol, preferably from the group consisting of phenolic resins, phenol-formaldehyde resins and phenol-acetylene resins.
  • aliphatic hydrocarbon resins such as EscorezTM 1102 RM from ExxonMobil, but also aromatic hydrocarbon resins.
  • aliphatic hydrocarbon resins improve adhesion to other rubber components of the tire. They typically have lower adhesion than the phenolic-based resins and can be used alone or in admixture with the phenolic-based resins.
  • adhesion-promoting resins are preferably those selected from the group consisting of phenolic-based resins, aromatic hydrocarbon resins, and aliphatic hydrocarbon resins. Their proportion is preferably 0 to 15 phr or 1 to 15 phr, particularly preferably 2 to 10 phr and very particularly preferably 3 to 8 phr.
  • the rubber composition according to the invention can also contain additives which promote vulcanization but are not capable of independently triggering it.
  • additives include, for example, vulcanization accelerators such as saturated fatty acids having 12 to 24, preferably 14 to 20 and particularly preferably 16 to 18 carbon atoms, such as stearic acid and the zinc salts of the aforementioned fatty acids.
  • Thiazoles can also be among these additives.
  • vulcanization-promoting additives in the vulcanization systems described below.
  • vulcanization-promoting additives and in particular the aforementioned fatty acids and/or their zinc salts, preferably stearic acid and/or zinc stearate are used in the rubber compositions according to the invention, their proportion is 0 to 10 phr, particularly preferably 1 to 8 phr and particularly preferably 2 to 6 phr.
  • the rubber composition according to the invention can also already contain certain vulcanizers such as zinc oxide, which is preferred. However, it is also possible to only use such vulcanizers in the vulcanization systems described below. Are vulcanizers such as zinc oxide in the invention
  • rubber compositions are used, their proportion is preferably from 0 to 10 phr, particularly preferably from 1 to 8 phr and particularly preferably from 2 to 6 phr.
  • Vulcanizable rubber composition according to the invention
  • Another object of the present invention is a vulcanizable rubber composition
  • a vulcanizable rubber composition comprising the invention
  • All preferred embodiments described hereinabove in connection with the modified organic filler according to the invention are also preferred embodiments with regard to the vulcanizable rubber composition according to the invention.
  • the vulcanization systems are not counted among the rubber compositions according to the invention here, but are treated as additional systems that cause the crosslinking.
  • the addition of the vulcanization systems to the rubber compositions according to the invention gives rise to the vulcanizable rubber compositions according to the invention.
  • the rubber component used according to the invention of the vulcanizable rubber composition according to the invention which contains at least one rubber, allows the use of a wide variety of different vulcanization systems.
  • the vulcanization of the rubber compositions of the present invention is preferably carried out using at least zinc oxide and/or at least sulfur and/or at least one peroxide, such as in particular at least one organic peroxide.
  • zinc oxide it can be added to the rubber component (A) or to component (B).
  • Zinc oxide is preferably added to component (A).
  • sulfur it is preferably added to component (B).
  • At least zinc oxide and/or at least sulfur is preferably used in combination with different organic compounds for the vulcanization. This can be done with the various additives
  • a saturated fatty acid with 12 to 24, preferably 14 to 20 and particularly preferably 16 to 18 carbon atoms, for example stearic acid and/or zinc stearate are preferably added to the zinc oxide as a vulcanization accelerator. This allows the vulcanization rate to be increased. However, the final extent of vulcanization is usually reduced when the fatty acids mentioned are used.
  • thiurams such as thiuram monosulfide and/or thiuram disulfide and/or tetrabenzylthiuram disulfide (TbzTD) and/or dithiocarbamates and/or sulfenamides are added to the zinc oxide in the absence of sulfur or alternatively in the presence of sulfur. to shorten the scorch time and improve the vulcanization efficiency while forming particularly stable networks.
  • 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-benzothiazylsulfenamide (TBBS).
  • a vulcanization based at least on zinc oxide an alkylphenol disulfide is added to the zinc oxide in order to adjust the scorch times, in particular to accelerate them.
  • a further, fourth variant of a vulcanization based at least on zinc oxide uses a combination of zinc oxide with polymethylolphenol resins and their halogenated derivatives, in which preferably neither sulfur nor sulfur-containing compounds are used.
  • the vulcanization is carried out using a combination of zinc oxide with thiazoles and/or thiurams and/or sulfenamides and preferably sulfur.
  • sulfur to such systems increases both the rate and extent of vulcanization and contributes to the processability of the rubber compositions during the vulcanization process.
  • the use of this vulcanization system preferably provides heat-resistant and fatigue-resistant vulcanizates which, even in the vulcanized state, have good adhesion to other components of vehicle tires, in particular rubber compositions of the carcass.
  • a particularly advantageous cure system includes zinc oxide, a thiuram such as tetrabenzylthiuram disulfide (TbzTD), a sulfenamide such as N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and sulfur.
  • the combination of the first variant with the fifth variant is particularly preferred, ie the use of one Vulcanization systems 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.
  • vulcanization systems are based on pure sulfur vulcanization or peroxide vulcanization, with the latter being able to lead to an undesired reduction in molecular weight due to splitting of the molecules, particularly when using butyl rubber or other rubbers.
  • the rubber composition according to the invention is vulcanized in the presence of the organic fillers according to the invention, such as HTC lignins.
  • Rubber composition may be contained in the rubber composition of the present invention, ie already part of the rubber composition according to the invention and therefore do not necessarily have to be contained in the vulcanization system.
  • the stearic acid and/or optionally zinc stearate in particular may already be present in the rubber composition according to the invention and for the complete vulcanization system to form in situ, for example by mixing/adding at least zinc oxide and at least sulfur.
  • the present invention also relates to a kit of parts comprising a rubber composition according to the invention in spatially separated form as part (A ) (also as Part (A) referred to) and a vulcanization system as part (B) (also referred to as part (B)), preferably a vulcanization system comprising at least zinc oxide and/or at least sulfur.
  • a vulcanization system comprising at least zinc oxide and/or at least sulfur.
  • the kit of parts is used to produce a vulcanizable rubber composition.
  • the rubber composition according to the invention that makes up part of the kit-of-parts can be used as part (A) in step 1 of the process described below for producing a vulcanizable rubber mixture, and the second part of the kit-of-parts, namely the Vulcanization system as part (B) in stage 2 of said process.
  • the rubber composition according to the invention and the vulcanization system are in the kit-of-parts according to the invention spatially separated from each other. All systems which have already been described above in connection with the vulcanizable rubber composition according to the invention can be used as the vulcanization system.
  • 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, where at least zinc oxide can alternatively be present within part (A).
  • the kit-of-parts according to the invention particularly preferably 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, where at least zinc oxide can alternatively be present within part (A).
  • kit-of-parts according to the invention very particularly preferably 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, with at least zinc oxide and/or stearic acid and/or zinc stearate alternatively within Part (A).
  • 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, with at least zinc oxide and/or stearic acid and/or zinc stearate alternatively within Part (A).
  • 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, with at least zinc oxide and/or stearic acid and /or zinc stearate may alternatively be present within Part (A).
  • 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, with at least zinc oxide and/or stearic acid and /or zinc stearate may alternatively be present within Part (A).
  • a further object of the present invention is a process for preparing the rubber composition according to the invention and a process for preparing the vulcanizable rubber composition according to the invention. All preferred embodiments described above in connection with the modified organic filler according to the invention, the rubber composition 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 with regard to the method according to the invention.
  • the vulcanizable rubber composition according to the invention is preferably prepared in two stages in stages 1 and 2, the rubber composition according to the invention preferably being obtainable after going through the first stage of this two-stage process.
  • the rubber composition according to the invention is first produced as a masterbatch by mixing together all the components that are used to produce the rubber composition according to the invention.
  • the components of the vulcanization system are admixed to the rubber composition according to the invention. step 1
  • the at least one rubber which is contained in the rubber component of the rubber composition according to the invention, and optionally usable resins that are different and preferably improve adhesion are preferably initially introduced. However, the latter can also be added with the other additives.
  • the rubbers are preferably at least room temperature (23.degree. C.) or are preferably used preheated to temperatures of at most 50.degree. C., preferably at most 45.degree. C. and particularly preferably at most 40.degree. More preferably, the rubbers are pre-kneaded for a short period of time before the other ingredients are added. If inhibitors are used for subsequent vulcanization control, such as magnesium oxide, they are preferably also added at this point in time.
  • At least one organic filler according to the invention and optionally further fillers are then added, preferably with the exception of zinc oxide, since this is used in the rubber compositions according to the invention as a component of the vulcanization system and is therefore not considered a filler herein.
  • the at least one organic filler according to the invention and optionally further fillers are preferably added incrementally.
  • plasticizers and other components such as stearic acid and/or zinc stearate and/or zinc oxide are only added after the addition of the at least one organic filler according to the invention or the other fillers, if used.
  • This facilitates the incorporation of the at least one organic filler according to the invention and, if present, the other fillers.
  • the highest temperatures obtained during the preparation of the rubber composition in the first stage (“dump temperature”) should not exceed 170° C., since partial decomposition of the reactive rubbers and/or the organic fillers according to the invention is possible above these temperatures.
  • the maximum temperature in the preparation of the rubber composition of the first stage is between 80°C and ⁇ 200°C, more preferably between 90°C and 190°C, most preferably between 95°C and 170°C.
  • the mixing of the components of the rubber composition according to the invention is usually carried out using internal mixers which are equipped with tangential or intermeshing (ie intermeshing) rotors. The latter usually allow better temperature control. Mixers with tangential rotors are also referred to as tangential mixers. However, the mixing can also be carried out, for example, using a twin-roller mixer. After the rubber composition has been prepared, it is preferably cooled before the second stage is carried out. Such a process is also referred to as aging. Typical aging periods are 6 to 24 hours, preferably 12 to 24 hours. Level 2
  • the rubber composition of the first stage is incorporated with the components of the vulcanization system, thereby obtaining a vulcanizable rubber composition according to the present invention.
  • a vulcanization system based at least on zinc oxide and at least on sulfur is used as the vulcanization system, at least the 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 possible to add zinc oxide in stage 2 as well, and also optionally to add at least one saturated fatty acid such as stearic acid. However, it is preferred to integrate these constituents into the rubber composition according to the invention as early as stage 1.
  • the highest temperatures obtained in the second stage (“dump temperature”) during the production of the admixture of the vulcanization system to the rubber composition should preferably not exceed 130.degree. C., particularly preferably 125.degree.
  • a preferred temperature range is between 70°C and 125°C, particularly preferably 80°C and 120°C. At temperatures above the maximum temperature of 105 to 120 °C for the curing system, premature vulcanization can occur.
  • the composition is preferably cooled.
  • a rubber composition according to the invention is thus initially obtained in the first stage, which is supplemented in the second stage to form a vulcanizable rubber composition
  • the vulcanizable rubber compositions that are produced undergo shaping processes that are preferably tailored to the end article.
  • Rubber compositions are preferably brought into a suitable form, which is necessary for the vulcanization process, by means of extrusion or calendering.
  • the vulcanization can take place in vulcanization molds using pressure and temperature, or the vulcanization can take place without pressure in temperature-controlled channels in which air or liquid materials ensure heat transfer.
  • Vulcanized Rubber Composition According to the Invention Another object of the present invention is a vulcanized rubber composition which is obtainable by vulcanizing the vulcanizable rubber composition according to the invention or by vulcanizing one obtainable by combining and mixing the two parts (A) and (B) of the kit-of-parts according to the invention vulcanizable rubber composition.
  • vulcanization is carried out under pressure and/or the action of heat. Suitable vulcanization temperatures are preferably from 140°C to 200°C, more preferably from 150°C to 180°C.
  • the vulcanization takes place at a pressure in the range from 50 to 175 bar. However, it is also possible to carry out the vulcanization in a pressure range of 0.1 to 1 bar, for example in the case of profiles.
  • the vulcanized rubber compositions obtained from the vulcanizable rubber compositions according to the invention preferably have a Shore A hardness in the range from more than 50 to less than 70, more preferably from 53 to 65 and most preferably from 55 to 62 and/or a resilience at 70° C ranging from greater than 60% to less than 75%, more preferably greater than 61% to less than 73%, most preferably greater than 62% to less than 72%.
  • Shore A hardness in the range from more than 50 to less than 70, more preferably from 53 to 65 and most preferably from 55 to 62 and/or a resilience at 70° C ranging from greater than 60% to less than 75%, more preferably greater than 61% to less than 73%, most preferably greater than 62% to less than 72%.
  • Another object of the present invention is a use of at least one organic filler according to the invention for the production of rubber compositions and vulcanizable rubber compositions for / for use in the production of tires such as pneumatic tires and solid rubber tires, in particular pneumatic tires, preferably in each case for their tread, sidewall and / or Inner liner and/or in the manufacture of technical rubber items, preferably profiles, seals, dampers and/or hoses.
  • tires such as pneumatic tires and solid rubber tires, in particular pneumatic tires, preferably in each case for their tread, sidewall and / or Inner liner and/or in the manufacture of technical rubber items, preferably profiles, seals, dampers and/or hoses.
  • Rubber composition Another object of the present invention is a method for producing a pneumatic tire, preferably comprising a tread of the vulcanizable rubber composition according to the invention.
  • the treads are typically vulcanized under pressure and/or heat along with the tire carcass and/or other tire components.
  • Suitable vulcanization temperatures are preferably from 140°C to 200°C, more preferably from 150°C to 180°C.
  • the method can be carried out, for example, in such a way that the green tire is formed into the closing mold by closing the press.
  • an inner bellows heating bellows
  • a small pressure ⁇ 0.2 bar
  • the press and thus the mold are then completely closed.
  • the pressure in the bellows is increased (crowning pressure, usually around 1.8 bar). This embosses the profile into the tread as well as the sidewall lettering.
  • the press is locked and the closing force is applied.
  • the closing force varies depending on the press type and tire size and can be up to 2500 kN using hydraulic cylinders. After the closing forces have been applied, the actual vulcanization process begins.
  • the mold is continuously heated with steam from the outside. Here, temperatures are generally set between 150 and 180 °C.
  • temperatures are generally set between 150 and 180 °C.
  • the internal pressures can vary and differ depending on the type of tire such as car or truck tires.
  • the Shore A hardness of vulcanized rubber compositions was determined using a Zwick 3150 hardness tester in accordance with DIN 53505 at 23.degree. Three measurements were performed on each sample. The results obtained represent the average value of these three measurements. Between vulcanization and testing, the samples were stored at room temperature for at least 16 hours. 2. Determination of resilience
  • the rebound resilience of vulcanized rubber compositions was determined in accordance with DIN 53512 using a Zwick/Roell 5109 tester. The rebound resilience was measured at 23 °C and at 70 °C. Between vulcanization and testing, the samples were stored at room temperature for at least 16 hours.
  • Tensile strength of vulcanized rubber compositions was determined according to ASTM D412. For the tests, the vulcanized specimens were punched into dumbbell-shaped specimens. Tensile strength was measured in a Zwick/Roell Z1.0 universal tensile tester (Germany) at a crosshead speed of 500 mm/min. Five specimens were used for the evaluation of the tensile data. The mean tensile property values taken from these five samples are reported. Between vulcanization and testing, the samples were stored at room temperature for at least 16 hours.
  • the crosslink densities of the rubber compositions were determined by swelling tests. Before each swelling test, vulcanized samples were extracted with acetone in a Soxhlet apparatus for 48 h in order to remove low-molecular polar substances such as unreacted accelerators, flattening agents or vulcanization by-products. The extracted samples were then dried in a vacuum oven at 40°C for 24 h. The acetone-extracted samples were immersed in toluene at room temperature for one week. At the end of After the immersion time, the samples were removed and blotted with filter paper and transferred to a weighing bottle to obtain the weight of the swollen vulcanizates.
  • the vulcanization properties and the vulcanization behavior were each determined using a suitable device (rheometer) (Elite Rubber Process Analyzer (TA Instruments, USA)), with the vulcanization being carried out at 160 °C for 30 minutes at a frequency of 1.67 Hz and an elongation (strain) of 6.98% according to ISO 3417:2008.
  • the minimum and maximum torque (ML, MH) were determined from the measurement curves. From this, the difference D (MH-ML) can be calculated. Furthermore, for each of the measurement curves, the minimum torque ML is defined as 0% of the maximum torque MH and the maximum torque MH is standardized as 100%.
  • the time periods were determined in which the torque, starting from the point in time of the minimum torque ML, reached 2%, 10%, 50% or 90% of the maximum torque MH. The periods were designated T2, T10, T50 and T90.
  • the specific surface area of the filler to be examined was determined by nitrogen adsorption in accordance with the ASTM D 6556 (2019-01-01) standard provided for carbon blacks (carbon black). According to this standard, the BET surface (specific total surface according to Brunauer, Emmett and Teller) and the external surface (STSA surface; Statistical Thickness Surface Area) were also determined as follows. Before the measurement, the sample to be analyzed was dried to a dry substance content of >97.5% by weight at 105°C. In addition, the measuring cell was dried for several hours in a drying oven at 105 °C before the sample was weighed. The sample was then filled into the measuring cell using a funnel.
  • the upper shaft of the measuring cell became dirty during filling, it was cleaned with a suitable brush or pipe cleaner.
  • glass wool was weighed in in addition to the sample. The purpose of the glass wool was to hold back any flying material that could soil the device during the heating process.
  • the anhydrous ash content of the samples was determined according to the standard DIN 51719 by thermogravimetric analysis as follows: Before weighing, the sample was ground or ground in a mortar. Before the ash is determined, the dry matter content of the weighed material is determined. The sample material was weighed into a crucible with an accuracy of 0.1 mg. The furnace together with 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 h. The furnace was then cooled down to 300 °C before the samples were taken. The samples were cooled to ambient temperature in the desiccator and weighed again. The remaining ash was related to the weight and the weight percent content of ash was determined. A triplicate determination was carried out for each sample and the mean value was given.
  • the pFI value was determined based on the ASTM D 1512 standard as follows. If the dry sample was not already in the form of a powder, it was ground or ground into a powder. In each case 5 g sample and 50 g deionized water were weighed into a beaker. The suspension was heated to a temperature of 60° C. with constant stirring using a magnetic stirrer with a felt function and stirrer bar, and the temperature was kept at 60° C. for 30 min. The stirring function of the stirrer was then deactivated so that the batch was able to cool while being stirred. After cooling, the water that had evaporated was made up by adding more deionized water and stirring again for 5 minutes. The pFI value of the suspension was determined using a calibrated measuring device. The temperature of the suspension should be 23°C ( ⁇ 0.5°C). A duplicate determination was carried out for each sample and the mean value was given. 10. Determination of the heat loss of the organic fillers used
  • the heat loss of the sample was determined based on ASTM D 1509 as follows. For this purpose, the MA100 moisture balance from Sartorius was heated to a drying temperature of 125.degree. The dry sample, if not already present as a powder, was ground or ground into a powder. Approx. 2 g of the sample to be measured was weighed into a suitable aluminum pan in the moisture balance and the measurement was then started. As soon as the weight of the sample did not change by more than 1 mg for 30 s, this weight was considered constant and the measurement was terminated. The heating loss then corresponds to the displayed moisture content of the sample in % by weight. At least one duplicate determination was carried out for each sample. The weighted mean values are given.
  • the acidic hydroxyl groups available on the surface were determined qualitatively and quantitatively colorimetrically according to Sipponen.
  • the Sipponen method is based on the adsorption of the basic dye Azure B on the acidic hydroxyl groups accessible on the filler surface and is described in detail in the article "Determination of surface-accessible acidic hydroxyls and surface area of lignin by cation dye adsorption" (Bioresource Technology 169 ( 2014) 80-87).
  • the amount of acidic hydroxyl groups available on the surface is given in mmol/g of filler. Regardless of how the filler was obtained, the process was not only applied to lignin-based fillers, but also, for example, to the comparison carbon black N660.
  • the 14 C content (content of bio-based carbon) can be determined using the radiocarbon method in accordance with DIN EN 16640:2017-08.
  • the carbon content can be determined by elemental analysis according to DIN 51732: 2014-7. 14. Determination of the oxygen content
  • the oxygen content can be determined by high-temperature pyrolysis using the EuroEA3000 CHNS-0 analyzer from EuroVector S.p.A. determine. 15. Determination of the grain size distribution
  • the grain size distribution can be determined using laser diffraction of the material dispersed in water according to ISO 13320:2009.
  • the volume fraction is given, for example, as d99 in pm (diameter of the grains of 99% of the volume of the sample is below this value)
  • the solubility is determined in triplicate. For this purpose, 2.0 g of dry filler are weighed into 20 g of 0.1 M NaOH. However, if the determined pH value of the sample is ⁇ 10, this sample is discarded and instead 2.0 g of dry filler are weighed into 20 g of 0.2 M NaOH. Depending on the pH value ( ⁇ 10 or >10), either 0.1 M NaOH (pH >10) or 0.2 M NaOH (pH ⁇ 10) is used. The alkaline suspension is shaken at room temperature for 2 hours at a speed of 200 shakers per minute. If the liquid touches the lid, the number of shakers should be reduced so that this does not happen. The alkaline suspension is then centrifuged at 6000 ⁇ g.
  • the supernatant from the centrifugation is filtered through a Por 4 frit.
  • the solid after centrifugation is washed twice with distilled water, repeating the centrifugation and filtration described above after each washing.
  • the solid is dried for at least 24 h at 105 °C in a drying oven to constant weight.
  • the lignin V1 obtainable by hydrothermal treatment was produced analogously to the method described in WO 2017/085278 A1 for the production of lignins obtainable by hydrothermal treatment.
  • a liquid containing the renewable raw material is provided for this purpose.
  • water and lignin are mixed and a lignin-containing liquid with an organic dry matter content of 15% by weight is prepared.
  • the lignin is then completely dissolved in the lignin-containing liquid.
  • the pH is adjusted to 9.8 by adding NaOH.
  • the preparation of the solution is supported by thorough mixing at 80° C. for 3 hours.
  • the liquid containing the renewable raw material is subjected to hydrothermal treatment and a solid is obtained in this way.
  • the solution produced is heated at 2 K/min to the reaction temperature of 230° C., which is maintained for a reaction time of 5 h. Then there is a cooling down. As a result, an aqueous suspension of solids is obtained.
  • the solid is largely dewatered and washed by filtration and washing.
  • the dewatered and washed solid is dried in a circulating air drying cabinet at 105° C. to a residual moisture content of 3%.
  • the dried solid is deagglomerated to d99 ⁇ 10 ⁇ m in a NETZSCH CGS 32 counter-jet mill under nitrogen.
  • the subsequent thermal treatment takes place under nitrogen in an oven, with heating at 2 K/min to a temperature of 180° C., holding for a period of 3 h and cooling again.
  • the lignin V1 obtainable by hydrothermal treatment was characterized as indicated in Table 1.1 below using the methods mentioned above. Table 1.1 - Properties of lignin V1 obtainable by hydrothermal treatment
  • a series of modified organic fillers according to the invention were produced, the lignin V1 described above under item 1.1 being used as the starting material in each case.
  • L-cystine ((2R,2'R)-3,3'-dithiobis(2-amino-propanoic acid; LC), 1,2-epoxy-9-decene (ED), dodecen-1yl-succinic anhydride (DSA) and hexanethiol (HT).
  • the modified organic fillers 11 with LC), I2 (with ED) and I3 (with DSA) and I4 (with HT) according to the invention
  • 20 g of the HTC lignin V1 were weighed into a 500 mL round-bottom flask in which 250 up to 300 mL n-decane.
  • the resulting mixture was then heated to a temperature ranging from 150 to 165°C. Once this temperature was reached, one of the organic modifiers LC (0.7g), ED (2.0g), DSA (1.7g) or HT (1.2g) was added.
  • the resulting mixture was then stirred at this temperature for a period of 24 h to ensure complete reaction of the To ensure lignins V1 with the modifier used.
  • the resulting mixture was then transferred to a Soxhlet apparatus to extract solvent, unreacted modifier, and possible reaction by-products.
  • the extraction was carried out using toluene at a boiling point of 111°C for a period of 16 h.
  • the product obtained in each case was dried in an oven under vacuum at a temperature of 70°C for a period of 24 hours.
  • the surface-modified HTC lignins I1, I2, I3 and I4 obtained in this way were characterized using the methods mentioned above, as indicated in Table 1.2 below, and used in this form below.
  • the mixing chamber was heated to 50°C.
  • the amounts of the ingredients were each calculated for a filling level of the mixing chamber of 70%.
  • the mixing chamber was charged with rubber (SSBR and BR according to positions 1 and 2 of Table 2.1), the charging device to the mixing chamber was pneumatically locked and mixed for 1 minute.
  • the filling device of the mixing chamber was opened, 1/4 of the amount of the organic filler according to position 3 of table 2.1 was added together with the process oil (TDAE) according to position 4 of table 2.1, the mixing chamber was closed again and mixed for 1 minute (total mixing time: 2 minutes).
  • the filling device of the mixing chamber was then opened, another 1/4 of the amount of the organic filler according to item 3 in Table 2.1 was added, the mixing chamber was closed again and mixed for 1 minute (total mixing time: 3 minutes).
  • the filling device of the mixing chamber was then opened, another 1/4 of the amount of the organic filler according to item 3 in Table 2.1 was added, the mixing chamber was closed again and mixed for 1 minute (total mixing time: 4 minutes).
  • the filling device of the mixing chamber was opened again, the last 1/4 of the amount of the organic filler according to position 3 of table 3.1 and the additives of positions 5, 6, 7 and 8 according to table 2.1 were added and for 1
  • total mixing time 5 minutes. Mixing was then continued for a further 5 minutes up to a total mixing time of 10 minutes.
  • the ejection temperature which was in the range from 70 to 80 °C, was controlled and measured after the total mixing time. The ejection temperature was determined using a thermocouple. After this
  • SSBR styrene-butadiene rubber produced by polymerization of styrene and butadiene in solution
  • Buna® CB 24 from Arlanxeo Deutschland GmbH was used as the BR (butadiene rubber).
  • TDAE is a commercially available aromatic mineral oil from Hansen and Rosenthal KG.
  • ZnO is zinc oxide.
  • TMQ is 2,2,4-TrimethyM,2-dihydroquinoline.
  • 6-PPD is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine.
  • One of the rubber compositions KV1 and KI1 to KI3 was introduced into a tangential mixer (Brabender internal mixer 350S). Before the The mixing chamber was heated to 50° C. before mixing began. The amounts of the ingredients were each calculated for a filling level of the mixing chamber of 70%. After the rotors had started (30 rpm), the ingredients were metered in according to items 9 to 12 in Table 3.1, the filling device to the mixing chamber was pneumatically locked and mixed for 5 minutes. (So total mixing time 5 minutes). By regulating the speed, the ejection temperature was controlled and measured after the total mixing time, which was in the range from 80 to 90 °C. The ejection temperature was determined using a thermocouple. After mixing, the mixture was removed from the mixer and discharged onto a laboratory mill (Schwabenthan Polymix 80T two-roll mill with a gap of 2.5 mm).
  • DPG is 1,3-diphenylguanidine.
  • TBBS is N-tert-butyl-2-benzothiazole sulfenamide.
  • TbzTD is tetrabenzylthiuram disulfide.
  • the vulcanizable rubber compositions KV1VS, KI1VS, KI2VS and KI3VS are rubber compositions particularly suitable for use and for the manufacture of tire treads.
  • the vulcanizable rubber compositions KV1VS, KI1VS, KI2VS and KI3VS were also fully vulcanized by vulcanization at 160° C. and 100 bar in a vulcanizing press (Wickert laboratory press WLP 1600/5*4/3).
  • Specimens KVIVS-v, KMVS-v, KI2VS-V and KI3VS-V corresponding to the vulcanizable rubber compositions KV1VS, KI1VS, KI2VS and KI3VS were obtained.
  • the vulcanization time to be set is based on the T9o time.
  • the vulcanized test specimens were immediately removed and cooled after the pressing time had elapsed.
  • vulcanized plates measuring 90 x 90 x 2 mm were used.
  • the vulcanization time to be set resulted from the T9o time plus one minute per millimeter of panel thickness (i.e. plus two minutes).
  • vulcanized cylindrical specimens each having a thickness of 12.5 mm were used.
  • the vulcanization time to be set resulted from the T9o time plus 5 minutes. 5. Examination of the vulcanized test pieces and the vulcanization behavior
  • the modified lignins used have good vulcanization behavior, in particular since the basicity of the lignin is increased due to the modification carried out and the vulcanization speed and extent of vulcanization is thus improved.
  • the faster vulcanization kinetics can be explained in particular by the presence of end-chain double bonds (i.e. vinyl groups) on the surface, which are more reactive towards vulcanization and increase the MH value by containing the filler -Increase polymer interaction compared to other blends.
  • the presence of a long alkyl chain can effectively shield the phenolic OH groups of the lignin.
  • the good vulcanization behavior can be explained in particular by a pH neutralization effect, ie by an equilibrium/stabilization reaction that occurs between the acidic COOH group and the basic amino group. As soon as the cross-linking reaction begins, the sulfur from the L-cystine takes over
  • modified lignins used enable improved mechanical properties in terms of tensile strength compared to unmodified lignin obtainable by hydrothermal treatment. This makes it clear that the addition of these modified lignins results in better filler Polymer interaction is achieved, in particular a better reaction between the end-chain double bond of ED-modified lignin and the disulfide group of LC-modified lignin and rubber during sulfur vulcanization. This is also consistent with the M H value.
  • Shore A hardness tests were also carried out on the vulcanized rubber compositions according to the method described above. It can be seen from FIG. 4 that the modified lignins used lead to an improved Shore A hardness compared to unmodified lignin obtainable by hydrothermal treatment. This is consistent with the improved crosslinking properties achieved. Further, resilience tests were carried out on the vulcanized rubber compositions according to the method described above.

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Abstract

La présente invention concerne une charge organique, caractérisée en ce que (i) au moins sur une partie des atomes d'oxygène d'au moins un groupe fonctionnel de la charge, choisi parmi les groupes OH phénoliques, les groupes phénolates, les groupes OH aliphatiques, les groupes acides carboxyliques, les groupes carboxylates et des mélanges de ceux-ci et/ou (ii) au moins sur une partie des atomes de carbone de la charge se trouvant en position ortho vi-à-vis des groupes OH phénoliques et/ou des groupes phénolates, une liaison covalente est formée entre au moins un agent de modification organique et la charge organique. L'invention concerne en outre une composition de caoutchouc comprenant au moins un caoutchouc et au moins ladite charge, une composition de caoutchouc vulcanisable comprenant en outre un système de vulcanisation, une composition de caoutchouc vulcanisée pouvant être obtenue à partir de celle-ci, ainsi qu'une utilisation de ladite charge pour la fabrication de compositions de caoutchouc (vulcanisables) destinées à être utilisées dans la fabrication de bandages, de préférence de bandages pneumatiques et de bandages pleins, de préférence dans chaque cas pour leur bande de roulement, leur flanc et/ou leur revêtement intérieur, et/ou destinées à être utilisées dans la fabrication d'articles techniques en caoutchouc, de préférence de profilés, de joints d'étanchéité, d'amortisseurs et/ou de flexibles.
EP22730165.2A 2021-05-20 2022-05-19 Charges organiques à surface modifiée et compositions de caoutchouc les contenant Pending EP4341342A1 (fr)

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EP4438676A1 (fr) 2023-03-29 2024-10-02 SunCoal Industries GmbH Composition de caoutchouc contenant des charges organiques et pouvant être réticulée au moyen de soufre
WO2026073541A1 (fr) * 2024-10-01 2026-04-09 Upm-Kymmene Corporation Charge à base de lignine contenant des compositions de caoutchouc pour améliorer la conductivité thermique et l'isolation électrique

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US11124653B2 (en) * 2015-06-27 2021-09-21 Godavari Biorefineries Ltd. Biofiller for rubber reinforcement
DE102016201801A1 (de) 2015-11-21 2017-05-24 Suncoal Industries Gmbh Partikelförmiges Kohlenstoffmaterial herstellbar aus nachwachsenden Rohstoffen und Verfahren zu dessen Herstellung
US10920048B2 (en) * 2016-05-09 2021-02-16 Nokian Renkaat Oyj Tyre comprising hydrothermally carbonized lignin
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FI3470457T4 (fi) 2017-10-10 2023-12-19 Continental Reifen Deutschland Gmbh Rikin avulla silloitettava kautsuseos, kautsuseoksen vulkanoitu kumi ja ajoneuvon rengas

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