Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• • 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
  • C08K3/041—Carbon nanotubes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
  • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
  • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
• • 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
• • 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
  • B60C19/00—Tyre parts or constructions not otherwise provided for
  • B60C19/08—Electric-charge-dissipating arrangements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2307/00—Characterised by the use of natural rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08J2409/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2471/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2310/00—Masterbatches

Definitions

• Sulfur-crosslinked rubber mixture for vehicle tires comprising carbon nanotubes (CNT), vehicle tires having the sulfur-crosslinked rubber mixture, and processes for producing the sulfur-crosslinked rubbers
• the invention relates to a sulfur-crosslinked rubber mixture for vehicle tires comprising carbon nanotubes (CNT), a vehicle tire having the sulfur-crosslinked rubber mixture, and a process for preparing the sulfur-crosslinked rubber mixture containing CNT.
• CNT carbon nanotubes
• the rubber compositions of the individual components of vehicle tires, in particular the composition of the tread, to a large extent determine their driving characteristics.
• WO 2012/080160 A1 discloses a rubber compound for treads of vehicle tires, which comprises a masterbatch of carbon nanotubes (CNT;
• Carbon nanotube) in ESBR emulsion-polymerized styrene-butadiene rubber
• ESBR emulsion-polymerized styrene-butadiene rubber
• the invention is based on the prior art based on the object to provide a sulfur-crosslinked rubber mixture containing carbon nanotubes (CNT), which is characterized by optimized electrical conductivity properties, the other properties, in particular the abrasion behavior remain at the same level or even improved become.
• This object is achieved in that the CNT are predispersed in at least one polyisoprene in the sulfur-crosslinked rubber mixture.
• Rubber composition thereby has an unexpectedly good electrical conductivity. This effect is particularly evident when compared with rubber blends containing polymer blends of styrene-butadiene rubbers and polyisoprene; in the case where the CNTs are predispersed in at least one polyisoprene (polyisoprene-CNT masterbatch), the surprisingly high electrical conductivity occurs.
• Another object underlying the present invention is to provide a vehicle tire having an improvement over the prior art in terms of conductivity.
• the vehicle tire has at least one component in a component at least one sulfur-crosslinked rubber mixture with the above-mentioned or below detailed features.
• the abrasion behavior remains at least at the same level or is also improved.
• the rubber mixture according to the invention can be used both for the cap and for the base.
• at least the cap has at least one
• sulfur-crosslinked rubber mixture is to be understood as meaning a rubber mixture which consists of a rubber final mixture (or rubber raw mixture)
• a sulfur-crosslinked rubber compound is thus a vulcanizate.
• a conductivity track is any type of rubber compound known to the person skilled in the art which is suitable for conducting the conductivity between at least two tire components and / or at least one inner tire component and the road surface or other external surfaces with which the tire in FIG Touch comes, make sure.
• the conductive sheet may be a so-called "carbon center beam” or else a strip which is in the
• vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, passenger car and two-wheeled tires.
• the rubber mixture according to the invention is also suitable for other components of
• Vehicle tires suitable such. B. in particular the, horn profile, and inner
• the rubber mixture according to the invention is also for others technical rubber articles, such as bellows, conveyor belts, air springs, straps, belts or hoses, as well as shoe soles.
• phr parts per hundred parts of rubber by weight
• the dosage of the parts by weight of the individual substances in this document is based on 100 parts by weight of the total mass of all rubbers present in the mixture, ie the at least one polyisoprene plus optionally further sulfur-vulcanizable rubbers which are added to the rubber mixture according to the invention.
• the subject of the invention is a sulfur-crosslinked one
• Carbon nanotubes Rubber mixture containing carbon nanotubes (CNT), which is also known as
• Carbon nanotubes or tubes Carbon nanotubes or tubes.
• CNT discrete carbon nanotubes
• the form factor is the quotient of the average length of the CNT divided by the
• the CNT have a
• the dimensions of the CNT are known to those skilled in the art
• the CNT have a length of 0.2 ⁇ to 1.4 ⁇ , preferably 0.5 ⁇ to 1 ⁇ , ie 200 nm to 1400 nm, preferably 500 nm to 1000 nm, on.
• the CNTs are predispersed in at least one polyisoprene. Surprisingly, only the predispersion of CNT in at least one polyisoprene results in a surprisingly high electrical conductivity.
• the CNT preferably only in at least one
• Polyisoprene are predispersed and not additionally masterbatches in the
• Rubber mixture are included, in which CNTs are predispersed in a different rubber matrix than polyisoprene.
• inventive rubber mixture are included, in which CNTs are predispersed in a different rubber matrix than polyisoprene.
• Rubber mixture does not prefer a masterbatch in which CNT are predispersed in ESBR.
• a polyisoprene-CNT masterbatch may contain other substances, such as plasticizers, s. below.
• the at least one polyisoprene may be a natural polyisoprene (NR, natural rubber) and / or a synthetic polyisoprene (IR).
• All embodiments may be both cis-1,4-polyisoprene and 3,4-polyisoprene. However, preference is given to the use of cis-1,4-polyisoprenes having an iron content of> 90% by weight. For one, such a
• NR natural rubber
• NR is such an iron-1,4-polyisoprene
• the cis-1,4-content in natural rubber is greater than 99% by weight.
• the at least one polyisoprene is at least one natural polyisoprene. This results in particularly good properties with regard to the requirements of the rubber mixture for use in at least one tire component with an excellent electrical
• Essential to the invention is that the CNT in the at least one polyisoprene
• the CNT are predispersed, i.
• the CNT are therefore present as a single, separate CNT in the at least one polyisoprene, but it can not be ruled out that even so
• the CNT can be present as a single CNT and possibly also as agglomerates. Both of the separate CNTs as well as the agglomerates can be measured by REM length and
• Diameter are determined, which reference is made at this point for details to the statements in WO 2012/080160 AI.
• an effective form factor "English, effective aspect ratio" as a quotient of the average length (arithmetic mean) and the
• Bundle diameter determined.
• the dispersion of the CNT in the at least one polyisoprene is carried out by methods known to the person skilled in the art, for example in accordance with the following
• the dispersion of CNT can be carried out by shear forces, namely z.
• CNTs may be incorporated into a rubber matrix via a prior wetting with ethanol followed by evaporation of the ethanol, such as
• the CNT and the at least one polyisoprene in which they are predispersed form a masterbatch which may contain other ingredients.
• the viscosity of the masterbatch (Mooney ML 1 + 4 at 100 ° C.) is preferably 80 to 120 MU.
• the content by weight of the CNT in the masterbatch is preferably from 0.1 to 20% by weight, based on the total amount of the masterbatch.
• the proportion of CNT in the masterbatch is 13 to 20 wt .-%, particularly preferably 14 to 18 wt .-%, in particular and for example 15 to 17 wt .-%.
• the masterbatch may, as a further constituent, in particular at least one
• the weight fraction of the plasticizer based on the total amount of the masterbatch is in this case preferably 0.1 to 20 wt .-%. According to an advantageous embodiment of the invention, it is 6 to 16 wt .-%, particularly preferably 8 to 14 wt .-%, in particular and for example 9 to 10 wt .-%.
• the proportion by weight of the CNT in the masterbatch here is also preferably 0.1 to 20% by weight, based on the total amount of the masterbatch, and according to a particularly advantageous embodiment of the invention 13 to 20% by weight, particularly preferably 14 to 18% by weight. %, in particular and for example 15 to 17 wt .-%.
• the sulfur-crosslinked rubber mixture contains, in addition to the polyisoprene in which the CNTs are predispersed, at least one further sulfur vulcanizable prior to vulcanization and thus at least one further diene rubber.
• the at least one further diene rubber is preferably selected from the group consisting of natural polyisoprene and / or synthetic polyisoprene and / or epoxidized polyisoprene and / or butadiene rubber and / or butadiene-isoprene rubber and / or solution-polymerized styrene-butadiene rubber and or emulsion-polymerized styrene-butadiene rubber and / or styrene-isoprene rubber and / or liquid rubbers having a molecular weight M w greater than 20,000 g / mol and / or halobutyl rubber and / or polynorbornene and / or isoprene-isobutylene copolymer and / or ethylene-propylene-diene rubber and / or nitrile rubber and / or chloroprene rubber and / or acrylate rubber and / or fluorinated
• nitrile rubber hydrogenated acrylonitrile-butadiene rubber
• Chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are used in the manufacture of technical rubber articles such as straps, belts and hoses, and / or shoe soles.
• the rubber compound is particularly suitable for vehicle tires, and it can be used in principle in any component, such as in particular the tread, the
• the diene rubber is preferably selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR) and butyl rubber (HR) and
• the diene rubber is particularly preferably selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR),
• Polybutadiene may be any of the types known to those skilled in the art. These include u.a. the so-called high-cis and low-cis types, wherein polybutadiene with an eis content greater than or equal to 90 wt .-% as high-cis type and polybutadiene with an eis content less than 90 wt .-% as low cis type is called.
• a low-cis polybutadiene is e.g. Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20 to 50 wt .-%. With a high-cis BR will be particularly good
• the employed polybutadiene (s) can be modified with and
• the modification may be those having hydroxy groups and / or ethoxy groups and / or epoxy groups and / or siloxane groups and / or amino groups and / or aminosiloxane and / or carboxy groups and / or
• Phthalocyanine groups and / or silane-sulfide groups are also known to the expert person, modifications, as well
• Functionalizations referred to, in question. Part of such functionalizations may be metal atoms.
• styrene-butadiene rubber styrene-butadiene copolymer
• SSBR solution-polymerized styrene-butadiene rubber
• ESBR emulsion-polymerized styrene-butadiene rubber
• SSBR styrene-butadiene rubber
• ESBR emulsion-polymerized styrene-butadiene rubber
• the styrene-butadiene copolymer used can be end-group-modified with the modifications and functionalizations mentioned above for the polybutadiene and / or be functionalized along the polymer chains.
• the rubber mixture contains at least one further reinforcing filler, wherein the ratio of further reinforcing fillers to CNT 1000 is from 1 to 2 to 1.
• the ratio is 200 to 1 to 2 to 1, most preferably 80 to 1 to 2 to 1.
• the amount of the at least one further reinforcing filler is preferably from 0.1 to 250 phr, more preferably from 20 to 250 phr, most preferably from 20 to 150 phr.
• the further reinforcing filler is preferably at least one carbon black and / or at least one silica.
• the rubber mixture contains 0.1 to 250 phr, preferably 2 to 200 phr, more preferably 10 to 100 phr, again preferably 20 to 80 phr of at least one carbon black.
• carbon black which has an iodine adsorption number according to ASTM D 1510 of 20 to 180 g / kg, more preferably 30 to 140 g / kg, and a DBP number according to ASTM D 2414 of 30 to 200 ml / 100 g 90 to 180 ml / 100g, more preferably 110 to 180 ml / 100g.
• a particularly suitable carbon black in the context of the present invention is, for example, a carbon black of the
• ASTM type N339 with an iodine adsorption number of 90 g / kg and a DBP number of 120 ml / 100g. This is for use in vehicle tires, especially in
• the rubber mixture contains 0.1 to 30 phr at least one silicic acid, preferably 5 to 30 phr of at least one silica. It can therefore also be a so-called partial silica mixture.
• silica and silica "are used synonymously in the context of the present invention.
• the silicas may be the silicas known to those skilled in the art which are suitable as a filler for tire rubber mixtures. However, it is particularly preferred if a finely divided, precipitated silica is used which has a nitrogen surface area (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 350 m 2 / g, preferably from 35 to 260 m 2 / g, more preferably from 70 to 235 m 2 / g and most preferably from 70 to 205 m 2 / g, and a CTAB surface (according to ASTM D 3765) from 30 to 400 m 2 / g, preferably from 30 to 255 m 2 / g, particularly preferably from 65 to 230 m 2 / g and very particularly preferably from 65 to 200 m 2 / g.
• BET surface area nitrogen surface area
• CTAB surface accordinging to ASTM D 3765
• Such silicas lead z. B. in rubber blends for inner tire components to particularly good physical properties of the vulcanizates.
• silicas can thus z. B. both those of the type Ultrasil® VN3
• the rubber mixture according to the invention may contain, preferably very small amounts, ie preferably 0 to 3 phr, further non-reinforcing fillers non-reinforcing fillers are within the scope of the present invention
• Zinc oxide does not belong to the fillers in the context of the present invention.
• the optional silica may be in the form of tethered or not
• the rubber mixture preferably contains at least one silane coupling agent.
• Silane coupling agents are also referred to in the context of the present invention as "silane”.
• the rubber mixture may thus contain a mixture of different silanes.
• silane coupling agents react with the superficial silanol groups of the silica or other polar groups during the mixing of the rubber or the rubber mixture (in situ) or even before the addition of the filler to the
• Rubber blends known silane coupling agents can be used.
• Such known from the prior art coupling agents are bifunctional organosilanes having on the silicon atom at least one alkoxy, cycloalkoxy or phenoxy group as a leaving group and have as other functionality a group which may optionally undergo a chemical reaction with the double bonds of the polymer after cleavage , In the latter group may be z.
• they may be the following chemical groups:
• silane coupling agents z. 3-mercaptopropyltriethoxysilane
• TESPT Sulfur atoms with different contents of the different sulfides.
• TESPT can also be used as a mixture with carbon black
• silane mixture which comprises 40 to 100% by weight of disulfides, particularly preferably 55 to 85% by weight of disulfides and very particularly preferably 60 to 80% by weight of disulfides.
• a silane mixture is e.g. available under the trade name Si 266® Evonik, which is e.g. is described in DE 102006004062 AI.
• blocked mercaptosilanes, as z. B. from WO 99/09036 are known, can be used as a silane coupling agent.
• Silanes as described in WO 2008/083241 Al, WO 2008/083242 Al, WO 2008/083243 Al and WO 2008/083244 Al, can also be used. Suitable for.
• silanes sold under the name NXT eg 3- (octanoylthio) -l-propyl-triethoxysilane
• NXT eg 3- (octanoylthio) -l-propyl-triethoxysilane
• VP Si 363® e.g 3- (octanoylthio) -l-propyl-triethoxysilane
• 3-mercaptopropyltriethoxysilane in combination with processing aids (which are listed below), in particular PEG carboxylic acid ester, can be used.
• the rubber mixture contains a combination of 3-mercaptopropyltriethoxysilane and PEG carboxylic acid ester, which gives particularly good properties, in particular with regard to the technical problem to be solved and overall a good level of properties in terms of other properties.
• the rubber mixture may contain further activators and / or agents for the binding of fillers, in particular carbon black. This can happen
• the rubber mixture according to the invention contains a maximum of 35 phr of at least one plasticizer, wherein the
• Rubber mixture in particular the extrudates before crosslinking, while good properties in view of the problem to be solved.
• plasticizer s
• the heat buildup properties hysteresis
• the conflict of objectives is made up of reinforcing properties
• the plasticizer can also be completely or partly pass through the above-described masterbatch comprising CNT and polyisoprene into the rubber base mixture in the appropriate amounts.
• plasticizers used in the present invention include all known in the art plasticizers such as aromatic, naphthenic or
• paraffinic mineral oil softening agents such as e.g. MES (mild extraction solvate) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or rubber-to-liquid oils (RTL) or biomass-to-liquid oils (BTL) are preferred with a content of polycyclic Aromatics of less than 3 wt .-% according to method IP 346 or rapeseed oil or resin acids in particular or fact or liquid polymers whose average molecular weight (determined by GPC gel permeation chromatography, based on BS ISO 11344: 2004) between 500 and 20,000 g / mol is located. Be in the
• rubber mixture used additional liquid polymers as plasticizers, they do not go as a rubber in the calculation of the composition of the polymer matrix.
• the plasticizer is preferably selected from the group consisting of the above-mentioned plasticizers. According to a particularly preferred embodiment of the invention contains the
• Masterbatch already at least one plasticizer (see above), preferably in this case at least one resin acid, in particular disproportionated resin soap (eg.
• Rubber mixture additionally - added to any existing plasticizer in the masterbatch - at least one plasticizer.
• Mineral oils are particularly preferred as plasticizers.
• mineral oil this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and / or RAE (Residual Aromatic Extract) and / or TDAE (Treated Distilled Aromatic Extracts) and / or MES (Mild Extracted Solvents) and / or naphthenic oils.
• the rubber mixture contains at least one mineral oil plasticizer, preferably at least TDAE and / or RAE as plasticizer. This results in particularly good processability, in particular a good miscibility of the rubber mixture.
• the plasticizer (s) which are not already contained in the masterbatch are preferably added in at least one basic mixing stage during the preparation of the rubber mixture according to the invention. Furthermore, the rubber mixture customary additives in conventional
• anti-aging agents such as. N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine (6PPD), N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-ditolyl-p-phenylenediamine (DTPD ), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), b) activators, such. As zinc oxide and fatty acids (eg., Stearic acid) and / or other activators, such as zinc complexes such as zinc ethylhexanoate,
• Mastikationswhismittel such. 2,2'-dibenzamidodiphenyl disulphide (DBD); and f) process aids such as, in particular, fatty acid esters and metal soaps, e.g.
• Zinc soaps and / or calcium soaps Zinc soaps and / or calcium soaps.
• the proportion of the total amount of further additives is 3 to 150 phr, preferably 3 to 100 phr and more preferably 5 to 80 phr.
• the total amount of other additives zinc oxide (ZnO) may be included in the above amounts.
• zinc oxides may be any type of zinc oxide known to those skilled in the art, such as ZnO granules or powder.
• the conventionally used zinc oxide usually has a BET surface area of less than 10 m 2 / g. However, it is also possible to use a zinc oxide having a BET surface area of from 10 to 100 m 2 / g, for example so-called "nano-zinc oxides".
• the rubber mixture according to the invention is sulfur-crosslinked, which means that the vulcanization of the underlying crude mixture in the presence of sulfur and / or sulfur donors is carried out with the aid of vulcanization accelerators.
• Some vulcanization accelerators can also act as sulfur donors.
• the accelerator is preferably selected from the group consisting of
• Thiourea accelerators and / or xanthate accelerators and / or guanidine accelerators Thiourea accelerators and / or xanthate accelerators and / or guanidine accelerators.
• a sulfenamide Beschleumgers which is selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamid (CBS) and / or N, N Dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and / or benzothiazyl-2-sulfenmorpholide (MBS) and / or N-tert-butyl-2-benzothiazyl sulfenamide (TBBS).
• CBS N-cyclohexyl-2-benzothiazolesufenamid
• DCBS N Dicyclohexylbenzothiazole-2-sulfenamide
• MBS benzothiazyl-2-sulfenmorpholide
• TBBS N-tert-butyl-2-benzothiazyl sulfenamide
• Sulfur donating substances are used. If the rubber mixture contains a sulfur-donating substance, it is preferably selected from the group comprising e.g. Thiuram disulfides, e.g. Tetrabenzylthiuram disulfide (TBzTD) and / or
• TMTD Tetramethylthiuram disulfide
• TETD tetraethylthiuram disulfide
• thiuramate tetrasulfides e.g. Dipentamethylene thiuram tetrasulfide (DPTT), and / or dithiophosphates, e.g.
• DipDis bis (diisopropyl) thiophosphoryl disulfide) and / or bis (0,0-2-ethylhexyl thiophosphoryl) polysulfide (eg Rhenocure SDT 50®, Rheinchemie GmbH) and / or zinc dichloro dithiophosphate (eg Rhenocure ZDT / S®, Rheinchemie GmbH) and / or zinc alkyl dithiophosphate, and / or 1, 6-bis (N, N-dibenzylthiocarbamoyldithio) hexane and / or diaryl polysulfides and / or dialkyl polysulfides.
• the vulcanizing agent which has a functionality of greater than four crosslinked, for example, the general formula D):
• G is a polyvalent cyclic hydrocarbon group and / or a polyvalent heterohydrocarbon group and / or a polyvalent siloxane group containing 1 to 100 atoms; wherein each Y independently selected from a rubber active group contains sulfur-containing functionalities; and wherein a, b and c are integers for which independently: a is 0 to 6; b is 0 to 8; and c is 3 to 5.
• the rubber-active group is preferably selected from a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a
• vulcanization retarders may be present in the rubber compound.
• Another object of the present invention is a vehicle tire, the at least one sulfur-crosslinked in at least one component according to the invention
• Rubber mixture has.
• the vehicle tire according to the invention can in
• the at least one component is particularly preferably at least one tread and / or one side wall and / or one conductivity track.
• a further subject of the present invention is a process for preparing a sulfur-crosslinked rubber mixture containing CNT comprising at least the following process steps: a) preparation of a masterbatch of at least one polyisoprene and CNT, the CNTs being intensively mixed into the polyisoprene; and
• step b) optionally providing further ingredients comprising at least one reinforcing filler and / or at least one sulfur crosslinkable rubber and / or antiaging agent and / or at least one silane coupling agent; and c) optionally mixing the further constituents from step b) with the polyisoprene CNT masterbatch; and
• step f) vulcanization of the mixture from step e) to a sulfur-crosslinked
• a masterbatch comprising at least one polyisoprene and CNT is prepared, which is subsequently optionally mixed with further constituents to form a rubber base mixture.
• the masterbatch itself constitutes a rubber masterbatch to which, according to step e), a sulfur vulcanization system may also be added, thereby providing a final rubber compound.
• step a) The preparation of the polyisoprene NR masterbatch according to step a) is carried out by methods known to the person skilled in the art, as described above.
• the ready mix is e.g. further processed by an extrusion process or calendering and brought into the appropriate form. Subsequently, the further processing by vulcanization according to step f), wherein due to the vulcanization system added in the context of the present invention, a sulfur crosslinking takes place.
• the mixture is preferably pre-vulcanized in the form of a tread and / or sidewall and / or a conductivity track and deposited as known in the manufacture of the vehicle tire blank.
• Mixtures here are mixtures according to the invention, while the mixtures marked with “V” are comparative mixtures
• the preparation of the mixture was carried out under customary conditions in three stages in a laboratory tangential mixer.
• test specimens were prepared by vulcanization and determined with these specimens typical for the rubber industry material properties.
• test procedures were used:
• Mooney viscosity according to ASTM D1646; e.g. ML1 + 4 at 100 ° C (Mooney units M.E.
• Dispersion by means of a dispergrader microwave disperGRADER
• FIG. 1 is a diagrammatic representation of FIG. 1:
• NR-CNT masterbatch CNT predispersed in NR: 67.3 wt% NR, 18.7 wt% CNT, 14 wt% resin acids; Density 1.03 g / cm 3
• Other additives Process auxiliaries: PEG carboxylic acid ester;
• Hydrocarbon resin Anti-aging agents; Antiozonant wax, zinc oxide;
• ESBR1500_CNT_1 ESBR as the sole rubber matrix, partly from an ESBR-CNT masterbatch and partially added separately:
• NR_CNT_1 NR as sole rubber matrix, partly from an NR-CNT masterbatch and partially added separately:
• CNT 60 phr of an NR-CNT masterbatch containing 82.8% by weight of NR and 17% by weight of CNT and the remainder of plasticizer and 50.32 phr of NR.
• E4 6.5 vol% CNT: 90 phr of the NR-CNT masterbatch (as described under 4.5 vol% CNT) and 25.48 phr NR.
• NR CNT MB The rubber matrix consists of 50% by weight of ESBR and 50% by weight of NR; the CNTs are predispersed exclusively in the NR (NR-CNT masterbatch):
• CNT 24.91 phr of the same NR-CNT masterbatch and 29.37 phr of NR and 50 phr of ESBR;
• CNT 37.75 phr of the same NR-CNT masterbatch and 18.74 phr of NR and 50 phr of ESBR;
• CNT 60.39 phr of the same NR-CNT masterbatch and no additional NR, i. 0 phr NR and 50 phr ESBR;
• ESBR CNT MB The rubber matrix consists of 50% by weight ESBR and 50% by weight NR; the CNT are predispersed exclusively in the ESBR (ESBR-CNT masterbatch):
• ESBR1500 CNT 1 ESBR1500 CNT 1
• no additional ESBR i. 0 phr ESBR and 50 phr NR
• NR / 50 ESBR (1/2 NR CNT MB, 1/2 ESBR CNT_MB): The rubber matrix consists of 50% by weight of ESBR and 50% by weight of NR; the CNT are both in
• ESBR-CNT-MB ESBR predispersed (ESBR-CNT-MB) as well as in the NR (NR-CNT masterbatch):
• V7 1.5% by volume
• CNT 9.29 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 42.3 phr of NR and 9.91 phr of the ESBR-CNT masterbatch ( as under
• V8 2% by volume
• CNT 12.46 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 39.69 phr of NR and 13.27 phr of the ESBR-CNT masterbatch (as described in US Pat
• V9 5% by volume CNT: 32.12 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and 23.4 phr of NR and 34.24 phr of the ESBR-CNT masterbatch (as described in US Pat ESBR1500 CNT 1 described) and 21.61 phr ESBR;
• V10 8.7% by volume CNT: 60.39 phr of the NR-CNT masterbatch (as described under 4.5% by volume of CNT) and no additional ie 0 phr NR and 60.31 phr of the ESBR-CNT Masterbatches (as described under ESBR1500 CNT 1) and no additional ie 0 phr ESBR;
• Polyisoprene here NR
• NR Polyisoprene

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• 2017
  • 2017-05-15 DE DE102017208137.6A patent/DE102017208137A1/de active Pending
• 2018
  • 2018-03-19 EP EP18713170.1A patent/EP3625288A1/de active Pending
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