Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/25—Incorporating silicon atoms into the molecule
• • 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
• • 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
  • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
  • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • 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
• • 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
• • 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
  • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
  • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
  • B60C2011/0016—Physical properties or dimensions
  • B60C2011/0025—Modulus or tan delta
• • 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
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking

Definitions

• the invention relates to a sulfur-crosslinkable rubber mixture containing a rubber blend, and a vehicle tire containing such a rubber mixture.
• Improvement of the wet grip and the dry braking generally further deteriorates the rolling resistance, the winter properties and the abrasion performance.
• tread compounds based on carbon black known as a filler for a good grip on ice, inter alia, a liquid polymer, eg. B.
• Rolling resistance which contains a liquid butadiene rubber in addition to a solid styrene-butadiene rubber.
• a polymer mixture of a high molecular weight SSBR and a low molecular weight SSBR is generated, wherein the SSBR can also be functionalized.
• This polymer blend is used in rubber compounds for tires.
• DE 102008058996 A1 and DE102008058991 AI disclose terminally amine-modified liquid polybutadienes or carboxyl-terminally modified liquid polybutadienes in tread mixtures with a high amount of unfunctionalized synthetic rubber as a substitute for conventional plasticizer oils.
• the tires should be characterized by a very good balance between low fuel consumption and good
• EP 2060604 Bl discloses a rubber mixture comprising a functionalized polymer having an M w of 20,000 g / mol and carbon black as filler in combination with 60 phr of natural rubber.
• Rubber mixture based on unfunctionalized synthetic rubber Rubber mixture based on unfunctionalized synthetic rubber
• EP 1 535 948 B1 discloses a styrene-butadiene rubber which is known as
• Functionalization carries polyorganosiloxane groups containing epoxy groups, wherein three or more polymer chains are attached to a polyorganosiloxane group.
• This polymer with an unfunctionalized butadiene rubber in a siliceous rubber composition is expected to provide improved rolling resistance, abrasion and wet grip properties.
• EP 1 925 363 B1 discloses a rubber composition for tires comprising a modified (functionalized) low molecular weight SBR
• the invention is based on the object to provide a rubber mixture that can be processed well. Furthermore, the object of the invention is to provide a rubber mixture with a rubber blend which, in the case of the resulting tires, leads to improved winter properties and / or
• Functionalization center can be more polymers) having at least one group selected from epoxy groups, hydroxy groups, carboxy groups, silane-sulfide groups, amino groups, siloxane groups, organosilicon groups,
• Phthalocyanine groups and amino groups containing alkoxysilyl groups is functionalized
• a vulcanization system containing at least one accelerator and elemental sulfur and / or at least one sulfur-donating substance, wherein the molar ratio of accelerator to sulfur is 0.18 to 5, the
• Polymer B in combination with the special vulcanization system is especially good can process.
• the polymer B acts similar to a plasticizer. This good processing behavior was evident even in blends with a high degree of filling and with a high proportion of plasticizer (composed of polymer B and other plasticizers present).
• phr parts per hundred parts of rubber by weight
• the dosage of the parts by weight of the individual substances is based on 100 parts by weight of the total mass of all the high-molecular and thus generally solid rubbers present in the mixture or in the blend.
• Polymer B according to the invention with an M w of 1300 to 10000 g / mol is therefore not included as a rubber in the hundred parts of the phr calculation.
• the rubber blend for the rubber composition contains a high molecular weight diene polymer A, which would normally be a solid rubber at room temperature, and a low molecular weight polymer B, which would normally be liquid at room temperature.
• Compound (s) can be a variety of diene polymers based on z. As butadiene, isoprene and styrene act. If the diene polymer A contains substituted, conjugated diene units, then the indication of the vinyl moiety is equivalent, e.g. B. in isoprene units on the 3,4-linked moieties, while in the presence of Butadiene units refers to the indication of the vinyl moiety on the 1, 2-linked moieties.
• the diene polymer A is polybutadiene or styrene-butadiene rubber (styrene-butadiene copolymer).
• the rubber mixture according to the invention also contains in the rubber blend a low molecular weight, solution-polymerized polymer B of at least one conjugated diene
• At least one of the polymers A or B comprises at least one of the polymers A or B at the chain end and / or along the polymer chain and / or in a coupling center with at least one group selected from epoxy groups,
• Alkoxysilyl groups is functionalized. In the functionalization, it is possible that several polymer chains are attached to a functionalization center or a coupling center.
• the functionalizations allow optimal processability in one
• the rubber blends for the rubber mixtures according to the invention can be prepared by processes known to those skilled in the art. For example, that can be prepared by processes known to those skilled in the art. For example, that can be prepared by processes known to those skilled in the art. For example, that can be prepared by processes known to those skilled in the art. For example, that can be prepared by processes known to those skilled in the art. For example, that can be prepared by processes known to those skilled in the art. For example, that can
• Diene polymer A and polymer B separated from each other by anionic polymerization be produced in organic solvent with subsequent addition of functionalizing reagents. Then, the two reaction solutions are combined and worked up together to form a rubber blend without solvent (removal of solvent, for example by distillation or vacuum evaporation), so that a readily transportable and processable blend is obtained.
• the high molecular weight, solution-polymerized diene polymer A is functionalized. This further improves the processability and the positive influence on the properties of resulting rubber mixtures.
• the polymers A or B are functionalized with a wide variety of groups. It may be z.
• R 1 , R 2 , R 3 in the structures may be the same or different and may be selected from linear or branched alkoxy, cycloalkoxy, alkyl, cycloalkyl or aryl groups having 1 to 20 carbon atoms, and wherein the functionalization according to formula I) is attached directly or via a bridge to the polymer chain of the polymer and wherein the bridge of a saturated or unsaturated
• Carbon chain which may also contain cyclic and / or aliphatic and / or aromatic elements and heteroatoms in or on the chain.
• the radicals R 1 , R 2 , R 3 are preferably alkoxy groups, for. B. ethoxy groups. If the structure I) is bound to the polymer via a bridge, it may, for example, be. B. to connect a following structure II) act
• At least one of the polymers A or B at the chain end with an amino-containing alkoxysilyl group and at least one further amino group and / or at least one further alkoxysilyl group and / or at least one other Amino group-containing alkoxysilyl group is functionalized, wherein the amino groups are bonded with or without spacer to the chain end of the polymer chain.
• Silane-sulfide groups in the context of the present invention are organic radicals which contain at least one sulfur atom and at least one substituted silyl group -SiR 3 .
• Rolling resistance indicators and / or improved abrasion behavior and / or tear properties and / or improved handling predictors such as
• Polymers functionalized with silane-sulfide groups are disclosed, for example, in EP 2 853 558 A1. They can be obtained by anionic polymerization in the presence of a silane-sulfide functionalization reagent.
• a silane-sulfide functionalizing reagent z.
• B. (MeO) 2 (Me) Si (CH 2 ) 2 -S-SiMe 2 C (Me) 3 , (MeO) 2 (Me) Si- (CH2) 2-S-SiMe2C (Me) 3 or (MeO) 3 Si- (CH 2) 2 -S-SiMe 2 C (Me) are used.
• Siloxane group is functionalized.
• Such siloxane groups are disclosed, for example, in WO 2009077295 A1 and WO 2009077296 A1.
• Polymers A or B a coupling center. These coupling centers may be z. B. tin (Sn) or silicon (Si) act.
• the rubber blend has from 5 to 100 phr (based on the at least one high molecular weight, solution-polymerized diene polymer A) of the at least one low molecular weight solution-polymerized polymer B. So he can
• the processing performance can be further improved by having the rubber blend for the rubber blend having a Mooney viscosity (ML 1 + 4, 100 ° C according to ASTM-D 1646) of 40 to 100 Mooney units.
• Mooney viscosity ML 1 + 4, 100 ° C according to ASTM-D 1646
• the sulfur-crosslinkable rubber mixture according to the invention having the improved winter properties and / or abrasion properties and / or
• the vulcanization system contains at least one accelerator and elemental sulfur and / or at least one sulfur donating substance, wherein the molar ratio of accelerator to sulfur (accelerator / sulfur ratio) is 0.18 to 5, preferably 0.18 to 2, is. Such a vulcanization system is also considered efficient
• Vulcanization system called.
• the molar amount of accelerator compared to the amount of sulfur is comparatively high and form predominantly monosulfidic sulfur bridges between the polymer chains in the networking.
• the accelerator is selected from the group consisting of thiazole accelerators and / or mercapto accelerators and / or sulfenamide accelerators and / or
• Guanidine accelerators and / or xanthate accelerators are examples of Guanidine accelerators and / or xanthate accelerators.
• sulfenamide Beschleumgers which is selected from the group consisting of N-cyclohexyl-2-benzothiazolsufenamid (CBS) and / or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and / or benzothiazyl-2-sulfenmorpholid ( MBS) and / or N-tert-butyl-2-benzothiazyl sulfenamide (TBBS).
• CBS N-cyclohexyl-2-benzothiazolsufenamid
• DCBS N-dicyclohexylbenzothiazole-2-sulfenamide
• MBS benzothiazyl-2-sulfenmorpholid
• TBBS N-tert-butyl-2-benzothiazyl sulfenamide
• Rubber mixture usually added as a powder or granules.
• Sulfur-donating substances containing crosslinking agents that deliver sulfur to the network are known to those skilled in the art or z. B. in Hofmann & Gupta: Handbook of Rubber Technology, Gupta- Verlag (2001), Chapter 7 described. Sulfur donating substances are also referred to as sulfur donors or sulfur donors.
• the sulfur-donating substance is preferably selected from the group comprising e.g. Thiuram disulfides, e.g. Tetrabenzylthiuram disulfide (TBzTD) and / or tetramethylthiuram disulfide (TMTD) and / or tetramethylthiuram monosulfide (TMTM) and / or tetraethylthiuram disulfide (TETD), and / or thiuramate tetrasulfides, e.g.
• DPTT Dipentamethylene thiuram tetrasulfide
• 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 and / or
• TESPT 3,3'-bis (triethoxysilylpropyl) tetrasulfide
• the sulfur-donating substance can therefore also be a sulfur-donating
• z. B. TBzTD releases two sulfur atoms that participate in the vulcanization.
• TBzTD as a sulfur-donating accelerator, it is possible in a low-sulfur rubber mixture (very small amounts, ⁇ 0.3 phr, with added elemental / free sulfur) or in a rubber mixture without added free sulfur, to have a predominantly monosulfidic network, ie an efficient network for vulcanization adjust.
• the rubber mixture contains one or more sulfidic silanes, only these, when calculating the molar ratio of accelerator to sulfur, are included in the total moles of sulfur that can release sulfur atoms. That's how it counts disulfide silanes TESPD (3,3'-bis (triethoxysilylpropyl) disulfide) in the context of the invention not as sulfur-donating substance, which in the calculation of the
• tetrasulfidic silane TESPT (3,3'-bis (triethoxysilylpropyl) tetrasulfide) gives, as known to those skilled in the art, two sulfur atoms and is therefore included in the calculation of the molar ratio.
• the added amount of accelerator is between 1.5 and 10 phr and the amount of elemental sulfur between 0.3 and 1 phr, preferably 0.4 to 0.9 phr , more preferably 0.5 to 0.85 phr.
• all accelerators added as accelerators enter the molar ratio of accelerator to sulfur and the sum of all amounts of added accelerators is between 2 and 10 phr.
• the vulcanization system contains a guanidine accelerator and a further accelerator and elemental sulfur.
• the added amounts of the guanidine accelerator and of the further accelerator are between 2 and 10 phr, preferably between 2 and 8 phr, more preferably between 3 and 8 phr.
• the vulcanization system contains 0 to 3 phr, but at least 0.1 phr of DPG (diphenylguanidine) and 1.5 to 7 phr of the further accelerator. In a preferred embodiment, it is in the other
• the cure system contains 1.0 to 2.5 phr of DPG and 1.5 to 7 phr of TBBS and 0.4 to 0.9 phr of elemental sulfur. In another preferred embodiment, the cure system contains 1.0 to 2.5 phr of DPG and 2.5 to 7 phr of CBS and 0.5 to 0.8 phr of elemental sulfur.
• the rubber mixture may contain other rubbers in addition to the special rubber blend.
• These further rubbers may be selected from the group consisting of natural polyisoprene, synthetic polyisoprene, butadiene rubber,
• solution-polymerized styrene-butadiene rubber emulsion-polymerized styrene-butadiene rubber, halobutyl rubber, polynorbornene, isoprene-isobutylene copolymer, ethylene-propylene-diene rubber, nitrile rubber, chloroprene rubber, acrylate rubber, fluororubber, silicone rubber, polysulfide rubber,
• the further rubbers are preferably at least one
• the at least one diene rubber is selected from the group consisting of synthetic polyisoprene (IR) and natural polyisoprene (NR) and styrene-butadiene rubber (SBR) and polybutadiene (BR).
• IR synthetic polyisoprene
• NR natural polyisoprene
• SBR styrene-butadiene rubber
• BR polybutadiene
• the natural and / or synthetic polyisoprene of all embodiments may be both cis-1,4-polyisoprene and 3,4-polyisoprene.
• Polymerization in solution can be obtained with Ziegler-Natta catalysts or using finely divided lithium alkyls. On the other hand it concerns with
• Natural rubber is greater than 99% by weight.
• Li-BR lithium-catalyzed butadiene rubber
• With a high-cis BR are particularly good Abriebeigenschaften and a low hysteresis of
• the styrene-butadiene rubber as a further rubber can be both solution-polymerized styrene-butadiene rubber (SSBR) and
• ESBR emulsion-polymerized styrene-butadiene rubber
• SSBR styrene-butadiene rubber
• ESBR emulsion-polymerized styrene-butadiene rubber
• Rubber mixture at least 50 phr based on the total amount in the
• Rubber mixture existing solid rubbers which - as already mentioned above, the low molecular weight polymer B is not included in the determination of the hundred rubber parts for the phr base.
• the rubber mixture may contain as filler up to 300 phr of silica,
• silica present may be those known to those skilled in the art
• Silicic acid types which are usually suitable as a filler for tire rubber mixtures act.
• a finely divided, precipitated silica is used, the nitrogen surface (BET surface area) (according to DIN ISO 9277 and DIN 66132) of 35 to 400 m7g, preferably from 35 to 350 m7g, particularly preferred from 100 to 320 m 2 / g and most preferably from 120 to 235 m 2 / g, and a CTAB surface area (according to ASTM D 3765) of 30 to 400 m7g, preferably from 50 to 330 m 2 / g, particularly preferred from 100 to 300 m 2 / g and most preferably from 110 to 230 m 2 / g.
• Such silicas lead z. B. in rubber mixtures for tire tread to particularly good physical properties of the vulcanizates.
• silicas can thus z. B. both those of the type Ultrasil ® VN3 (trade name) from Evonik and highly dispersible silicas, so-called HD silicas (eg., Zeosil ® 1165 MP from Solvay) are used.
• the rubber mixture may contain further fillers known to those skilled in conventional amounts. This can be soot or others
• Fillers such as alumo silicates, kaolin, chalk, starch, magnesia, titania, rubber gels, fibers (such as aramid fibers, glass fibers,
• Suitable carbon blacks are all types of carbon black known to those skilled in the art.
• the carbon black has an iodine value, according to ASTM D 1510, which is also referred to as Jodadsorptionskohl between 30 g / kg and 250 g / kg, preferably 30 to 180 g / kg, particularly preferably 40 to 180 g / kg, and most preferably 40 to 130 g / kg, and a DBP number according to ASTM D 2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100g, more preferably 90 to 200 ml / 100g.
• ASTM D 1510 which is also referred to as Jodadsorptionsiere between 30 g / kg and 250 g / kg, preferably 30 to 180 g / kg, particularly preferably 40 to 180 g / kg, and most preferably 40 to 130 g / kg
• a DBP number according to ASTM D 2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100g, more preferably 90 to 200 ml
• the DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light filler by means of dibutyl phthalate.
• Vehicle tires ensures the best possible compromise between abrasion resistance and heat build-up, which in turn affects the ecologically relevant rolling resistance.
• the rubber mixture contains 0.1 to 20 phr of carbon black. With these low amounts of soot, it was possible to achieve the best tire performance in terms of rolling resistance and wet grip.
• silica and other optional polar fillers to diene rubber silane coupling agents can be used in rubber mixtures.
• one or more different silane coupling agents can be used in combination with each other.
• the rubber mixture may thus contain a mixture of different silanes.
• the 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 optionally after cleavage a chemical reaction with the double bonds of Polymers can enter.
• a chemical reaction with the double bonds of Polymers can enter.
• 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 coupling agent 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. B. silanes which are sold under the name NXT in various variants by the company Momentive, USA, or those sold under the name VP Si 363 ® by Evonik Industries.
• the rubber mixture contains a 3,3'-bis (triethoxysilylpropyl) polysulfide having 2 to 8 sulfur atoms as silane, preferably a mixture with 70 to 80 wt .-% of 3,3'-bis (triethoxysilylpropyl) disulfide.
• Rubber mixture at least one blocked and / or unblocked mercaptosilane.
• Unblocked mercaptosilanes are to be understood as meaning silanes which have an -SH group, ie a hydrogen atom on the sulfur atom.
• Blocked mercaptosilanes are silanes which have an S-SG group, SG being the abbreviation for a protecting group on the sulfur atom.
• Preferred protecting groups are acyl groups.
• the blocked mercaptosilane used is preferably 3-octanoylthio-1-propyltriethoxysilane.
• the amount of the coupling agent is preferably 0.1 to 20 phf, more preferably 1 to 15 phf.
• the term phf (parts per hundred parts of filament by weight) used in this document is the quantity used in the rubber industry for
• Coupling agents for fillers In the context of the present application, phf refers to the available silicic acid, which means that other possible fillers such as carbon black are not included in the calculation of the amount of silane.
• the rubber mixture may contain further activators and / or agents for the binding of fillers, in particular carbon black. This can happen
• Aminopropyl) thiosulphuric acid and / or their metal salts resulting in very good physical properties of the rubber mixture, in particular when combined with at least one carbon black as filler.
• the silanes and activators mentioned are preferably added in at least one basic mixing stage in the preparation of the rubber mixture.
• the rubber mixture according to the invention may contain up to 150 phr, preferably 80 phr, of at least one plasticizer.
• plasticizers used in the present invention include all known in the art plasticizers such as aromatic, naphthenic or
• paraffinic mineral oil plasticizers such as. 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 at polycyclic aromatics of less than 3 wt .-% according to method IP 346 or rapeseed oil or factitious or plasticizer resins or other liquid polymers other than polymer B.
• the plasticizer (s) are preferably added in at least one basic mixing stage in the preparation of the rubber composition of the invention.
• the rubber mixture according to the invention may contain customary additives in customary parts by weight. These additives include a) 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), N, N'-bis (l, 4-dimethylpentyl) - p-phenylenediamine (77PD) b) activators, such as. Zinc oxide and fatty acids (eg stearic acid),
• B. 2,2'-Dibenzamidodiphenyldisulfid (DBD and f) processing aids such as.
• the rubber mixture according to the invention when using the rubber composition according to the invention for the inner components of a tire or a technical rubber article, which have direct contact with existing reinforcements, the rubber mixture is usually added to a suitable adhesive system, often in the form of adhesive resins.
• 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 conventionally used zinc oxide usually has a BET surface area of less than 10 m 2 / g. However, it is also possible to use so-called nano-zinc oxide having a BET surface area of 10 to 60 m 2 / g.
• the vulcanization is carried out in the presence of the vulcanization system according to claim 1.
• the preparation of the sulfur-crosslinkable rubber mixture according to the invention is carried out according to the usual method in the rubber industry, in which first in one or more mixing stages, a base mixture with all components except the Vulkanisationssystem (sulfur and vulcanization-influencing substances) is produced. By adding the vulcanization system in a final mixing stage, the finished mixture is produced. The finished mixture is z. B. further processed by an extrusion process and brought into the appropriate shape. Subsequently, the further processing by vulcanization, wherein due to the added in the context of the present invention Vulkanisationssystems sulfur crosslinking takes place.
• Vulkanisationssystem sulfur and vulcanization-influencing substances
• the rubber compound can be used for a wide variety of rubber goods, such as bellows,
• Conveyor belts air springs, belts, straps, hoses or soles are used.
• the rubber mixture is preferably used in vehicle tires, including pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, car and two-wheeled tires are to be understood.
• vehicle tires including pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction vehicles, truck, car and two-wheeled tires are to be understood.
• the rubber mixture according to the invention can be used in different components of vehicle tires, in particular pneumatic vehicle tires. It may be z. B. act around the side wall, the horn profile and inner tire components.
• the rubber mixture is preferably used for the part of the tread of a vehicle tire which comes into contact with the roadway. This results in tires that are characterized by improved winter properties and / or Abriebeigenschaften and / or rolling resistance properties, without affecting the wet grip properties.
• the tread may consist entirely or only partly of the rubber mixture.
• the tread may have a cap / base construction, with only the cap or base being made of the rubber composition of claim 1.
• cap in the context of the present invention refers to the part of the tread which comes into contact with the roadway and which is arranged radially outward (tread cap or tread cap).
• Base in the context of the present invention is understood to mean the part of the tread which is disposed radially inward, and Thus, when driving or not at the end of the tire life comes into contact with the road (tread base or LaustNeillbase).
• the rubber mixture according to the invention is also suitable for treads, which are arranged from different side by side and / or one below the other
• the mixture is extruded in the form of the desired component and applied to the green tire by known methods. It is also possible that the component by winding a narrow
• Rubber mix strip is produced. Afterwards, the tire is vulcanised under normal conditions.
• the copolymerization was carried out in a double-walled 40 L steel reactor which, prior to the addition of the organic solvent, the monomers, the polar
• Coordinator compound, initiator compound and other components were purged with nitrogen.
• the following components were added in the order listed: cyclohexane solvent (18,560 g), butadiene monomer (1,777 g), styrene monomer (448 g) and tetramethylethylenediamine (TMEDA, 1.0 g) and the mixture was adjusted to 40 C., followed by titration with n-butyllithium to remove traces of moisture or other contaminants.
• n-BuLi 14.08 mmol
• the polymerization was carried out for 20 minutes while the polymerization temperature was allowed to rise to not higher than 70 ° C.
• butadiene (1.202 g) and styrene (91 g) were added as monomers over 55 minutes.
• the polymerization was for for another 20 minutes, followed by the addition of 63 g of butadiene monomer.
• the polymerization was stopped by addition of hexamethylcyclotrisiloxane (D3) for functionalization (0.5 equivalent based on the initiator).
• D3 hexamethylcyclotrisiloxane
• the resulting polymer is functionalized siloxane groups.
• the polymer solution was 0.25 wt .-% IRGANOX ® 1520, BASF, based on the total weight of monomer, is added as a stabilizer. This mixture was stirred for 10 minutes.
• Hexamethylcyclotrisiloxan (D3) terminated the polymerization reaction by addition of methanol.
• the copolymerization was carried out in a jacketed 5 L steel reactor which, prior to the addition of the organic solvent, the monomers, the polar
• Coordinator compound, initiator compound and other components were purged with nitrogen.
• the following components were added in the order listed: cyclohexane solvent (3000g), tetrahydrofuran (45g), butadiene monomer (375g), styrene monomer (125g), and the mixture was heated to 25 ° C, followed by titration with n-butyllithium to remove traces of moisture or other impurities.
• n-BuLi (5.6 g) was added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 15 minutes, during which the polymerization temperature was allowed to rise to not higher than 70 ° C. After 15 minutes, the polymerization was terminated by the addition of
• Hexamethylcyclotrisiloxane (D3) terminated for functionalization (0.5 equivalent based on the initiator).
• the resulting polymer is functionalized siloxane groups.
• the copolymerization was carried out in a double-walled 40 L steel reactor which, prior to the addition of the organic solvent, the monomers, the polar
• Coordinator compound, initiator compound and other components were purged with nitrogen.
• the following components were added in the order listed: cyclohexane solvent (18,560 g), butadiene monomer (1,412 g), styrene monomer (507 g) and tetramethylethylenediamine (TMEDA, 7.8 g) and the mixture was adjusted to 40 C., followed by titration with n-butyllithium to remove traces of moisture or other contaminants.
• n-BuLi (8.32 mmol) was added to the polymerization reactor to start the polymerization reaction.
• the polymerization was terminated by addition of methanol.
• the resulting polymer is functionalized silanesulfide groups.
• the polymer solution was 0.25 wt .-% IRGANOX ® 1520, BASF, based on the total weight of monomer, is added as a stabilizer. This mixture was stirred for 10 minutes.
• Coordinator compound, initiator compound and other components were purged with nitrogen.
• the following components were added in the order listed: cyclohexane solvent (3000 g), 2,2-ditetrahydrofurylpropane (1.05 g), butadiene monomer (409 g), and the mixture was heated to 40 ° C, followed by titration with n-butyllithium to remove traces of moisture or others
• n-BuLi (5.2 g) was used to start the polymerization reaction in the Polymerization added. The polymerization was carried out for 15 minutes, during which the polymerization temperature was allowed to rise to not higher than 70 ° C. After 15 minutes, the polymer was terminated by the addition of 3-tert-butyldimethylsilylthiopropyl methoxydimethylsilane for functionalization (0.97 equivalents based on the initiator). After 60 minutes, the remaining living polymer chains are terminated by the addition of methanol. The resulting polymer is functionalized silanesulfide groups. To the polymer solution 0.25 wt .-% IRGANOX ® 1520, BASF based on the total monomer weight, was added as a stabilizer. This mixture was stirred for 10 minutes.
• the copolymerization was carried out in a jacketed 5 L steel reactor which, prior to the addition of the organic solvent, the monomers, the polar
• Coordinator compound, initiator compound and other components were purged with nitrogen.
• the following components were added in the order listed: cyclohexane solvent (3000g), tetrahydrofuran (45g), butadiene monomer (400g), styrene monomer (100g), and the mixture was heated to 25 ° C, followed by titration with n-butyllithium to remove traces of moisture or other impurities.
• n-BuLi (5.7 g) was added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 15 minutes, during which the polymerization temperature was allowed to rise to not higher than 70 ° C.
• the polymer was quenched by the addition of 3-tert-butyldimethylsilylthiopropylmethoxydimethylsilane for functionalization (0.97 equivalents based on the initiator). After 60 minutes, the remaining living polymer chains are terminated by the addition of methanol. The resulting polymer is functionalized silanesulfide groups.
• the polymer solution was 0.25 wt .-% IRGANOX ® 1520, BASF based on the total monomer weight, added as a stabilizer. This mixture was stirred for 10 minutes.
• Table 1 lists the analytical data of polymers A to D.
• Table 2a lists the names of the various blends produced.
• E denotes blends according to the invention, V denotes the corresponding blends
• Table 2 a shows the Mooney viscosities of the respective blends in MU (Mooney units) as the analytical index.
• the high filler rubber blends of Table 3 were prepared with the rubber blend V of the non-functionalized polymers Al and Bl and the rubber blends E1 to E-3 of the present invention having a cure system consisting of accelerator and elemental sulfur and a cure system consisting of accelerator, elemental sulfur and a sulfur-donating substance as comparison mixtures VI to V5. Furthermore, the rubber mixtures according to the invention are El to E3 with the special
• ABS wet braking behavior was determined by the braking distance of 80 km / h on a wet road.
• ABS dry braking performance was determined by the braking distance from 100 km / h on dry roads.
• the rolling resistance corresponds to the rolling resistance force measured on the corresponding machine at 90 km / h.
• the values for the abrasion represent the weight loss of the tire after 10,000 kilometers traveled.
• the snow traction i. H. determines the traction force during an acceleration ride on a snow track.
• Rubber blends in combination with a vulcanization system consisting of an accelerator, elemental sulfur and a sulfur-donating substance a significant improvement in terms of rolling resistance and in particular the
• Abrasion properties is achieved without negative wet braking properties winter properties and dry braking properties remain virtually unchanged.
• the rubber blends of Table 5 were prepared.
• the mixtures V6 to VI 1 contain a vulcanization system of accelerator and elemental sulfur, while the mixtures VI 2, VI 3 and E4 to E7 have accelerator, sulfur and a sulfur-donating substance.
• Mixture preparation was carried out under customary conditions to produce a masterbatch and then the
• test specimens were produced by optimal vulcanization under pressure at 160 ° C and determined with these specimens typical for the rubber industry material properties with the following test methods.
• Abrasion mm 3 138 149 119 131 152 155 131 139 104 112 120 125 b SBR, Sprintan ® SLR-4602, Fa Trinseo, vinyl content. 63 wt .-%, styrene content: 21 wt .-%, functionalized

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• 2017
  • 2017-08-14 US US16/325,728 patent/US20210363333A1/en not_active Abandoned
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