Vulcanizable rubber mixture, vulcanized rubber and rubber product

Abstract

The invention relates to a vulcanizable rubber compound comprising a) a diene rubber, b) silica, c) a specific polyetheramine in a combined part by weight in the range of 0.1 to 10 phr, and d) a specific organosilicon compound.

Description

Field of the Invention

[0001] The present invention relates to a vulcanizable rubber compound, to a vulcanized rubber producible therefrom, and to a rubber product, in particular a pneumatic vehicle tire, containing the vulcanized rubber. Background Art

[0002] The automotive industry has been facing fundamental challenges since the beginning of the 21st century and has been defined by numerous technological innovations. The increasing awareness of consumers regarding environmental issues such as emission characteristics and resource efficiency requires new mobility concepts. At the same time, the demand for improved vehicle characteristics and requirements related to driving safety are increasing. Meeting these challenges is not only the task of vehicle manufacturers. In practice, many of these issues are significantly influenced by the characteristics of vehicle tires, and thus the optimization of tire characteristics is an important area of innovation.

[0003] The main components for optimizing the characteristics of vehicle tires and other rubber products such as belts, conveyor belts, and hoses are the vulcanizable rubber compounds used for production and the rubber materials obtained therefrom by vulcanization. Many relevant characteristics of pneumatic vehicle tires, such as wet grip, rolling resistance, and wear behavior, are closely related to the composition of the rubber material of, for example, the tread. Therefore, much research work has focused on optimizing the characteristics of the rubber compositions used, which are often subject to very high requirements. At the same time, there are target conflicts regarding many characteristics of vehicle tires, which means that these characteristics cannot be optimized independently of each other and that the improvement of one parameter may lead to the deterioration of another parameter.

[0004] In recent decades, significant progress has been made in the field of composition development. The key innovations here are, for example, the at least partial replacement of carbon black fillers with silicon-containing compounds, in particular silica compounds such as fumed silica or precipitated silica.

[0005] EP 2725059 A1 discloses that the combination of polyetheramines and silica can result in advantageous rubber compounds that particularly have an improved performance level with respect to wear behavior and the target conflict between rolling resistance and wet grip. In addition, it was found that improved processing characteristics can be obtained in the corresponding rubber compounds. Further information regarding the technical background of polyetheramines is disclosed, for example, in WO 2013 / 092526 A1, US 2008 / 033082A1, and WO2016 / 030469 A1.

[0006] Although vulcanizable rubber compounds known from the prior art can achieve generally advantageous results in many respects, in many cases the corresponding compositions and the vulcanized rubber that can be produced therefrom are still considered to require improvement in terms of application-related properties, especially in order to meet the requirements for high-performance applications of modern pneumatic vehicle tires. Summary of the Invention

[0007] The main object of the present invention is to overcome or at least reduce the disadvantages of the prior art and to provide a vulcanizable rubber compound and a corresponding vulcanized rubber producible therefrom having an advantageous property profile.

[0008] In particular, the object of the present invention is to provide a vulcanizable rubber compound having excellent processing properties, and it is desirable to reduce the need for compounds that are potentially harmful to health and / or the environment (especially guanidine accelerators).

[0009] Furthermore, the object of the present invention is to provide a vulcanizable rubber compound and a corresponding vulcanized rubber producible therefrom having excellent rolling properties, especially a favorable rolling resistance.

[0010] Furthermore, the object of the present invention is to provide a vulcanizable rubber compound and a corresponding vulcanized rubber producible therefrom, which vulcanized rubbers have excellent mechanical properties, especially in terms of improved durability and improved tear properties, especially also in terms of improved tear properties on rough roads.

[0011] In particular, the object of the present invention is to optimally resolve the existing objective conflict between processing properties, mechanical properties, and rolling properties.

[0012] In this regard, another object of the present invention is that the vulcanizable rubber compound and the vulcanized rubber to be provided should be producible as far as possible using production methods and materials that are already used in the rubber processing field today.

[0013] Another object of the present invention is to provide corresponding rubber products, especially pneumatic vehicle tires having advantageous properties, comprising the vulcanized rubber to be provided.

[0014] The inventors of the present invention have now surprisingly found that when a vulcanizable rubber compound, as defined in the claims, contains not only a diene rubber and silica, but also specific parts by weight of specific polyetheramines and organosilicon compounds, the above objects can be achieved.

[0015] Therefore, the above objects are achieved by the subject matter of the present invention as defined in the claims. Preferred embodiments of the present invention will become apparent from the dependent claims and the following discussion.

[0016] In a particularly preferred embodiment, the features of what are hereinafter referred to as the preferred embodiments are combined with the features of other embodiments that are also referred to as preferred. Accordingly, combinations of two or more of the embodiments hereinafter referred to as particularly preferred embodiments are most particularly preferred. Embodiments in which the features of one embodiment that is referred to as being preferred to some extent are combined with one or more further features of other embodiments that are referred to as being preferred to some extent are likewise preferred. The features of the preferred vulcanizable rubber compounds, rubber products and uses will become apparent from the features of the preferred vulcanizable rubber blends.

[0017] In the following text, in cases where specific amounts / parts of a blend component (such as a diene rubber or a polyetheramine) are disclosed not only for the blend component, but also preferred embodiments of the blend component are disclosed, the text also discloses in particular the specific amounts / parts of the blend components of these preferred embodiments. In addition, it is disclosed that in the case of the respective specific total amounts / total parts of the blend components, at least some of these blend components can be of preferred embodiments, and in particular it is also disclosed that the blend components of the preferred embodiments can in turn be present in these specific amounts / parts within these specific total amounts or total parts.

[0018] The present invention relates to a vulcanizable rubber blend comprising:

[0019] a) one or more diene rubbers,

[0020] b) one or more fillers selected from the group consisting of silica,

[0021] c) one or more polyetheramines in a combined weight part range of from 0.1 to 10 phr,

[0022] These polyetheramines are selected from the group consisting of polyetheramines having the formula I):

[0023] I) R 1 R 2 N-(R 5 ) m -X-R 6 -NR 3 R 4 ,

[0024] wherein R 1 、R 2 、R 3 and R 4 are each independently hydrogen or a branched or unbranched hydrocarbon group having 1 to 10 carbon atoms, where m is 0 or 1, and wherein R 5 and R 6 are each independently a branched or unbranched hydrocarbon chain having 1 to 10 carbon atoms,

[0025] wherein X is a polyether chain of formula II):

[0026] II)-(CHR 7i -CHR 8i -O) x -

[0027] where x is in the range from 2 to 30, and wherein in each monomer unit i, R 7i and R 8i are each independently, in each case and independently of the other monomer units in the polyether chain, hydrogen or a hydrocarbon group having 1 or 2 carbon atoms, and

[0028] d) one or more organosilicon compounds selected from the group consisting of organosilicon compounds having formula III):

[0029] III)(R a R b R c )Si-Y-S-(C═O)-Z,

[0030] wherein the R a -, R b - and R c groups are each independently a straight-chain or branched organic group having 1 to 20 non-hydrogen atoms, and at least one of the R a -, R b - and R c groups is an organic group bonded to the Si atom via an oxygen atom, where Y is a straight-chain or branched organic linking unit having 3 to 30 non-hydrogen atoms, the number of non-hydrogen atoms in the linking chain between the Si atom and the S atom is 3 or more, and wherein Z is a straight-chain or branched organic group having 1 to 20 non-hydrogen atoms.

[0031] The vulcanizable rubber compound itself, its typical components, and also the customary production methods for obtaining the corresponding vulcanizable rubber compound (in particular by mixing these components) are well known to those skilled in the rubber processing art.

[0032] According to standard practice, the above-defined components of the vulcanizable rubber compound are each used in the form of "one or more". As is customary in the industry, the expression "one or more" refers to the chemical nature of the corresponding compound, not to its molar amount. For example, the vulcanizable rubber compound may contain only SBR as the diene rubber, which would mean that the vulcanizable rubber compound contains a large number of the corresponding molecules.

[0033] In the following text, where weight parts are indicated, as is customary in industry, they are in many cases indicated in the form of the combined weight parts of the one or more components, such that the added weight parts of the correspondingly formed components meet the respective criteria.

[0034] The measure phr (parts per hundred parts of rubber by weight) used herein is the customary representation of the amounts used in the formulation of rubber compounds in the rubber industry and indicates the parts by weight of the components in a rubber compound based on the weight of the high molecular weight rubber present in the rubber compound (weight average molar mass Mw determined by GPC greater than 60,000 g / mol), where the combined weight parts of the high molecular weight rubber in the rubber compound correspond to 100 phr. Similarly, the measure phf (parts per hundred parts of filler by weight) is the customary representation of the amount, particularly for coupling agents for fillers, based on the weight of the filler present in the rubber compound in the rubber industry. In the context of the present invention, the measure phf is based only on the silica present in the vulcanizable rubber compound, and the combined weight parts of this silica correspond to 100 phf, which means that other fillers that may be present (such as carbon black) are not included in the calculation of phf.

[0035] The vulcanizable rubber blend according to the invention comprises at least one diene rubber. As understood by those skilled in the art, a diene rubber refers to a rubber obtained by (co)polymerization of a diene and / or a cycloolefin and thus having C═C double bonds in the main chain or in side groups. It can be considered an advantage of the vulcanizable rubber blend according to the invention that it has a high degree of flexibility with respect to the diene rubber to be used and thus, in principle, all diene rubbers customary in industry can be used. However, in this regard, according to the inventors, it is preferred for the vulcanizable rubber blend according to the invention that the one or more diene rubbers are selected from the group consisting of natural polyisoprene, synthetic polyisoprene, epoxidized polyisoprene, butadiene rubber, solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, polynorbornene, ethylene-propylene-diene rubber, nitrile rubber, acrylate rubber, styrene-isoprene-butadiene terpolymer, butyl rubber and halogenated butyl rubber, wherein the one or more diene rubbers are preferably selected from the group consisting of natural polyisoprene (NR), synthetic polyisoprene (IR), butadiene rubber (BR), solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), and wherein the one or more diene rubbers are particularly preferably selected from the group consisting of solution-polymerized styrene-butadiene rubber and emulsion-polymerized styrene-butadiene rubber. In this regard, additionally or alternatively, it is also preferred for the vulcanizable rubber blend according to the invention that at least one of these diene rubbers, preferably all of the one or more diene rubbers, is a terminally modified and / or chain-modified diene rubber, preferably a terminally modified diene rubber. The modification can be one or more functional groups selected from the group consisting of hydroxyl, ethoxy, epoxy, siloxane groups, amino, aminosiloxane groups, carboxyl, phthalocyanine groups and silane-sulfide groups.

[0036] In particular, it has been found that SBR, BR and IR / NR are suitable diene rubbers for obtaining a vulcanizable rubber blend that can be converted by vulcanization into a particularly effective vulcanized rubber.

[0037] Therefore, first of all, it is preferred for the vulcanizable rubber blend according to the invention that the vulcanizable rubber blend comprises styrene-butadiene rubber, preferably solution-polymerized styrene-butadiene rubber, as the diene rubber, preferably in an amount in the range of 50 to 98 phr, particularly preferably in the range of 55 to 96 phr, and most particularly preferably in the range of 60 to 90 phr.

[0038] Additionally or alternatively, it is preferred that the vulcanizable rubber blend according to the invention, wherein the vulcanizable rubber blend comprises a butadiene rubber as the diene rubber, preferably in an amount in the range of 1 to 35 phr, particularly preferably in the range of 2 to 30 phr, and most particularly preferably in the range of 5 to 25 phr. The butadiene rubber can be, for example, a so-called high-cis or low-cis butadiene rubber, and a high-cis butadiene rubber means a polybutadiene having a cis content of 90% or more based on mass.

[0039] Furthermore, additionally or alternatively, it is preferred that the vulcanizable rubber blend according to the invention, wherein the vulcanizable rubber blend comprises natural polyisoprene and / or synthetic polyisoprene, preferably natural polyisoprene as the diene rubber, preferably in a combined amount in the range of 1 to 30 phr, particularly preferably in the range of 2 to 20 phr, and most particularly preferably in the range of 5 to 15 phr. However, amounts in the range of 60 to 100 phr, preferably 60 to 80 phr, are also conceivable, especially for applications in truck tires, where, for example, a blend containing 100 phr of NR, 40 phr of silica, and 10 phr of carbon black exhibits particularly favorable tear properties. Natural polyisoprene and / or synthetic polyisoprene can be cis-1,4-polyisoprene or 3,4-polyisoprene. However, it is preferred to use cis-1,4-polyisoprene, especially cis-1,4-polyisoprene having a cis-1,4 content of 90% or more based on mass.

[0040] In order to optimally adapt the physicochemical / mechanical properties of the producible vulcanized rubber to specific application requirements, it has been found advantageous to mix two or more diene rubbers together. Thus, it is preferred that the vulcanizable rubber blend according to the invention, wherein the vulcanizable rubber blend comprises two or more, preferably three or more, different diene rubbers as the diene rubber, and the vulcanizable rubber blend particularly preferably comprises SBR and NR and / or BR, most particularly preferably SBR, NR, and BR.

[0041] Additionally or alternatively, it is preferred that the vulcanizable rubber blend according to the invention, wherein the one or more diene rubbers have a weight-average molar mass Mw measured by GPC in the range of 150,000 to 5,000,000 g / mol, preferably in the range of 250,000 to 2,500,000, and particularly preferably in the range of 300,000 to 1,500,000. In the context of the present invention, the determination of the number-average or weight-average molar mass is carried out by gel permeation chromatography (GPC using tetrahydrofuran as the eluent and polystyrene standards; size exclusion chromatography) according to DIN 55672-1:2016-03.

[0042] The vulcanizable rubber compound according to the invention comprises one or more fillers selected from the group consisting of silica. In the context of the present invention, in the original German text of this application, the German terms customary in the industry were used [silicic acid], and related compounds are sometimes also referred to as "Silika" according to the English term "silica". For the person skilled in the rubber processing industry, this historically established German term refers to amorphous (i.e., non-crystalline) silica, in particular so-called fumed silica and precipitated silica. In other words, the vulcanizable rubber compound according to the invention is a rubber compound comprising one or more fillers selected from the group consisting of fumed silica and precipitated silica, particularly preferably precipitated silica.

[0043] Fundamentally preferred is the vulcanizable rubber compound according to the invention, wherein the one or more fillers have a nitrogen surface area (BET surface area) in the range from 35 to 400 m 2 / g, preferably in the range from 35 to 350 m 2 / g, particularly preferably in the range from 85 to 320 m 2 / g, and most particularly preferably in the range from 120 to 235 m 2 / g, according to DIN ISO 9277:2014-01. Additionally or alternatively, preferred is the vulcanizable rubber compound according to the invention, wherein the one or more fillers have a CTAB surface area in the range from 30 to 400 m 2 / g, preferably in the range from 30 to 330 m 2 / g, particularly preferably in the range from 80 to 300 m 2 / g, and most particularly preferably in the range from 115 to 200 m 2 / g, according to ASTM D 3765-03.

[0044] Regarding the amount of filler that can be used, the inventors have found that even with a high content of filler, the vulcanizable rubber compound according to the invention advantageously exhibits excellent results. However, according to the inventors, the solution determined in the context of the present invention exhibits the greatest advantages especially in the case of a medium filler content. Therefore, preferred is the vulcanizable rubber compound according to the invention, wherein the vulcanizable rubber compound comprises the one or more fillers in a combined weight portion in the range from 5 to 250 phr, preferably in the range from 20 to 180 phr, particularly preferably in the range from 30 to 140 phr, and most particularly preferably in the range from 40 to 110 phr.

[0045] In addition to the silica to be used according to the invention, additional fillers may additionally be present, thereby allowing for a specific adjustment of the properties of the vulcanizable rubber compound. Preferred is a vulcanizable rubber compound according to the invention, wherein the vulcanizable rubber compound comprises one or more additional fillers selected from the group consisting of carbon black, aluminum hydroxide, titanium dioxide, magnesium oxide and layered silicates, and the combined weight parts of these additional fillers are preferably in the range of 0.1 to 100 phr, and particularly preferably in the range of 0.5 to 50 phr. The carbon black used is preferably such that it has an iodine adsorption value according to ASTM D 1510 of 30 to 250 g / kg, preferably 30 to 180 g / kg, and particularly preferably 40 to 130 g / kg, and a DBP value according to ASTM D 2414 of 30 to 200 ml / 100 g, preferably 70 to 200 ml / 100 g, and particularly preferably 90 to 200 ml / 100 g.

[0046] The vulcanizable rubber compound according to the invention comprises at least one polyetheramine having a specific structure. Polyetheramines are well known to those skilled in the art. They are polyether polyols in which the terminal hydroxyl groups have been converted to amino groups in an amination reaction, thereby obtaining polyamines. In the case of aminating particularly preferred linear (i.e., unbranched) polyether diols, the polyetheramines are accordingly diamines of polyalkylene glycols. The polyether diols used as a basis are preferably prepared from alkylene oxides (such as butylene oxide, ethylene oxide or propylene oxide). Polyetheramines are commercially available, especially from Huntsman, for example, under the trade names Jeffamine D-230, ED-600, ED-900 or EDR-148.

[0047] The polyetheramine to be used according to the invention is selected from the group consisting of polyetheramines having the formula I):

[0048] I)R 1 R 2 N-(R 5 ) m -X-R 6 -NR 3 R 4 ,

[0049] wherein R 1 、R 2 、R 3 and R 4 are each independently hydrogen or a branched or unbranched hydrocarbon group having 1 to 10 carbon atoms, where m is 0 or 1, and wherein R 5 and R 6 are each independently a branched or unbranched hydrocarbon chain having 1 to 10 carbon atoms,

[0050] wherein X is a polyether chain having the formula II):

[0051] II)-(CHR 7i -CHR 8i -O) x -

[0052] wherein x ranges from 2 to 30, and wherein R in each monomer unit i 7i and R 8i are each independently, in each case, and independently of the other monomer units in the polyether chain, hydrogen or a hydrocarbon group having 1 or 2 carbon atoms.

[0053] R 1 、R 2 、R 3 and R 4 The organic groups define the groups of the amino groups of the diamine and are in particular produced by the substances used for the amination reaction. As understood by those skilled in the art, these groups are in principle independent of one another, which means that, for example, R 1 can be hydrogen, even if R 2 is a hydrocarbon group. In this regard, a preferred vulcanizable rubber compound according to the invention is one in which R 1 、R 2 、R 3 and R 4 are each independently hydrogen or a branched or unbranched, preferably unbranched, hydrocarbon group having 1 to 5 carbon atoms, preferably 2 to 5 carbon atoms. A particularly preferred vulcanizable rubber compound according to the invention is one in which at least one of the R 1 and R 2 groups and / or one of the R 3 and R 4 groups is hydrogen. Most particularly preferred is a vulcanizable rubber compound according to the invention in which the R 1 and R 3 groups and / or the R 2 and R 4 groups are the same. Particularly preferred is a vulcanizable rubber compound according to the invention in which the R 1 、R 2 、R 3 and R 4 groups are hydrogen.

[0054] One of these amino groups can be bonded directly (m = 0) or via a hydrocarbon chain (m = 1) to the polyether chain X. In the preferred polyetheramines, due to the preparation from alkylene oxides, one of these amino groups is bonded directly to the polyether chain X (m = 0), while the other amino group is bonded via an R 6 hydrocarbon chain, the R 6The hydrocarbon chain will ultimately be the last building block which is actually a polyether chain; however, this last building block no longer has an oxygen atom due to amination and thus can no longer be considered part of the polyether chain X. Thus, it is first preferred to have a vulcanizable rubber blend according to the invention, wherein R 5 and R 6 are each independently a branched or unbranched hydrocarbon chain having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. In this regard, it is particularly preferred to have a vulcanizable rubber blend according to the invention, wherein m = 0, wherein R 6 is preferably a branched or unbranched hydrocarbon chain having 2 or 3 carbon atoms, particularly preferably a branched or unbranched hydrocarbon chain having 3 carbon atoms.

[0055] The polyether chain X comprises x repeating units. It is preferred to have a vulcanizable rubber blend according to the invention, wherein x is in the range from 2 to 15.

[0056] In each unit of the polyether chain X, i.e., in the different monomer units identified herein by the sequential number i numbered accordingly from i = 1 to i = x, R 7i and R 8i are fundamentally independent of each other, specifically not only are R 7i and R 8i in each monomer unit fundamentally independent of each other, but also all R 7i and all R 8i in the polyether chain are fundamentally independent of each other. Due to the fundamental advantage of alkylene oxides having a relatively short chain length, it is preferred to have a vulcanizable rubber blend according to the invention, wherein R 7i and R 8i in each monomer unit i are each independently and independently of the other monomer units in the polyether chain hydrogen or methyl. It is particularly preferred to have a vulcanizable rubber blend according to the invention, wherein, in each monomer unit i, at least one of the R 7i and R 8i groups is hydrogen in each case.

[0057] In this regard, those skilled in the art will understand that the nature of the R 7i and R 8i groups depends in particular on the chemical nature of the compounds (especially the alkylene oxides used) used in the preparation of the polyetheramine, and in particular when different alkylene oxides are mixed together in the preparation of the polyetheramine, more complex polyetheramines can be obtained.

[0058] According to the inventors, it is preferred to have a vulcanizable rubber blend according to the invention, wherein the polyether chain comprises one or more first monomer units i1 having the formula (IV):

[0059] IV)-(CHR 7i -CH2-O)-,

[0060] wherein R 7i is preferably the same for all first monomer units i1, wherein R 7i is particularly preferably methyl for all first monomer units i1, and / or

[0061] wherein the polyether chain comprises one or more second monomer units i2 having the formula V):

[0062] V)-(CH2-CH2-O)-, and / or

[0063] wherein the polyether chain comprises one or more third monomer units i3 having the formula VI):

[0064] VI)-(CH2-CHR 8i -O)-,

[0065] wherein R 8i is preferably the same for all third monomer units i3, wherein R 8i is particularly preferably methyl for all third monomer units i3, and the polyether chain preferably consists of these monomer units.

[0066] Fundamentally preferred for these monomer units is the vulcanizable rubber blend according to the invention, wherein the number x1 of first monomer units i1 in the polyether chain is in the range from 1 to 7, preferably in the range from 2 to 6, and particularly preferably in the range from 2 to 5, and / or wherein the number x2 of second monomer units i2 in the polyether chain is in the range from 1 to 15, preferably in the range from 2 to 12, and particularly preferably in the range from 3 to 10, and / or wherein the number x3 of third monomer units i3 in the polyether chain is in the range from 1 to 7, preferably in the range from 2 to 6, and particularly preferably in the range from 2 to 5. In this regard, particularly preferred is the vulcanizable rubber blend according to the invention, wherein the combined number x 1 / 3 of first monomer units i1 and third monomer units i3 in the polyether chain is in the range from 2 to 10, preferably in the range from 3 to 7.

[0067] In this regard, most particularly preferred first is the vulcanizable rubber blend according to the invention, wherein the polyether chain consists of first monomer units i1 preferably to an extent of more than 50%, particularly preferably to an extent of more than 75%, and most particularly preferably substantially all, and the number x1 of first monomer units i1 in the polyether chain is in the range from 1 to 5, and preferably in the range from 2 to 4. A corresponding polyetheramine is commercially available, for example, under the trade name Jeffamine D-230, wherein x1 is about 2.5.

[0068] Additionally or alternatively, it is also particularly preferred to use a vulcanizable rubber compound according to the invention having a mixed polyether chain, i.e., wherein the polyether chain contains two or more, preferably three or more monomer units selected from the group consisting of a first monomer unit i1, a second monomer unit i2, and a third monomer unit i3, and the polyether chain preferably consists of these monomer units. Relevant for most applications is a vulcanizable rubber compound according to the invention, wherein at least some and preferably all of the two or more monomer units are randomly distributed in the polyether chain.

[0069] For a mixed polyether chain, first and most particularly preferred is a vulcanizable rubber compound according to the invention, wherein the combined number x of the first monomer unit i1 and the third monomer unit i3 in the polyether chain 1 / 3 is in the range of 2 to 5, and wherein the number x2 of the second monomer unit i2 in the polyether chain is in the range of 7 to 12. A corresponding polyetheramine is commercially available, for example, under the trade name Jeffamine ED-600, wherein x2 is about 9 and x 1 / 3 is about 3.6.

[0070] For a mixed polyether chain, additionally or alternatively, most particularly preferred is also a vulcanizable rubber compound according to the invention, wherein the combined number x of the first monomer unit i1 and the third monomer unit i3 in the polyether chain 1 / 3 is in the range of 4 to 8, and wherein the number x2 of the second monomer unit i2 in the polyether chain is in the range of 10 to 15. A corresponding polyetheramine is commercially available, for example, under the trade name Jeffamine ED-900, wherein x2 is about 12.5 and x 1 / 3 is about 6.

[0071] The inventors particularly believe that the use of such polyetheramines, of which typical representatives are the commercial products Jeffamine D-230 and ED-600, is preferred for achieving the object of the present invention.

[0072] Accordingly, particularly preferred is a vulcanizable rubber compound according to the invention, wherein the one or more polyetheramines are selected from the group consisting of:

[0073] - a polyetheramine having the formula VII):

[0074] VII) H2N-(CH(CH3)-CH2-O) x1 -CH2CH(CH3)-NH2,

[0075] wherein x1 is in the range of 2 to 6, preferably in the range of 2 to 5, particularly preferably in the range of 2 to 4, and most particularly preferably in the range of 2 to 3, and

[0076] - a polyetheramine having the formula VIII):

[0077] VIII) H2N-X-CH2CH(CH3)-NH2,

[0078] wherein X is a polyether chain composed of two or more monomer units selected from the group consisting of

[0079] a first monomer unit i having the formula IV b ): 1b :

[0080] IV b )-(CH(CH3)-CH2-O)-,

[0081] a second monomer unit i having the formula V b ): 2b :

[0082] V b )-(CH2-CH2-O)-, and

[0083] a third monomer unit i having the formula VI b ): 3b :

[0084] VI b )-(CH2-CH(CH3)-O)-,

[0085] wherein the combined number x of the first monomer unit i 1b and the third monomer unit i 3b in the polyether chain is in the range of 2 to 5, and the number x of the second monomer unit i 1b / 3b in the polyether chain is in the range of 8 to 10. 2b 2b Based on the preparation or preparability of the polyetheramine, it is also highly preferred to have a vulcanizable rubber compound according to the present invention, wherein the one or more polyetheramines are preparable by polymerization of an alkylene oxide followed by amination, and the alkylene oxide is preferably selected from the group consisting of butylene oxide, ethylene oxide, propylene oxide, and mixtures of these compounds (preferably propylene oxide). Additionally or alternatively, it is also particularly preferred to have a vulcanizable rubber compound according to the present invention, wherein the one or more polyetheramines are saturated compounds.

[0086]

[0087] ​​The preferably used polyetheramines are compounds having a relatively short chain length. Specifically, particularly preferred is a vulcanizable rubber blend according to the invention, wherein the one or more polyetheramines have a weight-average molar mass in the range from 100 to 800 g / mol, preferably in the range from 130 to 650 g / mol, and particularly preferably in the range from 190 to 400 g / mol.

[0088] In order to further optimize the properties of the vulcanizable rubber blends according to the invention and of the vulcanized rubbers producible therefrom, different polyetheramines can be combined, wherein combinations of polyetheramines, in particular, such as can be achieved, for example, by combining the commercial products Jeffamine D-230 and ED-600, are considered to be advantageous by the inventors. Accordingly, preferred is a vulcanizable rubber blend according to the invention, wherein the vulcanizable rubber blend comprises two or more different polyetheramines.

[0089] Regardless of the exact chemical nature of the polyetheramines, the inventors have successfully determined particularly advantageous parts by weight of these components, by means of which the abovementioned objects can be achieved particularly well. Specifically, preferred is a vulcanizable rubber blend according to the invention, wherein the vulcanizable rubber blend comprises the one or more polyetheramines in combined parts by weight in the range from 0.2 to 8 phr, and preferably in the range from 0.4 to 6 phr.

[0090] The vulcanizable rubber blend according to the invention further comprises one or more organosilicon compounds selected from the group consisting of organosilicon compounds having the formula III):

[0091] III)(R a R b R c )Si-Y-S-(C═O)-Z,

[0092] wherein the R a , R b and R c groups are each independently a straight-chain or branched organic group having from 1 to 20 non-hydrogen atoms, the organic group of at least one of the R a , R b and R c groups being bonded to the Si atom via an oxygen atom, where Y is a straight-chain or branched organic linking unit having from 3 to 30 non-hydrogen atoms, the number of non-hydrogen atoms in the linking chain between the Si atom and the S atom being 3 or more, and where Z is a straight-chain or branched organic group having from 1 to 20 non-hydrogen atoms.

[0093] In the above definitions, organic groups and organic linking units are defined. The term "organic" is clear to those skilled in the art and means that these units are or can be part of an organic molecule and in most cases means that these non-hydrogen atoms are selected from the group of non-metals. As understood by those skilled in the art, an organic group (e.g., -CH3) is attached to other components of a particular compound via one attachment point, and an organic linking unit (e.g., -CH2-CH2- or -CH2-CHR x -CH2-, where R x which in turn can be, for example, an organic group) is attached to other components of a particular compound via two attachment points.

[0094] The reference to "non-hydrogen atoms" in the organic groups and linking units is convenient for those skilled in the art and is familiar to them based on their common knowledge. Thus, it can be stated that the organic linking unit / organic group can not only be a pure hydrocarbon unit / hydrocarbon group, but usually also contain heteroatoms, which means that the organic linking unit / organic group also contains functional groups such as ester groups or ether groups. In this regard, those skilled in the art will automatically understand that in addition to the "non-hydrogen atoms" defined above, hydrogen atoms may of course also be present and will be present in the vast majority of cases. However, due to their monovalent nature, hydrogen atoms do not exist in the chain but fill the remaining valences on the "non-hydrogen atoms". As understood by those skilled in the art, the expression "an organic group having three non-hydrogen atoms" correspondingly means, for example, that the organic group contains three additional non-hydrogen atoms in addition to hydrogen atoms.

[0095] In this regard, as understood by those skilled in the art, for substantially all embodiments, it is preferred that the vulcanizable rubber blend according to the invention is such that the non-hydrogen atoms are selected from the group consisting of C, N, O, S, P, F, Cl and Br and preferably from the group consisting of C, N, O and S. It is clear to those skilled in the art that the definition of the organic chain / organic group results in implicit functional limitations, that is, they are of course groups / linking units having a constitution that does not conflict with any fundamental chemical principles, which means that the organic linking units defined above are not composed only of halides, for example.

[0096] According to the inventors, regardless of the specific embodiments of the silicone compound, first and preferably, the curable rubber blend according to the present invention, wherein the curable rubber blend comprises the one or more silicone compounds in a combined weight part range of from 1 to 30 phr, preferably in a range of from 2 to 20 phr, and particularly preferably in a range of from 5 to 15 phr. Based on the silica content, preferably, the curable rubber blend according to the present invention, wherein the curable rubber blend comprises the one or more silicone compounds in a combined weight part range of from 1 to 50 phf, preferably in a range of from 2 to 40 phf, and particularly preferably in a range of from 3 to 30 phf.

[0097] Those skilled in the art will understand that the role of the (R a R b R c )Si group is to bond with silica; possible embodiments of these groups are disclosed, for example, in WO 2019 / 105614 A1. The (R a R b R c )Si group can be quite flexible in the selection of the R a , R b and R c groups, provided that at least one of the R a , R b and R c groups has an organic group bonded to the Si atom via an oxygen atom. Thus, specific silicone compounds are organoalkoxysilyl organic compounds, which indicates to those skilled in the art that these silicone compounds are suitable for organosilanization. From the morpheme "organoalkoxysilyl", it can be seen that the corresponding silicone compound has at least one organic group bonded to the central Si atom of the (R a R b R c )Si group via an oxygen atom. The organoalkoxy group (such as an alkoxy group, such as ethoxy) is a leaving group, which can be released during the condensation reaction occurring at the filler surface, thereby generating an Si-O-Si linkage.

[0098] Even though it is fundamentally possible to use those in which the three R a , R b and R cOrganosilicon compounds in which two in the group are directly bonded to the central silicon via carbon atoms and thus have only one leaving group, but in practice organosilicon compounds having three (in most cases even identical) leaving groups are particularly preferred, and these leaving groups are usually ethoxy groups that can be released in the form of ethanol during the condensation reaction. In most cases, the corresponding examples are preferred in terms of the synthesis and production costs of the compound and the treatment of the released leaving groups (which can be relatively easily removed from the compound).

[0099] Although there is a high degree of flexibility in the design of the R a , R b and R c groups, in view of the above discussion, any restriction towards the direction of a particularly preferred (R a R b R c )Si group having three alkoxy groups (which in most cases have relatively short chains) is preferred. Thus, a vulcanizable rubber blend according to the invention is particularly preferred, wherein R a , R b and R c groups are each independently a straight-chain or branched-chain alkoxy group or alkyl group having 1 to 10 carbon atoms, and at least one of the R a , R b and R c groups is an alkoxy group. A vulcanizable rubber blend according to the invention is preferred, wherein R a , R b and R c groups are each independently a straight-chain alkoxy group or alkyl group. In this regard, additionally or alternatively, a vulcanizable rubber blend according to the invention is also preferred, wherein R a , R b and R c groups are each independently an alkoxy group or alkyl group having 1 to 5 carbon atoms, preferably having 2 or 3 carbon atoms. Additionally or alternatively, a vulcanizable rubber blend according to the invention is also preferred, wherein at least two, preferably all, of the R a , R b and R c groups are alkoxy groups. Fundamentally, a vulcanizable rubber blend according to the invention is particularly preferred, wherein R a , R b and R c groups are the same. Most particularly preferred is a vulcanizable rubber blend according to the invention, wherein R a , R b and R c groups are ethoxy groups.

[0100] The organosilicon compound having the formula (III) is a compound also known as a blocked mercaptosilane. The sulfur intended to react with the diene rubber is protected by a thiol ester which can be converted into a thiol.

[0101] Advantageously, the organic linking unit Y can be chosen quite freely and, in a preferred embodiment, can also contain heteroatoms. However, in the context of the present invention, the condition is that the number of non-hydrogen atoms in the linking chain between the Si atom and the S is 3 or more. This means that the silicon and the sulfur atom of the thiol ester are separated from each other by at least three additional atoms or four covalent bonds, as can be achieved, for example, by a straight-chain alkyl chain having 3 or more carbon atoms.

[0102] As long as the minimum distance between the silicon atom and the sulfur atom is observed, there are practically no restrictions on the form taken by the organic linking unit Y, which means that the person skilled in the art has a wide range of choices when designing. However, according to the inventors, for the production costs of the corresponding compounds, the possible raw material base and the feasible synthesis routes, it is preferred that the organic linking unit Y has as simple a design as possible and that very long chains and / or a large number of branches are dispensed with, for example. In this context, first of all, preference is given to a vulcanizable rubber blend according to the invention, in which Y is a straight-chain organic linking unit. Additionally or alternatively, preference is given to a vulcanizable rubber blend according to the invention, in which Y is an organic linking unit having 3 to 20, preferably 3 to 15, particularly preferably 3 to 10 and most particularly preferably 3 to 7 non-hydrogen atoms. For many applications, particular preference is given to a vulcanizable rubber blend according to the invention, in which Y is a straight-chain alkyl chain, preferably a straight-chain alkyl chain having 3 to 8 carbon atoms.

[0103] The inventors have recognized that particularly advantageous embodiments become apparent when using a special form of the blocked mercaptosilane according to formula (III), which is particularly preferred by the inventors. Specifically, it has been found that particularly advantageous results can be achieved when Y contains one or more thioether groups, such that (in other words) Y itself contains additional sulfur atoms. Excellent results have been obtained with the corresponding blocked mercaptosilanes, in particular in combination with the organosilicon compounds having the formula (X) further disclosed below. In other words, preference is given to a vulcanizable rubber blend according to the invention, in which Y is an organic linking unit having the formula -Y a -(S-Y b ) j - so as to obtain an organosilicon compound having the formula (IX):

[0104] IX) (R a R b R c )Si-Y a -(S-Yb ) j -S-(C═O)-Z,

[0105] where j is an integer in the range from 1 to 3, where Y a and Y b are each independently a straight-chain or branched organic linking unit having from 1 to 20 non-hydrogen atoms, where Y b can be the same or different for each repeating unit, such that not all Y b j need to be the same, even though this is preferred. This means that preferably the vulcanizable rubber blend according to the invention, wherein the one or more organosilicon compounds are selected from the group consisting of organosilicon compounds having the formula IX). Preferably the vulcanizable rubber blend according to the invention, wherein j is 1 or 2, preferably 1.

[0106] The foregoing also applies to the organic linking units Y a and Y b , specifically, from many aspects of synthesis and manufacture, it is advantageous to design these groups to have a relatively simple structure. In this regard, first preferably the vulcanizable rubber blend according to the invention, wherein Y a and Y b are each independently a straight-chain or branched, preferably straight-chain, organic linking unit having from 1 to 15, preferably 2 to 10, and particularly preferably 3 to 8 non-hydrogen atoms. Additionally or alternatively, particularly preferably the vulcanizable rubber blend according to the invention, wherein Y a and Y b are alkyl chains.

[0107] According to the inventors, in this embodiment, although the (poly)thioether has an inherent length, it is advantageous to select a relatively long distance or provide a minimum distance between the silicon atom and the first sulfur. Thus, preferably the vulcanizable rubber blend according to the invention, wherein Y a is a straight-chain or branched organic linking unit, wherein the number of non-hydrogen atoms in the linking chain between the Si atom and the first S atom is 3 or more.

[0108] According to the inventors, for these (poly)thioether-based blocked mercapto silanes, when they are used together with additional (poly)thioether-based organosilicon compounds in a vulcanizable rubber blend, a very particularly advantageous vulcanizable rubber blend according to the invention is obtained. Thus, preferably the vulcanizable rubber blend according to the invention, which additionally comprises an organosilicon compound having the formula X):

[0109] X)(R a R b Rc )Si-W a -(S-W b ) k -S-W c -Si(R a R b R c ),

[0110] where k is an integer in the range from 1 to 3, and where W a 、W b and W c are each independently a straight-chain or branched organic linking unit having from 1 to 20 non-hydrogen atoms.

[0111] This means that it is particularly preferred if the vulcanizable rubber compound according to the invention, in particular additionally contains these (poly) sulfide-based organosilicon compounds of formula X) in addition to the (poly) sulfide-based organosilicon compound of formula IX). Preferred is the vulcanizable rubber compound according to the invention, wherein the quotient of the combined parts by weight of the organosilicon compound having formula III) or IX) divided by the combined parts by weight of the (poly) sulfide-based organosilicon compound of formula X) is in the range from 10:1 to 1:5, preferably in the range from 5:1 to 1:2, and particularly preferably in the range from 3:1 to 1:1.

[0112] Similar to the above discussion regarding (poly) sulfide-based blocked mercapto silanes, preferred embodiments of the (poly) sulfide-based organosilicon compounds of formula X) will become apparent. Preferred is the vulcanizable rubber compound according to the invention, wherein W a 、W b and W c are each independently a straight-chain or branched, preferably straight-chain, organic linking unit having from 1 to 15 and preferably 2 to 10 non-hydrogen atoms. Additionally or alternatively, preferred is the vulcanizable rubber compound according to the invention, wherein W a 、W b and W c are alkyl chains. Additionally or alternatively, also preferred is the vulcanizable rubber compound according to the invention, wherein W a and W c are the same. Also in formula X), for each repeating unit, W b can be the same or different, such that not all W b k need to be the same, even though this is preferred. In this regard, further preferred is the vulcanizable rubber compound according to the invention, wherein k is 1 or 2, preferably 1.

[0113] For matching with (poly) sulfide - based blocked mercapto silanes, it is preferred if the (poly) sulfide - based organosilicon compound having the formula (X) is as similar as possible to the preferred (poly) sulfide - based organosilicon compound having the formula (III). In this context, a curable rubber blend according to the invention is preferred, wherein Y a and W a are the same and / or wherein Y b and W b are at least partially the same and / or wherein j = k.

[0114] According to the preliminary rough estimates of the inventors, for all types of blocked mercapto silanes, the situation is that the group of the protecting group Z has a rather small effect on the performance characteristics of the blocked mercapto silane, and thus for cost and handling reasons, a group with a relatively simple structure is preferred instead. Therefore, a curable rubber blend according to the invention is preferred, wherein Z is an organic group having 1 to 15, preferably 2 to 10, and particularly preferably 3 to 8 non - hydrogen atoms. Additionally or alternatively, a curable rubber blend according to the invention is preferred, wherein Z is an alkyl group.

[0115] In addition to diene rubber, filler, polyetheramine, and organosilicon compound, other typical components can also be used in the curable rubber blend according to the invention, for example, to affect the physicochemical properties (such as processing and vulcanization properties) of the curable rubber blend or to optimize the mechanical properties of the vulcanized rubber producible therefrom.

[0116] In this regard, first of all, a curable rubber blend according to the invention is preferred, wherein the curable rubber blend contains one or more additionally added substances, which are preferably selected from the group consisting of reinforcing resins and plasticizers, and the curable rubber blend preferably contains these additionally added substances in a combined weight part range of 10 to 100 phr, preferably in the range of 20 to 80 phr, and particularly preferably in the range of 30 to 60 phr.

[0117] Examples that may be mentioned are vulcanizable rubber compounds according to the invention, wherein the reinforcing resin is selected from the group consisting of: resorcinol-formaldehyde resins (in particular resorcinol-hexamethoxymethylmelamine resin (HMMM) or resorcinol-hexamethylenetetramine resin (HEXA)), and modified phenolic resins. A person skilled in the rubber processing field can easily distinguish the resin from the diene rubber, and in practice, this is especially achieved by the average molar mass. In this regard, examples that may be mentioned are vulcanizable rubber compounds according to the invention, wherein the one or more additional resins have a weight-average molar mass Mw measured by GPC in the range of 200 to 50,000 g / mol, preferably in the range of 400 to 40,000 g / mol, particularly preferably in the range of 600 to 30,000 g / mol, and most particularly preferably in the range of 800 to 20,000 g / mol.

[0118] Furthermore, examples that may be mentioned are vulcanizable rubber compounds according to the invention, wherein the plasticizer is selected from the group consisting of mineral oil, synthetic plasticizer, fatty acid, fatty acid derivative, plasticizer resin, ointment, glyceride, terpene, biomass-to-liquid oil (BTL oil), and rubber-to-liquid oil (RTL oil), and the vulcanizable rubber compound preferably contains the plasticizer in a combined weight part in the range of 1 to 100 phr, preferably in the range of 10 to 80 phr, and particularly preferably in the range of 20 to 60 phr.

[0119] Additionally or alternatively, preferred are vulcanizable rubber compounds according to the invention, wherein the vulcanizable rubber compound contains one or more additional additives, and these additional additives are preferably selected from the group consisting of: methylene donors, anti-aging agents such as N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), N,N'-diphenyl-p-phenylenediamine (DPPD), N,N'-dimethylxyl-p-phenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), activators such as zinc oxide and fatty acid, wax, mastication aids such as 2,2'-dibenzamidodiphenyl disulfide (DBD), and processing aids. Preferred are vulcanizable rubber compounds according to the invention, wherein the vulcanizable rubber compound contains these additional additives in a combined weight part in the range of 0.1 to 20 phr, preferably in the range of 0.5 to 15 phr, and particularly preferably in the range of 1 to 10 phr.

[0120] Regarding the vulcanization behavior, preference is given to a vulcanizable rubber compound according to the invention, wherein the vulcanizable rubber compound comprises 0.5 to 8.0 phr, preferably 0.8 to 6 phr, and particularly preferably 1 to 4 phr of sulfur. In this regard, additionally or alternatively, preference is also given to a vulcanizable rubber compound according to the invention, wherein the vulcanizable rubber compound comprises further vulcanization components selected from the group consisting of crosslinking agents, vulcanization retarders, and vulcanization accelerators (such as thiazole accelerators, mercapto accelerators, sulfenamide accelerators, thiocarbamate accelerators, thiuram accelerators, thiophosphate accelerators, thiourea accelerators, xanthate accelerators, or guanidine accelerators).

[0121] Particular preference is given to dispensing with the use of guanidine accelerators (especially diphenylguanidine). Thus, preference is given to a vulcanizable rubber compound according to the invention, wherein the vulcanizable rubber compound comprises 2 phr or less, preferably 1 phr or less, particularly preferably 0.5 phr or less, and most particularly preferably substantially 0 phr of guanidine accelerators, especially diphenylguanidine.

[0122] From the vulcanizable rubber compound according to the invention, vulcanized rubber and rubber products can be produced in a conventional manner. The corresponding method for producing a vulcanized rubber or a rubber product additionally includes, in addition to producing the vulcanizable rubber compound according to the invention, for example, the following steps:

[0123] x) Vulcanizing the vulcanizable rubber compound according to the invention, preferably as part of a rubber blank and particularly preferably as part of an unvulcanized vehicle tire blank, to obtain vulcanized rubber, preferably as part of a rubber product and preferably as part of an inflated vehicle tire.

[0124] Herein, the vulcanizable rubber compound according to the invention is vulcanized, for example, by conventional methods in the tire industry, such as by sulfur-based crosslinking.

[0125] Accordingly, the invention also relates to a vulcanized rubber that can be produced or is produced by vulcanizing a vulcanizable rubber compound according to the invention. In this regard, preference is given to a vulcanized rubber according to the invention, wherein the vulcanized rubber can be produced by vulcanization at a temperature in the range of 130 °C to 200 °C, preferably in the range of 150 °C to 180 °C.

[0126] Accordingly, the present invention also relates to a rubber product comprising the vulcanized rubber according to the present invention. Examples that may be mentioned are rubber products according to the present invention, wherein the rubber product is selected from the group consisting of shoe soles, conveyor belts, hoses, conveyor belts, and belts. However, for substantially all cases, preferably a rubber product according to the present invention, wherein the rubber product is a vehicle tire, preferably a pneumatic vehicle tire, and the pneumatic vehicle tire preferably comprises the vulcanized rubber according to the present invention in its tread.

[0127] Finally, the use of the vulcanizable rubber compound according to the present invention and / or the vulcanized rubber according to the present invention in the production of rubber products (especially vehicle tires) is also disclosed. Detailed Description

[0128] The present invention and its preferred embodiments will be explained and described in more detail below with reference to experiments.

[0129] A. Production of Vulcanizable Rubber Compounds:

[0130] The vulcanizable rubber compounds are produced in a laboratory tangential mixer in three stages by conventional methods in the rubber industry under conventional conditions. The method includes first preparing a base compound containing all components except the vulcanization system (sulfur and substances affecting vulcanization) in one or more mixing stages, and then adding the vulcanization system thereto to obtain the final compound.

[0131] The substances used in this regard are listed in Table 1.

[0132] Table 1 - Substances Used

[0133]

[0134]

[0135] Each of these vulcanizable rubber compounds is used to produce test specimens by vulcanizing under pressure at 160 °C to 170 °C for t 95 -t 100 (measured using a moving die rheometer according to ASTM D 5289-19 / ISO 6502), and the material properties typical of the rubber industry are determined for the test specimens thus produced using the test methods specified in Part B.

[0136] B. Determination of the Physicochemical Properties of Vulcanized Rubber:

[0137] The following physicochemical properties are determined for the vulcanizable rubber compounds and the vulcanized rubbers produced therefrom using the determination methods listed in Table 2:

[0138] Table 2 - Determination Methods Used

[0139]

[0140] C. Series 1 Tests:

[0141] In the Series 1 tests, nine vulcanizable rubber compounds were produced, and their compositions are detailed in Table 3.

[0142] Table 3 - Vulcanizable Rubber Compounds According to Series 1 Tests (All data are in phr)

[0143] Components V1 V2 V3 V4 E1 E2 V5 E3 E4 NR 10 10 10 10 10 10 10 10 10 BR 18 18 18 18 18 18 18 18 18 SSBR 72 72 72 72 72 72 72 72 72 Filler 95 95 95 95 95 95 95 95 95 Polyether-amine 1 - 2.31 - - 2.31 - - 2.31 - Polyether-amine 2 - - 6.02 - - 6.02 - - 6.02 Silane 1 6.84 6.84 6.84 - - - - - - Silane 2 - - - 9.69 9.69 9.69 - - - Silane 3 - - - - - - 10.54 10.54 10.54 Plasticizer 35 35 35 35 35 35 35 35 35 Additive 1 2 2 2 2 2 2 2 2 2 Additive 2 2 2 2 2 2 2 2 2 2 Additive 3 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Additive 4 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 DPG 2 - - 2 - - 2 - - CBS 2 2 2 2 2 2 2 2 2 Sulfur 2 2 2 2 2 2 2 2 2

[0144] The parts by weight of silane and polyetheramine were adjusted in each case to introduce a constant molar amount. The material properties measured for the relevant vulcanized rubbers are summarized in Table 4.

[0145] Table 4 - Material Properties of Series 1 Tests

[0146]

[0147]

[0148] The results of the Series 1 tests summarized in Table 4 show that polyetheramines 1 and 2 exhibit a favorable accelerating effect, which is manifested as a shortening of the t10 and t90 times. This means that advantageously, a favorable accelerating effect can be achieved without using DPG and a shorter vulcanization time can be achieved.

[0149] When using silane 1, in combination with polyetheramine 1 (in V2) and polyetheramine 2 (in V3), compared with V1, an undesired decrease in crosslink density was caused, while in samples E1 to E4 of the present invention, basically no deterioration within the measurement accuracy range was found compared with V4 and V5, thus confirming the favorable accelerating effect. This means that advantageously, effective substitution can be carried out in existing formulations.

[0150] In samples V1 to V3, it is obvious that the use of polyetheramine 1 (in V2) and polyetheramine 2 (in V3) compared with V1 caused an undesired increase in E'(0.15%) and E'(0.15%) - E'(8%), indicating an undesired increase in filler - filler interaction and deterioration of rolling resistance. In contrast, in samples E1 to E4 of the present invention, compared with V4 and V5, E'(0.15%) and E'(0.15%) - E'(8%) unexpectedly remained constant within the measurement accuracy range or even showed a decrease, which means that better rolling resistance was obtained. Here, the development trend of resilience at room temperature and 70 °C is advantageously comparable to that of samples V1 to V3.

[0151] Similarly, it can be seen that the use of polyetheramine 1 (in V2) and polyetheramine 2 (in V3) results in an undesired increase in G'(100%) compared to V1, while the samples E1 to E4 of the present invention even surprisingly show lower values compared to V4 and V5, thus indicating particularly advantageous resistance, especially also with regard to the tear characteristics on rough sections.

[0152] D. Series 2 tests:

[0153] In the Series 2 tests, eight vulcanizable rubber blends that are not of the present invention (disclosed as additional comparative systems in the context of the present invention) were produced, and their compositions are detailed in Table 5.

[0154] Table 5 - Vulcanizable rubber blends according to Series 2 tests (all data in phr)

[0155]

[0156]

[0157] The parts by weight of the silane were adjusted in each case in order to introduce a constant molar amount.

[0158] The material properties determined for the relevant vulcanized rubbers are summarized in Table 6.

[0159] Table 6 - Material properties of Series 2 tests

[0160]

[0161] The results of the Series 2 tests summarized in Table 6 demonstrate the accelerating effect of polyetheramine 1 and show a positive impact on the tear characteristics in the form of an increased elongation at break. This indicates higher durability in this field.

Claims

1. A vulcanizable rubber compound, comprising: a) one or more diene rubbers, b) one or more fillers selected from the group consisting of silica, c) one or more polyetheramines in a combined weight portion in the range of 0.1 to 10 phr, wherein these polyetheramines are selected from the group consisting of polyetheramines having formula (I): I)R 1 R 2 N-(R 5 ) m -X-R 6 -NR 3 R 4 , wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen or a branched or unbranched hydrocarbon group having 1 to 10 carbon atoms, wherein m is 0 or 1, wherein R 5 and R 6 are each independently a branched or unbranched hydrocarbon chain having 1 to 10 carbon atoms, wherein X is a polyether chain having formula (II): II)-(CHR 7i -CHR 8i -O) x - where x is in the range from 2 to 30 and where R in each monomer unit i 7i and R 8i is, in each case independently and independently of the other monomer units in the polyether chain, hydrogen or a hydrocarbon group having 1 or 2 carbon atoms, and d) one or more silicone compounds selected from the group consisting of silicone compounds having formula (III): III)(R a R b R c )Si-Y-S-(C=O)-Z, Wherein the R a , R b and R c groups are each independently a straight-chain or branched-chain organic group having 1 to 20 non-hydrogen atoms, and the organic group of at least one of the R a , R b and R c groups is bonded to the Si atom via an oxygen atom, wherein Y is a straight-chain or branched-chain organic linking unit having 3 to 30 non-hydrogen atoms, the number of non-hydrogen atoms in the linking chain between the Si atom and the S atom is 3 or more, and wherein Z is a straight-chain or branched-chain organic group having 1 to 20 non-hydrogen atoms.

2. The vulcanizable rubber compound according to claim 1, wherein, The vulcanizable rubber compound comprises styrene-butadiene rubber as the diene rubber, and / or wherein the vulcanizable rubber compound comprises butadiene rubber as the diene rubber, and / or wherein the vulcanizable rubber compound comprises natural polyisoprene and / or synthetic polyisoprene as the diene rubber.

3. The vulcanizable rubber blend according to any one of claims 1 and 2, wherein, The vulcanizable rubber compound comprises the one or more fillers in a combined weight portion in the range of 5 to 250 phr.

4. The vulcanizable rubber compound according to any one of claims 1 to 3, wherein, R in each monomer unit i 7i and R 8i are each independently of one another and independently of the other monomer units in the polyether chain hydrogen or methyl in each case.

5. The vulcanizable rubber blend according to any one of claims 1 to 4, wherein, The polyether chain comprises one or more first monomer units i1 having formula (IV): IV)-(CHR 7i -CH2-O)-, and / or wherein the polyether chain comprises one or more second monomer units i2 having formula (V): V)-(CH2-CH2-O)-, and / or wherein the polyether chain comprises one or more third monomer units i3 having formula (VI): VI)-(CH2-CHR 8i -O)-。 6. The vulcanizable rubber compound according to any one of claims 1 to 5, wherein, The one or more polyetheramines are selected from the group consisting of: - polyetheramines having formula (VII): VII) H2N-(CH(CH3)-CH2-O) x1 -CH2CH(CH3)-NH2, wherein x1 is in the range of 2 to 6, and - polyetheramines having formula (VIII): VIII)H2N-X-CH2CH(CH3)-NH2, wherein X is a polyether chain composed of two or more monomer units selected from the group consisting of having the formula III b ) of the first monomer unit i 1b : III b )-(CH(CH3)-CH2-O)-, Having the formula IV b ) of the second monomer unit i 2b : IV b )-(CH2-CH2-O)-, and having the formula V b ) of the third monomer unit i 3b : V b )-(CH2-CH(CH3)-O)-, wherein the number x of combinations of the first monomer unit i and the third monomer unit i in the polyether chain is in the range of 2 to 5, and the number x of the second monomer unit i in the polyether chain is in the range of 8 to 10. 1b and the third monomer unit i 3b is in the range of 2 to 5, where the number x of the second monomer unit i 1b / 3b in the polyether chain 2b is in the range of 8 to 10. 2b ​ 7. The vulcanizable rubber blend according to any one of claims 1 to 6, wherein, The one or more silicone compounds are selected from the group consisting of silicone compounds having formula (IX): IX)(R a R b R c )Si-Y a -(S-Y b ) j -S-(C=O)-Z, where j is an integer in the range from 1 to 3, where Y a and Y b are each independently a straight-chain or branched organic linking unit having from 1 to 20 non-hydrogen atoms, where Y b is the same or different for each repeating unit.

8. The vulcanizable rubber compound according to any one of claims 1 to 7, further comprising a silicone compound having formula (X): X)(R a R b R c )Si-W a -(S-W b ) k -S-W c -Si(R a R b R c ), where k is an integer in the range of 1 to 3, where W a , W b and W c are each independently a straight-chain or branched-chain organic linking unit having 1 to 20 non-hydrogen atoms.

9. A vulcanized rubber produced or producible by vulcanizing the vulcanizable rubber compound according to any one of claims 1 to 8.

10. A rubber product, in particular a pneumatic vehicle tire, comprising the vulcanized rubber according to claim 9.

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