Sulfur-crosslinkable rubber mixture, vulcanized rubber of rubber mixture and vehicle tire

文档序号：1315767 发布日期：2020-07-10 浏览：4次中文

阅读说明：本技术 硫可交联的橡胶混合物、橡胶混合物的硫化橡胶和车辆轮胎 (Sulfur-crosslinkable rubber mixture, vulcanized rubber of rubber mixture and vehicle tire ) 是由尤利娅·舍费尔诺贝特·米勒卡拉·雷克克里斯蒂娜·韦伯格萨·塔拉托拉大卫-拉斐尔· 于 2018-09-04 设计创作，主要内容包括：本发明涉及一种硫可交联的橡胶混合物、涉及一种其硫化橡胶、并且涉及一种车辆轮胎。该硫可交联的橡胶混合物含有至少以下成分：-至少一种二烯橡胶；以及-10phr至300phr的至少一种二氧化硅；以及-1phf至30phf的至少一种硅烷A,其具有经验通式A-I) A-I) (R1)oSi-R2-S-H；以及-0.5phf至30phf的至少一种硅烷B,其具有经验通式B-I) B-I) (R1)oSi-R3-(S-R4)u-(S-R5)v-Si(R1)o,其中u是0、1、2或3并且v是0或1。(The invention relates to a sulfur-crosslinkable rubber mixture, to a vulcanized rubber thereof, and to a vehicle tire. The sulfur-crosslinkable rubber mixture contains at least the following components: -at least one diene rubber; and-10 phr to 300phr of at least one silica; and-1 phf to 30phf of at least one silane A of empirical formula A-I) A-I) (R 1 ) o Si‑R 2 -S-H; and-0.5 phf to 30phf of at least one silane B of empirical formula B-I) B-I) (R 1 ) o Si‑R 3 ‑(S‑R 4 ) u ‑(S‑R 5 ) v ‑Si(R 1 ) o Wherein u is 0, 1,2 or 3 and v is 0 or 1.)

1. A sulfur-crosslinkable rubber mixture comprising at least the following components:

-at least one diene rubber; and

-from 10phr to 300phr of at least one silica; and

-1phf to 30phf of at least one silane A of empirical formula A-I)

A-I) (R¹)_oSi-R²-S-H; and

0.5phf to 30phf of at least one silane B of empirical formula B-I)

B-I) (R¹)_oSi-R³-(S-R⁴)_u-(S-R⁵)_v-Si(R¹)_o

Wherein o may be 1 or 2 or 3, and the radical R¹May be the same or different and is selected from C₁-C₁₀-alkoxy groups,

C₆-C₂₀-phenoxy group, C₂-C₁₀-cyclic dialkoxy, C₂-C₁₀Di-alkoxy, C₄-C₁₀Cycloalkoxy, C₆-C₂₀-an aryl group,

C₁-C₁₀Alkyl radical, C₂-C₂₀-alkenyl, C₂-C₂₀-an alkynyl group,

C₇-C₂₀Aralkyl, halide or

Alkyl polyether radical-O- (R)⁶-O)_r-R⁷Wherein the radical R⁶Identical or different and branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C₁-C₃₀A hydrocarbon radical, R is an integer from 1 to 30, and the radical R⁷Is an unsubstituted or substituted, branched or unbranched, monovalent alkyl, alkenyl, aryl or aralkyl radical, or

Two R¹Corresponding toolA dialkoxy radical having 2 to 10 carbon atoms, where in this case o<3，

Or two or more silanes of the formulae A-I) and/or B-I) may be via the radical R¹Or bridged by condensation; and is

With the proviso that in each of the formulae A-I) and B-I), in each of (R)¹)_oIn the Si group, at least one R¹Selected from the above options, wherein R is¹: i) bonded to a silicon atom via an oxygen atom, or ii) is a halide; and is

Wherein each molecule neutralizes the intramolecular radical R²、R³、R⁴And R⁵May be identical or different and are branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C₁-C₃₀A hydrocarbyl group; and wherein u is 0 or 1 or 2 or 3 and v is 0 or 1.

2. A sulfur-crosslinkable rubber composition according to claim 1, wherein u is 0 or 1.

3. Sulfur-crosslinkable rubber mixture according to any one of the preceding claims, characterized in that R³Is an alkyl group having 4 to 12 carbon atoms, especially when u is 0 and v is 0.

4. The sulfur-crosslinkable rubber mixture of any one of claims 1 to 3, wherein R is³Is an alkyl group having 2 or 3 carbon atoms, especially when u and/or v is 1.

5. Sulfur-crosslinkable rubber mixture according to any one of the preceding claims, characterized in that R⁴Is an alkyl group having 4 to 8 carbon atoms, especially when u and v are 1.

6. Sulfur-crosslinkable rubber mixture according to any one of the preceding claims, characterized in that R⁵Is an alkyl group having 2 or 3 carbon atoms when v is 1.

7. A sulfur-crosslinkable rubber mixture according to claim 1, characterized in that the silane B has the following structure according to formula B-II):

B-II)

8. a sulfur-crosslinkable rubber mixture according to claim 1, characterized in that the silane B has the following structure according to the formula B-III):

B-III) (EtO)₃Si-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃。

9. a sulfur-crosslinkable rubber mixture according to claim 1, characterized in that the silane B has the following structure according to the formula B-IV):

B-IV) (EtO)₃Si-(CH₂)₈-Si(OEt)₃。

10. sulfur-crosslinkable rubber mixture according to any one of the preceding claims, characterized in that R²Is an alkyl group having 2 or 3 carbon atoms.

11. A sulfur-crosslinkable rubber mixture according to any one of the preceding claims, characterized in that the silane a has the following structure according to the formula a-II):

A-II) (EtO)₃Si-(CH₂)₃-S-H。

12. a vulcanized rubber obtained by sulfur vulcanization of at least one rubber mixture according to any one of claims 1 to 11.

13. A vehicle tyre, characterized in that it comprises at least one vulcanized rubber according to claim 12 in at least one component part.

14. Vehicle tyre according to claim 13, characterized in that it comprises at least one vulcanized rubber according to claim 12 at least in the tread.

Technical Field

The invention relates to a sulfur-crosslinkable rubber mixture, to a vulcanized rubber thereof, and to a vehicle tire.

Background

The rubber composition of the tread determines to a large extent the driving characteristics of vehicle tires, in particular pneumatic vehicle tires.

Likewise, rubber mixtures, which are used in particular in drive belts and other belts and in mechanically stressed parts of hoses, play an important role in the stability and life of these rubber articles. Therefore, high demands are placed on these rubber mixtures for pneumatic vehicle tires, belts (including transmission belts) and hoses.

There are conflicts between most known tire characteristics, such as wet grip behavior, dry braking, handling behavior, rolling resistance, winter characteristics, wear behavior, and tear characteristics.

In particular in pneumatic vehicle tires, many attempts have been made, in particular in tread mixtures, to positively influence the properties of the tire by modifying the polymer components, fillers and other additives.

It must be noted that an improvement in one tire characteristic often entails a deterioration in another characteristic.

In a given mixture system, for example, there are various known options for optimizing the handling behavior by increasing the stiffness of the rubber mixture. Mention may be made here, for example, of increasing the filler level and increasing the crosslink density of the vulcanized rubber mixtures. Although increasing the filler content brings about disadvantages in terms of rolling resistance, the reinforcing network leads to a deterioration of the tear properties and wet grip performance of the rubber mixtures.

It is also known that rubber mixtures, in particular for treads for pneumatic vehicle tires, may contain silica as filler. It is also known that advantages are obtained in terms of the rolling resistance behavior and the processability of the rubber mixtures when silica is bonded to one or more polymers by means of silane coupling agents.

Silane coupling agents known from the prior art are disclosed, for example, in DE 2536674C 3 and DE 2255577C 3.

It is possible in principle to distinguish silanes which are bonded only to silica or equivalent fillers, and to this end in particular silanes which comprise at least one silyl group and, in addition to the silyl group, also a reactive sulfur moiety, such as, in particular, S_xMoiety (wherein x>Or equal to 2) or mercapto groups S-H or block S-PG moieties (in which PG represents a protecting group) such that, after removal of the protecting group during sulfur vulcanization, there is a passage through S_xOr the reaction of S-H moieties or S-PG moieties can also produce silanes that are capable of bonding to the polymer.

In some cases, the prior art also discloses combinations of selected silanes.

EP 1085045B 1 discloses a rubber mixture containing a combination of polysulphide silanes (a mixture having a disulphide content of 69 to 79% by weight, a trisulphide content of 21 to 31% by weight and a tetrasulphide content of 0 to 8% by weight) and silanes containing only one sulphur atom and therefore being unable to bond to a polymer. When used in the tread of a vehicle tyre, such a silane mixture makes it possible, in combination with carbon black and silica as fillers, to obtain an optimum distribution of properties in terms of laboratory prediction, in particular rolling resistance and wear, and optimum tyre characteristics.

WO 2012092062 and JP 2016069551 each disclose different combinations of blocked mercaptosilanes (NXT) and filler reinforcing silanes that contain non-reactive alkyl groups between silyl groups.

Disclosure of Invention

The problem addressed by the present invention was therefore to provide a rubber mixture which exhibits an improvement in the characteristic profile (profile), in particular in the stiffness, wear behavior and rolling resistance index, compared with the prior art. This will optimize the rubber mixture in terms of the conflict between handling, heat accumulation and wear, especially when used in vehicle tires. At the same time, the remaining properties, in particular for vehicle tires, should be kept at a comparable and acceptable level.

This problem is solved by a rubber mixture comprising the following components:

-at least one diene rubber; and

-from 10phr to 300phr of at least one silica; and

-1phf to 30phf of at least one silane A of empirical formula A-I)

A-I)(R¹)_oSi-R²-S-H; and

0.5phf to 30phf of at least one silane B of empirical formula B-I)

B-I)(R¹)_oSi-R³-(S-R⁴)_u-(S-R⁵)_v-Si(R¹)_o

Wherein o may be 1 or 2 or 3, and the radical R¹May be the same or different and is selected from C₁-C₁₀-alkoxy groups,

C₆-C₂₀-phenoxy group, C₂-C₁₀-a cyclic dialkoxy group,

C₂-C₁₀Di-alkoxy, C₄-C₁₀Cycloalkoxy, C₆-C₂₀-an aryl group,

C₁-C₁₀Alkyl radical, C₂-C₂₀-alkenyl, C₂-C₂₀-an alkynyl group,

C₇-C₂₀Aralkyl, halide or

Two R¹Corresponds to a dialkoxy radical having 2 to 10 carbon atoms, where in this case o<3，

Or two or more silanes of the formulae A-I) and/or B-I) may be via the radical R¹Or bridged by condensation; and is

It has now been found, surprisingly, that the combination of silanes A and B, where silane A can also bond to the polymer owing to the reactive S-H groups, achieves an improvement in the level of indices (handling and heat build-up or rolling resistance and wear behavior) of the rubber mixtures according to the invention.

The invention further provides at least one vulcanized rubber of the rubber mixture according to the invention.

The invention further provides a vehicle tire comprising at least one vulcanized rubber according to the invention of a rubber mixture according to the invention in at least one component part. It is preferred that the vehicle tyre comprises at least one vulcanized rubber at least in the tread.

The vulcanized rubber according to the invention and the vehicle tire according to the invention are characterized by an optimization in terms of conflict of steering behavior, rolling resistance and wear benefits.

In the case of a two-part tread (upper: crown and lower: base), the rubber mixtures according to the invention can be used both for the crown and for the base. Preference is given to vulcanizates according to the invention in which at least the crown or at least the base or at least the crown and the base comprise at least one rubber mixture according to the invention.

In the context of the present invention, vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction site vehicles, HGV tires, passenger car tires and bicycles, and motorcycle tires.

The rubber mixtures according to the invention are furthermore also suitable for other components of vehicle tires, such as in particular flange profiles, and also for internal tire components. The rubber mixtures according to the invention are further suitable for other industrial rubber articles, such as bellows, conveyor belts, air springs, belts (including drive belts) or hoses, and shoe soles.

The composition of the sulfur-crosslinkable rubber mixture according to the invention will be described in more detail hereinafter. All statements also apply to the vulcanizates according to the invention and to the vehicle tires according to the invention which comprise at least one vulcanizate according to the invention of the rubber mixtures according to the invention in at least one component part.

The unit "phr" (parts per hundred parts of rubber by weight) used in this document is the unit of quantity customary for the formulation of mixtures in the rubber industry. In this document, the dosage of the parts by weight of the various substances is based on the presence in the mixtureThe mixture has a molecular weight M of more than 20000 g/mol, based on 100 parts by weight of the total mass of all rubbers in (A)_w(GPC)。

The unit phf (parts per hundred parts filler by weight) used in this document is the unit of the customary quantity of coupling agent for fillers in the rubber industry.

In the context of the present application phf relates to the silica present, i.e. any other filler (such as carbon black) that may be present is not included in the calculation of the amount of silane.

According to the invention, the rubber mixture is sulfur-crosslinkable and contains for this purpose at least one diene rubber.

Diene rubbers are understood to mean rubbers which are formed by polymerization or copolymerization of dienes and/or cycloolefins and thus contain C ═ C double bonds in the main chain or in side groups.

The diene rubber is preferably selected from the group consisting of: natural polyisoprene and/or synthetic polyisoprene and/or epoxidized polyisoprene and/or butadiene rubber and/or butadiene-isoprene rubber and/or solution polymerized styrene-butadiene rubber and/or emulsion polymerized styrene-butadiene rubber and/or styrene-isoprene rubber and/or liquid rubber (having a molecular weight M of more than 20000 g/mol)_w) And/or halobutyl rubber and/or polynorbornene and/or isoprene-isobutylene copolymer and/or ethylene-propylene-diene rubber and/or nitrile rubber and/or chloroprene rubber and/or acrylate rubber and/or fluoro rubber and/or silicone rubber and/or polysulfide rubber and/or epichlorohydrin rubber and/or styrene-isoprene-butadiene terpolymer and/or hydrogenated acrylonitrile-butadiene rubber and/or hydrogenated styrene-butadiene rubber.

In particular, nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, neoprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are employed in the production of industrial rubber articles such as belts (including power transmission belts) and hoses and/or shoe soles. For these rubbers, it is preferred to use mixture formulations known to the person skilled in the art, and in particular in respect of fillers, plasticizers, vulcanization systems and additives.

The rubber mixtures are particularly suitable for vehicle tires, in particular and in principle can be used in any component parts, such as in particular treads, sidewalls, flange profiles, and also in other so-called body parts.

Preferably the diene rubber is selected from the group consisting of: natural polyisoprene (NR), synthetic polyisoprene (IR), Butadiene Rubber (BR), solution polymerized styrene-butadiene rubber (SSBR), emulsion polymerized styrene-butadiene rubber (ESBR), butyl rubber (IIR), and halobutyl rubber.

In a particularly preferred embodiment of the invention, the diene rubber is 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). The rubber mixtures are particularly suitable for treads for vehicle tires.

In a particularly advantageous embodiment of the invention, the rubber mixture contains at least one natural polyisoprene, preferably in an amount of from 2phr to 100phr, and in a particularly advantageous embodiment of the invention in an amount of from 5phr to 30phr, very particularly preferably in an amount of from 5phr to 15 phr. This achieves a particularly good processability of the rubber mixtures according to the invention.

In a particularly advantageous embodiment of the invention, the rubber mixture contains at least one polybutadiene (butadiene rubber), preferably in an amount of from 2phr to 100phr, and according to a particularly advantageous embodiment of the invention in an amount of from 5phr to 50phr, very particularly preferably from 10phr to 25 phr. This achieves particularly good wear and tear properties and good processability, as well as low hysteresis losses of the rubber mixtures according to the invention.

In a particularly advantageous embodiment of the invention, the rubber mixture contains at least one styrene-butadiene rubber (SBR) in an amount of preferably from 2phr to 100phr, and in a particularly advantageous embodiment of the invention in an amount of from 25phr to 80phr, very particularly preferably from 65phr to 85 phr. This achieves good processability and low hysteresis losses of the rubber mixtures according to the invention and also good wear and tear properties.

Here, the SBR is preferably an SSBR, which yields the best hysteresis properties.

In a particularly advantageous embodiment of the invention, the rubber mixture contains the polymer blends of the named rubbers NR, BR and SBR, preferably SSBR, preferably in the amounts named in each case in any possible combination, with the sum of all rubbers present being 100 phr.

In a particularly advantageous embodiment, the rubber mixture contains from 5phr to 30phr of at least one natural polyisoprene and/or at least one synthetic polyisoprene, and from 25phr to 80phr of at least one styrene-butadiene rubber and from 5phr to 50phr of at least one butadiene rubber.

The natural polyisoprene and/or the synthetic polyisoprene in all examples may be cis-1, 4-polyisoprene or 3, 4-polyisoprene. However, it is preferred to use cis-1, 4-polyisoprene having a cis-1, 4 content of > 90% by weight. First, such polyisoprenes can be obtained by stereospecific polymerization in solution using a Ziegler-Natta (Ziegler-Natta) catalyst or using finely divided alkyllithium. Secondly, Natural Rubber (NR) is cis-1, 4-polyisoprene of this type, wherein the cis-1, 4 content in natural rubber is more than 99% by weight.

Mixtures of one or more natural polyisoprenes with one or more synthetic polyisoprenes are also conceivable.

These include, inter alia, the so-called high cis type and the low cis type, wherein polybutadiene having a cis content of not less than 90% by weight is referred to as high cis type and polybutadiene having a cis content of less than 90% by weight is referred to as low cis type an example of low cis polybutadiene is L i-BR (lithium-catalyzed butadiene rubber) having a cis content of 20 to 50% by weight, high cis BR achieving particularly good wear characteristics and low hysteresis of the rubber mixture.

The polybutadiene or polybutadienes employed may be end-group modified and/or functionalized by modification and functionalization along the polymer chain. The modification can be with hydroxyl and/or ethoxy and/or epoxy and/or siloxane groups and/or amino and/or aminosiloxane and/or carboxyl and/or phthalocyanine groups and/or silyl sulfide groups. However, further modifications, also referred to as functionalisation, known to the person skilled in the art are also suitable. Such functionalization may comprise a metal atom as a constituent.

In the case where at least one styrene-butadiene rubber (styrene-butadiene copolymer) is present in the rubber mixture, it may be a solution-polymerized styrene-butadiene rubber (SSBR) or an emulsion-polymerized styrene-butadiene rubber (ESBR), and a mixture of at least one SSBR and at least one ESBR may also be employed. The terms "styrene-butadiene rubber" and "styrene-butadiene copolymer" are used synonymously in the context of the present invention.

The styrene-butadiene copolymer employed may be end-group modified and/or functionalized along the polymer chain with the modifications and functionalizations listed above for polybutadiene.

According to the invention, the rubber mixture contains from 10phr to 300phr of at least one silica.

The silica may be selected from the silica types known to those skilled in the art and suitable as fillers for tire rubber compounds. However, it is particularly preferred to use a composition having a particle size of 35 to 400m²A/g, preferably from 35 to 350m²Per g, particularly preferably from 85 to 320m²Per g and very particularly preferably from 120 to 235m²Nitrogen surface area (BET surface area) in g (according to DIN ISO9277 and DIN 66132) and from 30 to 400m²A/g, preferably from 30 to 330m²Per g, particularly preferably from 80 to 300m²G and very particularly preferably from 110 to 230m²Finely divided, precipitated silica of CTAB surface area (according to ASTM D3765) per g. Such silicas give rise, for example, to particular vulcanization of rubber in rubber mixtures for tire treadsGood physical properties. Advantages are also obtained in the processing of the mixture due to the reduction of the mixing time, while maintaining the same product characteristics resulting in improved productivity. The silicas used therefore include, for example, those from EvonikSilicas of the type VN3 (trade name) or highly dispersible so-called HD silicas (for example from Suwei corporation (Solvay))1165MP)。

In a preferred embodiment of the invention, the rubber mixtures according to the invention contain from 20phr to 300phr, preferably from 30phr to 250phr, particularly preferably from 30phr to 150phr and very particularly preferably from 80phr to 110phr, of at least one silica.

In particular, a relatively high silica content of up to 300phr or 250phr or 150phr or 110phr in combination with the two listed silanes A and B, set out in more detail below, leads in particular to advantageous properties in terms of rubber mixtures and their vulcanized rubber tire properties, in particular to an optimum steering and rolling resistance prediction.

In the case of the presence of at least two different silicas (for example differing in their BET surface area) in the rubber mixtures according to the invention, the amounts listed are always related to the total amount of all silicas present.

The rubber mixtures according to the invention may further contain at least one carbon black, in particular industrial carbon black.

Suitable carbon blacks include all carbon black types known to those skilled in the art.

In one embodiment, the carbon black has an iodine value according to ASTM D1510 (also known as iodine adsorption value) of between 30 and 250g/kg, preferably 30 to 180g/kg, particularly preferably 40 to 180g/kg, and very particularly preferably 40 to 130g/kg, and has a DBP value according to ASTM D2414 of 30 to 200ml/100g, preferably 70 to 200ml/100g, particularly preferably 90 to 200ml/100 g.

The specific absorption volume of carbon black or light weight filler was determined using dibutyl phthalate according to the DBP value of ASTM D2414.

The use of carbon black of this type in rubber mixtures, in particular for vehicle tires, ensures the greatest possible compromise between abrasion resistance and heat build-up, which in turn affects the ecologically relevant rolling resistance. It is preferred to use only one type of carbon black in a particular rubber mixture, but it is also possible to incorporate different types of carbon black into the rubber mixture. However, the total amount of carbon black present is preferably from 0phr to 250 phr.

In an advantageous embodiment of the invention, the rubber mixture contains from 0phr to 20phr, preferably from 0phr to 10phr, of at least one carbon black and from 30phr to 300phr, preferably from 30phr to 200phr, of at least one silica.

In another advantageous embodiment of the invention, the rubber mixture contains from 30phr to 150phr of at least one carbon black, and from 10phr to 30phr of at least one silica, and thus constitutes part of the silica mixture.

The rubber mixtures according to the invention may preferably contain the smallest possible amount of further fillers, i.e. preferably from 0phr to 20phr, particularly preferably from 0phr to 10 phr. In the context of the present invention, additional (non-reinforcing) fillers include aluminosilicates, kaolin, chalk, starch, magnesium oxide, titanium dioxide or rubber gels and also fibers (e.g. aramid fibers, glass fibers, carbon fibers, cellulose fibers).

Further optional reinforcing fillers include, for example, carbon nanotubes ((CNTs), including discrete CNTs, so-called Hollow Carbon Fibers (HCF) and modified CNTs containing one or more functional groups such as hydroxyl, carboxyl and carbonyl), graphite and graphene, and so-called "carbon-silica dual-phase fillers".

In the context of the present invention, zinc oxide is not included in the filler.

According to the invention, the rubber mixtures contain 1phf to 30phf, preferably 2phf to 20phf, particularly preferably 2phf to 10phf, at least one silane A of the empirical formula A-I)

A-I)(R¹)_oSi-R²-S-H；

And 0.5phf to 30phf, preferably 0.5phf to 20phf, particularly preferably 0.5phf to 10phf, of at least one silane B) of the empirical formula B-I)

B-I)(R¹)_oSi-R³-(S-R⁴)_u-(S-R⁵)_v-Si(R¹)_o，

Wherein o may be 1 or 2 or 3, and the radical R¹May be the same or different and is selected from C₁-C₁₀-alkoxy groups,

C₆-C₂₀-phenoxy group, C₂-C₁₀-cyclic dialkoxy, C₂-C₁₀-a dialkoxy group which is a radical of an oxygen atom,

C₄-C₁₀cycloalkoxy, C₆-C₂₀-an aryl group,

C₁-C₁₀Alkyl radical, C₂-C₂₀-alkenyl, C₂-C₂₀-an alkynyl group,

C₇-C₂₀Aralkyl, halide or

Two R¹Corresponding to a dialkoxy radical having 2 to 10 carbon atoms, wherein then o<3(o is less than 3),

or two or more silanes of the formulae A-I) and/or B-I) may be via the radical R¹Or bridged by condensation; and is

With the proviso that in each of the formulae A-I) and B-I), in each of (R)¹)_oIn the Si group, at least one R¹Selected from the above options, wherein R is¹: i) bonded to silicon atoms via oxygen atomsOr ii) is a halide; and is

The silanes A present according to the invention are silanes which can be bonded to the polymer owing to the S-H moiety (thio-hydrogen).

The silanes B present according to the invention do not have sulfur atoms or sulfur atoms alone which cannot be bonded to the polymer chain of the diene rubber, since the chemical moiety C-S-C is typically not opened during vulcanization. Silane B is therefore a silane which can react only with fillers, in particular silica.

The index u may take the value 0 or 1 or 2 or 3.

Preferably u is 0 or 1.

The index v may take the value 0 or 1.

In a preferred embodiment of the invention, u and v are both 0.

In a further preferred embodiment of the invention, u and v are both 1.

In a further preferred embodiment of the invention u is 0 and v is 1.

R²、R³、R⁴And R⁵May be, in particular and preferably, -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)-、-CH₂CH(CH₃)-、-CH(CH₃)CH₂-、-C(CH₃)₂-、-CH(C₂H₅)-，-CH₂CH₂CH(CH₃)-、-CH(CH₃)CH₂CH₂-、-CH₂CH(CH₃)CH₂-、-CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-，-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-or

In a preferred embodiment of the invention, R³Is an alkyl group having 4 to 12 carbon atoms, especially when u is 0 and v is 0. It is particularly preferred here when R³Is selected from the group consisting of₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-; very particular preference is given to-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-。

In a further preferred embodiment of the invention, R³Is an alkyl group having 2 or 3 carbon atoms, especially when u and/or v is 1. R is particularly preferred here³is-CH₂CH₂CH₂-time.

In a preferred embodiment of the invention, R⁴Is an alkyl group having 4 to 8 carbon atoms, especially when u and v are 1. It is particularly preferred here when R⁴Is selected from the group consisting of₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂-; very particular preference is given to-CH₂CH₂CH₂CH₂CH₂CH₂-。

In a preferred embodiment of the invention, R⁵Is an alkyl group having 2 or 3 carbon atoms (when v is 1). R is particularly preferred here⁵is-CH₂CH₂CH₂-time.

R²Preferably an alkyl group having 2 or 3 carbon atoms, and is preferably-CH₂CH₂-or-CH₂CH₂CH₂-, particularly preferably-CH₂CH₂CH₂-。

The following relates to R¹The statements made apply to the silanes according to the formulae A-I) and B-I), unless otherwise stated.

All radicals R enumerated¹And via the radical R¹The bridging silane or silanes may be combined with each other within the silyl group.

In which two R are¹Corresponding to a dialkoxy radical having 2 to 10 carbon atoms and then o<In the case of 3(o is less than 3), the silicon atom is part of a ring system.

In the case where two silanes of the formulae A-I) and/or B-I) are bridged to one another, they share the group R¹Or by two Si-R¹The combination of groups are linked to each other via an oxygen atom. This also allows more than two silanes to be attached to each other. After synthesis of the silanes of the formulae A-I) and/or B-I), it is thus conceivable for the two silanes of the formulae A-I) and/or B-I) to be present via an oxygen atom or via the radical R¹Are bridged to each other. This also allows more than two silanes to be attached to each other, for example via a dialkoxy group.

The rubber mixtures according to the invention may therefore also contain oligomers formed by hydrolysis and condensation or by bridging via dialkoxy groups, as R of silanes A and/or B (silanes of the formulae A-I) and/or B-I)¹。

Thus, with the proviso that in each of the formulae A-I) and B-I), in each of (R)¹)_oIn the Si group, at least one R¹Selected from the above options, wherein R is¹: i) bonded to the silicon atom via an oxygen atom, or ii) is a halide, the silanes of the formulae A-I) and B-I) each comprising at least one group R which can act as a leaving group¹。

These are therefore in particular alkoxy groups, phenoxy groups or any other radicals listed which are bonded to the silicon atom via an oxygen atom, or halides.

Preference is given to the radical R¹Containing an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms or a halide ion, particularly preferably an alkoxy group having 1 to 6 carbon atoms.

In a particularly advantageous embodiment of the invention, in the silyl radical (R)¹)_oRadical R in Si-¹Identical and are alkoxy having 1 or 2 carbon atoms, i.e. methoxy or ethoxy,ethoxy is very particularly preferred, where o is 3.

However, in the case of oligomers or in which two R are present¹In the case of formation of dialkoxy radicals, the remaining radicals R¹Preference is given to alkyl having 1 to 6 carbon atoms or halides or alkoxy having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, i.e. methoxy or ethoxy, very particularly preferably ethoxy.

In the context of the present invention, ethoxy groups in the formula of silanes are abbreviated EtO or OEt. Both symbols indicate that alkoxy groups (like ethoxy groups) are bonded to the silicon atom Si via the oxygen atom O.

However, the abbreviations OEt and EtO may in principle be used synonymously in the context of the present invention.

Silanes a of the formula a-I) may preferably be:

(EtO)₃Si-(CH₂)-S-H、(EtO)₃Si-(CH₂)₂-S-H、(EtO)₃Si-(CH₂)₃-S-H、(EtO)₃Si-(CH₂)₄-S-H、(EtO)₃Si-(CH₂)₅-S-H、(EtO)₃Si-(CH₂)₆-S-H、(EtO)₃Si-(CH₂)₇-S-H、(EtO)₃Si-(CH₂)₈-S-H、(EtO)₃Si-(CH₂)₉-S-H、(EtO)₃Si-CH₂CH(CH₃)-S-H、(EtO)₃Si-CH(CH₃)CH₂-S-H、(EtO)₃Si-C(CH₃)₂-S-H、(EtO)₃Si-CH(C₂H₅)-S-H、(EtO)₃Si-CH₂CH₂CH(CH₃)-S-H、(EtO)₃Si-CH(CH₃)CH₂CH₂-S-H、(EtO)₃Si-CH₂CH(CH₃)CH₂-S-H。

in a preferred embodiment of the invention, silane A has the following structure according to formula A-II):

A-II)(EtO)₃Si-(CH₂)₃-S-H。

it is also conceivable for the rubber mixture to comprise a mixture of different silanes of the formula A-I), it being possible for one of the silanes of the formula A-II) to be included.

The total amount of silanes A corresponding to the formula A-I) present is in each case from 1phf to 30phf, preferably from 2phf to 20phf, particularly preferably from 2phf to 10 phf.

In an advantageous development of the invention, the amount of silane a present is at least 2.5 phf.

In a further advantageous development of the invention, the amount of silane a present is at least 3 phf.

In a further advantageous development of the invention, the amount of silane a present is at least 3.5 phf.

The preferred minimum amounts of the respective amounts also apply when only one type a of silane is present.

The particularly preferred and particularly preferred amounts and the cited developments/embodiments result in very good properties as well as an optimum wear level in terms of rolling resistance and handling of the prediction index.

Silanes B of the formula B-I) may preferably be:

(EtO)₃Si-CH₂-S-CH₂-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-CH₂-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-CH₂-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-CH₂-S-(CH₂)₂-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₂-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₂-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-CH₂-S-(CH₂)₃-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₃-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-CH₂-S-(CH₂)₄-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₄-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₄-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-CH₂-S-(CH₂)₅-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₅-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₅-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-CH₂-S-(CH₂)₆-S-CH₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₆-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-(CH₂)-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-(CH₂)₄-Si(OEt)₃、(EtO)₃Si-(CH₂)₅-Si(OEt)₃、(EtO)₃Si-(CH₂)₆-Si(OEt)₃、(EtO)₃Si-(CH₂)₇-Si(OEt)₃、(EtO)₃Si-(CH₂)₈-Si(OEt)₃、(EtO)₃Si-(CH₂)₉-Si(OEt)₃、(EtO)₃Si-(CH₂)₁₀-Si(OEt)₃、(EtO)₃Si-(CH₂)-S-(CH₂)-Si(OEt)₃、(EtO)₃Si-(CH₂)₂-S-(CH₂)₂-Si(OEt)₃、(EtO)₃Si-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃、(EtO)₃Si-(CH₂)₄-S-(CH₂)₄-Si(OEt)₃、(EtO)₃Si-(CH₂)₅-S-(CH₂)₅-Si(OEt)₃、(EtO)₃Si-(CH₂)₆-S-(CH₂)₆-Si(OEt)₃、(EtO)₃Si-(CH₂)₇-S-(CH₂)₇-Si(OEt)₃、(EtO)₃Si-(CH₂)₈-S-(CH₂)₈-Si(OEt)₃、(EtO)₃Si-(CH₂)₉-S-(CH₂)₉-Si(OEt)₃、(EtO)₃Si-(CH₂)₁₀-S-(CH₂)₁₀-Si(OEt)₃。

in a preferred embodiment of the invention, silane B has the following structure according to formula B-II):

B-II)

that is, (EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃。

In particular, for silanes according to the formula B-II), a particularly optimized control and rolling resistance prediction index and also an optimized wear level are achieved.

In a preferred embodiment of the invention, silane B has the following structure according to formula B-III):

B-III)(EtO)₃Si-(CH₂)₃-S-(CH₂)₃-Si(OEt)₃。

in particular for silanes conforming to the formula B-III), a particularly optimized index of control and rolling resistance prediction is achieved.

In a preferred embodiment of the invention, silane B has the following structure according to the formulae B-IV):

B-IV)(EtO)₃Si-(CH₂)₈-Si(OEt)₃

in particular, for silanes according to the formulae B to IV), particularly optimized control and rolling resistance predictors and also optimized wear levels are achieved.

It is particularly surprising here that the combination of silanes A according to the formula A-I), preferably silanes according to the formula A-II), with silanes B according to the formula B-I) and/or B-II) and/or B-III) produces a synergistic effect in terms of the steering and rolling resistance prediction and wear behavior.

It is therefore also conceivable for the rubber mixtures according to the invention to contain a mixture of two silanes of the formula B-I), for example B-II), with another silane of the formula B-I).

The total amount of silanes B of the formula B-I) is in each case from 0.5phf to 30phf, preferably from 0.5phf to 20phf, particularly preferably from 0.5phf to 10 phf.

In an advantageous development of the invention, the amount of silane B present is at least 0.7 phf.

In a further advantageous development of the invention, the amount of silane B present is at least 1.0 phf.

In a further advantageous development of the invention, the amount of silane B present is at least 1.5 phf.

The respective preferred minimum amounts also apply when only one type B of silane is present.

Particularly preferred and particularly preferred amounts and developments or embodiments lead to very good properties with regard to rolling resistance and handling predictors and wear behavior.

The silanes A and/or B present according to the invention can be applied to a support, for example a wax, a polymer or carbon black, and can be added in this form to the rubber mixture. The silanes a and/or B present according to the invention can be applied to the silicon dioxide, wherein the bonding can be physical or chemical.

Silanes a and B may be applied to the silica separately from one another and then the silicas are added to the mixture, or silanes a and B may be applied together to one silica.

When ethoxy-substituted silanes (R) are used¹As ethoxy), the application of the silanes a and/or B present according to the invention to the silica reduces the emission of, for example, volatile by-products (e.g. ethanol).

Particular preference is given to silane A being present in a molar ratio to silane B being present of from 20:80 to 85:15, preferably from 30:70 to 85:15, particularly preferably from 40:60 to 85:15, very particularly preferably from 50:50 to 85: 15.

Preferably, at least silane a is present in an amount of at least 2phf, particularly preferably at least 2.5phf, and at least silane B is present in an amount of at least 0.7phf, preferably at least 1.0phf, particularly preferably at least 1.5 phf.

In an advantageous embodiment of the invention, the silane or silanes A and B are preferably mixed with one another in the molar ratios A and B listed before addition to the rubber mixture.

Thus the silane needs to be added only once and thus only one form of addition is needed.

The mixing of the silanes can be carried out with the exclusion of air. The mixing of the silanes can be carried out under a protective atmosphere, for example under argon or nitrogen, preferably under nitrogen.

The mixing of the silanes can be carried out at standard pressure, elevated pressure or reduced pressure. The mixing of the silanes can preferably be carried out at standard pressure. The high pressure can be a pressure of from 1.1 bar to 100 bar, preferably from 1.1 bar to 50 bar, particularly preferably from 1.1 bar to 10 bar and very particularly preferably from 1.1 bar to 5 bar. The reduced pressure can be a pressure of 1 mbar to 1000 mbar, preferably 250 mbar to 1000 mbar, particularly preferably 500 mbar to 1000 mbar.

The mixing of the silanes can be carried out at between 20 ℃ and 100 ℃, preferably between 20 ℃ and 50 ℃, particularly preferably between 20 ℃ and 30 ℃.

The mixing of the silane may be performed in a solvent such as methanol, ethanol, propanol, butanol, cyclohexanol, N-dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane, heptane, octane, decane, toluene, xylene, acetone, acetonitrile, carbon tetrachloride, chloroform, dichloromethane, 1, 2-dichloroethane, tetrachloroethylene, diethyl ether, methyl tert-butyl ether, methyl ethyl ketone, tetrahydrofuran, dioxane, pyridine or methyl acetate, or a mixture of the above solvents. The mixing of the silanes is preferably carried out in the absence of a solvent.

It is further conceivable that the rubber mixtures according to the invention contain at least one further silane coupling agent which is not silane a or silane B.

Furthermore, the rubber mixtures may contain further activators and/or agents for binding fillers, in particular carbon black. Examples thereof are the compounds S- (3-aminopropyl) thiosulfuric acid and/or metal salts thereof disclosed in EP 2589619A 1, which achieve very good physical properties of the rubber mixtures, in particular in combination with at least one carbon black as filler.

The rubber mixtures may further contain conventional additives in conventional weight fractions, which are preferably added in at least one basic mixing stage in the production of the mixtures. These additives include

a) Anti-aging additives, for example N-phenyl-N '- (1, 3-dimethylbutyl) -p-phenylenediamine (6PPD), N' -diphenyl-p-phenylenediamine (DPPD), N '-ditolyl-p-phenylenediamine (DTPD), N-isopropyl-N' -phenyl-p-phenylenediamine (IPPD), 2, 4-trimethyl-1, 2-dihydroquinoline (TMQ),

b) activators, for example zinc oxide and fatty acids (e.g. stearic acid) and/or other activators, such as zinc complexes, for example zinc ethylhexanoate,

c) the amount of wax is such that,

d) hydrocarbon resins, such as in particular optional binder resins,

e) plasticating auxiliaries, for example 2,2' -dibenzamidodiphenyl disulfide (DBD), and

f) processing aids, such as in particular fatty acid esters and metal soaps, for example zinc soaps and/or calcium soaps,

g) and (3) a plasticizer.

The plasticizers used in the context of the present invention comprise all plasticizers known to the person skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, for example MES (mild extraction solvate) or RAE (residual aromatic extract) or TDAE (treated distilled aromatic extract), or liquid rubber-to-liquid oil (RT L) or liquid biomass-to-liquid oil (BT L) preferably having a polycyclic aromatic content of less than 3% by weight according to method IP 346, or triglycerides, for example rapeseed oil or factice or hydrocarbon resins, or liquid polymers having an average molecular weight between 500g/mol and 20000 g/mol (determined by GPC, based on BS ISO 11344: 2004).

The plasticizer is preferably selected from the group consisting of the above plasticizers.

The plasticizer is particularly preferably selected from the group consisting of: hydrocarbon resins, liquid polymers and mineral oils.

When mineral oil is used, the oil is preferably selected from the group consisting of: DAE (distilled aromatic extract) and/or RAE (residual aromatic extract) and/or TDAE (treated distilled aromatic extract) and/or MES (mild extracted solvent) and/or naphthenic oils.

In a preferred embodiment of the invention, the rubber mixture contains at least one mineral oil plasticizer, preferably at least TDAE and/or RAE as plasticizer. This results in particularly good processability characteristics of the rubber mixtures, in particular good miscibility.

In a preferred embodiment of the invention, the rubber mixture contains at least one liquid polymer as plasticizer.

In a preferred embodiment of the invention, the rubber mixture contains at least one hydrocarbon resin as plasticizer.

The person skilled in the art will understand that hydrocarbon resins are polymers composed of monomers, and that hydrocarbon resins linked to each other via monomers formally consist of derivatives of the monomers. However, in the context of the present invention, these hydrocarbon resins are not included in the rubber. In the context of the present application, the term "hydrocarbon resin" includesAs a resin comprising carbon and hydrogen atoms and optionally heteroatoms such as, in particular, oxygen atoms. The hydrocarbon resin may be a homopolymer or a copolymer. In this application, according toAt line version 3.28, homopolymer is understood to mean a polymer "formed from only one type of monomer". These monomers may be chosen from any of the monomers of hydrocarbon resins known to the person skilled in the art, such as aliphatic C₅Monomers, and further unsaturated compounds which can be cationically polymerized, including aromatic compounds and/or terpenes and/or olefins and/or cyclic olefins.

In a preferred embodiment of the invention, the hydrocarbon resin is selected from the group consisting of: aliphatic C₅Resin and α -hydrocarbon resins of methyl styrene and styrene.

The hydrocarbon resins preferably have a softening point according to ASTM E28 (Ring and ball method) of from 10 ℃ to 180 ℃, particularly preferably from 60 ℃ to 150 ℃, very particularly preferably from 80 ℃ to 99 ℃. The hydrocarbon resins preferably also have a molecular weight Mw of from 500 to 4000g/mol, preferably from 1300 to 2500 g/mol.

The amount fraction of the total amount of further additives is from 3phr to 150phr, preferably from 3phr to 100phr and particularly preferably from 5phr to 80 phr.

Zinc oxide (ZnO) may be included in the total amount fraction of other additives.

It may be selected from all types of zinc oxide known to the person skilled in the art, such as ZnO particles or powders. Conventionally used zinc oxides generally have a particle size of less than 10m²BET surface area in g. However, it is also possible to use a filter having 10m²G to 100m²Zinc oxide with a BET surface area of/g, for example the so-called "nano-zinc oxide".

In particular, when using the rubber mixtures according to the invention for the interior components of tires or industrial rubber articles which are in direct contact with the strength members present, it is also customary to add suitable adhesive systems (often in the form of adhesive resins) to the rubber mixtures.

The vulcanization is preferably carried out in the presence of sulfur and/or a sulfur donor and with the aid of vulcanization accelerators, some of which can also act as sulfur donors.

In a final mixing step sulphur and/or a further sulphur donor and one or more accelerators are added to the rubber mixture. The accelerator is selected from the group consisting of: a thiazole accelerator and/or a mercapto group-containing accelerator and/or a sulfenamide accelerator and/or a thiocarbamate accelerator and/or a thiuram accelerator and/or a phosphorothioate accelerator and/or a thiourea accelerator and/or a xanthate accelerator and/or a guanidine accelerator.

It is preferred to use at least one sulfenamide accelerator selected from the group consisting of: n-cyclohexyl-2-benzothiazolesulfenamide (CBS) and/or N, N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and/or benzothiazolyl-2-sulfenylmorpholine (MBS) and/or N-tert-butyl-2-benzothiazolesulfenamide (TBBS).

The sulfur donating species that can be used can be any sulfur donating species known to those skilled in the art. When the rubber mixture contains a sulfur-donating substance, said substance is preferably selected from the group comprising, for example, thiuram disulfides, such as tetrabenzylthiuram disulfide (TBzTD) and/or tetramethylthiuram disulfide (TMTD) and/or tetraethylthiuram disulfide (TETD), and/or thiuram tetrasulfide, such as dipentamethylenethiuram tetrasulfide (DPTT) and/or dithiophosphates, such as

Dipdis (bis (diisopropyl) thiophosphoryl disulfide) and/or bis (O, O-2-ethylhexyl thiophosphoryl) polysulfides (e.g. Rhenocure SDT)Rheinchemie GmbH) and/or zinc dichlorooxydisulphosphate (e.g., Rhenocure)Rhine chemical company) and/or zinc alkyldithiophosphates, and/or 1, 6-bis (N, N-dibenzylthiocarbamoyldithio) hexane and/or diaryl polysulfides and/or dialkyl polysulfides.

Further additives such as, for example, those known under the trade name, may be used in the rubber mixture OrA network forming system available from below, or a network forming system as described, for example, in WO2010/049216a 2. This system contains a vulcanizing agent crosslinked with a functionality greater than four and at least one vulcanization accelerator.

The required amount of additional sulphur in the form of elemental sulphur and/or additional sulphur donors depends on the field of use of the respective rubber mixture. The corresponding amounts added are known to the person skilled in the art. For the addition of elemental sulphur, the amount in the case of a rubber mixture for the beads of vehicle tyres is for example between 0phr and 5 phr. For treads for vehicle tires, which generally have a lower sulfur content than the beads, the amount of elemental sulfur to be added is preferably from 0phr to 4 phr.

In an advantageous development of the invention, a plurality of accelerators is used. Preference is given to using sulfenamide accelerators, particularly preferably CBS, in combination with guanidine accelerator DPG (diphenylguanidine). The amount of DPG here is from 0phr to 5phr, preferably from 0.1phr to 3phr, particularly preferably from 0.5phr to 2.5phr, very particularly preferably from 1phr to 2.5 phr.

Curing retarders may also be present in the rubber mixture.

The terms "vulcanized" and "crosslinked" are used synonymously in the context of the present invention.

The invention further provides a process for producing the sulfur-crosslinkable rubber mixtures according to the invention, in which a base mixture comprising all the constituents except the vulcanization system is first produced in one or more mixing stages. The final mixture is produced in the final mixing stage by adding a vulcanization system. The final mixture is further processed, for example by an extrusion operation or calendering, and brought into a suitable shape. This is followed by further processing by vulcanization, wherein sulfur crosslinking occurs due to the vulcanization system added in the context of the present invention.

In an advantageous embodiment of the process according to the invention, the silane or silanes a and B are mixed with one another, preferably in the listed molar ratios a and B and under the abovementioned conditions, including all the specifications described, before being added to the rubber mixture.

In an advantageous embodiment of the process according to the invention, the silanes a and/or B have been applied to the silica, wherein the bonding can be physical or chemical, and is preferably added to the rubber mixture in this form in the basic mixing stage.

The rubber mixtures according to the invention are particularly suitable for use in vehicle tires, in particular pneumatic vehicle tires. In principle, use in any tire component is conceivable, in particular in a tread, in particular in the crown of a tread having the above-described crown/base construction.

For use in vehicle tyres, the mixture is preferably brought into the shape of the tread as the final mixture before vulcanization and applied in a known manner to the production process of a green vehicle tyre.

As mentioned above, the production of the rubber mixtures according to the invention is carried out, which are used as sidewalls or other body mixtures for vehicle tires. The difference is the formation after the extrusion operation/calendering of the mixture. The so obtained form of the not yet vulcanized rubber mixture for one or more different bulk mixtures is then used for the building of a green tyre.

The term "body mix" is understood to mean a rubber mix for other component parts of the tire, such as, mainly, separator plates, inner linings (inner layers), ring core profiles, belts, shoulders, belt profiles, carcasses, bead reinforcements, bead profiles, flange profiles and belts. In order to use the rubber mixtures according to the invention in transmission belts and other belts, in particular in conveyor belts, the extruded, not yet vulcanized mixture is shaped appropriately and often simultaneously or subsequently provided with strength members, such as synthetic fibers or steel cords. This generally provides a multilayer construction consisting of one and/or more rubber compound layers, one and/or more identical and/or different strength member layers and one and/or more additional layers of the same and/or another rubber compound.

Detailed Description

The invention will now be explained in more detail with the aid of comparative and working examples, which are summarized in the following table.

The general composition of the rubber mixtures on which the examples are based is summarized in table 1 as R1 (formulation 1). Both the type of silane and the amount of silane used were then varied in tables 2 to 5 to provide comparative and inventive mixtures. The comparative mixture is labeled V and the inventive mixture is labeled E. Tables 2 and 3 are related and related tests include the addition of silane B in addition to silane a. Tables 4 and 5 show further working examples and related test series, which here include the complete or partial replacement of silane A with silane B, starting from the comparative mixture.

In each case, the respective silanes are premixed with one another and then added to the rubber mixture in the basic mixing stage. The amount of silane reported (in phf) is related to 95phr of silica.

Silane^h)(silanes having the formula B-II): 1, 6-bis (thiopropyltriethoxysilyl) hexane) was prepared as follows:

to mercaptopropyltriethoxysilane (62.0 g; 0.260 mol; 2.10 equivalents) sodium methoxide (21% in EtOH; 82.3 g; 0.254 mol; 2.05 equivalents) was added in portions at a rate such that the reaction temperature did not exceed 35 ℃. Once the addition was complete, the mixture was heated at reflux for 2 hours. The reaction mixture was then added to 1, 6-dichlorohexane (19.2 g; 0.124 mol; 1.00 eq.) at 80 ℃ over 1.5 hours. Once the addition was complete, the mixture was heated at reflux for 3 hours and then allowed to cool to room temperature. The precipitated salt was filtered off and the product was freed of solvent under reduced pressure. The product (yield: 88%, purity:>99％，¹³C-NMR) as a clear liquidAnd (4) obtaining.

Silaneⁱ⁾(silanes having the formula B-III): bis (propyltriethoxysilyl) sulfide) was prepared as follows:

to a solution of chloropropyltriethoxysilane (361 g; 1.5 mol; 1.92 eq) in ethanol (360ml) was added in portions Na at a rate such that the temperature did not exceed 60 deg.C₂S (61.5 g; 0.78 mol; 1.00 eq.). Once the addition was complete, the mixture was heated at reflux for 3 hours and then allowed to cool to room temperature. The reaction product was filtered to remove precipitated salts. Purification by distillation (0.04 mbar; 110 ℃) gave the product (yield: 73%, purity:>99％，¹³C-NMR) as a clear liquid.

NMR method: the molar ratios and mass fractions reported in the examples as analytical results were determined by¹³Obtained by C-NMR measurement, using the following parameters: 100.6MHz, 1000 scans in CDCl solvent₃Internal standards for calibration: tetramethylsilane, relaxation agent Cr (acac)₃To determine the mass fraction in the product, a defined amount of dimethyl sulfone is added as an internal standard and the molar ratio of the product to it is used to calculate the mass fraction.

In addition, the mixture production is carried out by the methods customary in the rubber industry in three stages under typical conditions in a laboratory mixer having a capacity of 300 ml to 3 l, in the first mixing stage (basic mixing stage) all the ingredients except the vulcanization system (sulfur and substances influencing vulcanization) being first mixed at 145 ℃ to 165 ℃ (target temperature 152 ℃ to 157 ℃) for 200 to 600 seconds. In the second stage, the mixture from stage 1 is mixed again, i.e. subjected to so-called regrinding. In the third stage (final mixing stage) the vulcanization system is added, resulting in a final mixture, which is mixed at 90 to 120 ℃ for 180 to 300 seconds.

Passing t under pressure at 160 ℃ to 170 ℃₉₅To t₁₀₀Vulcanization (measured on a moving disk rheometer according to ASTM D5289-12/ISO 6502) all the mixtures were used to produce test samples and these test samples were used to determine typical materials for the rubber industry with the test methods reported hereinafterAnd (4) characteristics.

A loss factor tan D (10%) (tan) from a second strain scan at 1Hz and 70 ℃ of RPA (rubber processing analyzer) based on ASTM D6601;

maximum loss factor tan max according to DIN 53513 from dynamic mechanical measurement (strain sweep) at 55 deg.C

Stress at 200% elongation at room temperature (M200) according to DIN 53504

Rebound resilience at 70 ℃ according to ISO 4662

Abrasion at room temperature according to DIN/ISO 4649

The substances used were:

a) silicon dioxide: VN3 winning company

b) Other additives: anti-aging additive, antiozonant wax, zinc oxide, stearic acid

c)DPG+CBS

d) Silane variants according to e) to j)

e)SiWinning company, silanes of the formula A-II)

f)SiA winning and creating company; contains TESPD: a silane having the formula a:

A*)(EtO)₃Si-(CH₂)₃-S_x-(CH₂)₃-Si(OEt)₃

bonded but not inventive in the formula A-I), which contains 75% by weight of S in the silane mixture₂(x ═ 2) and 7% by weight of S₁(x ═ 1) (and also 18% by weight, x>2)

g) NXT, Momentive (miiki group); purity > 90% by weight, silane a-2:

A-2*)(EtO)₃Si-(CH₂)₃-S-C(＝O)-(CH₂)₁₆-CH₃

bonded but not according to the invention under the formula A-I)

h) Having the formula B-II) (EtO)₃Si-(CH₂)₃-S-(CH₂)₆-S-(CH₂)₃-Si(OEt)₃(1, 6-bis (thiopropyltriethoxysilyl) hexane) silane of purity>99% as described above

i) Containing a silane having the formula B-III): bis (propyltriethoxysilyl) sulfide, see production above

j) Silanes having the formulae B to IV): bis-triethoxysilyloctane from ABCR

k) Mole fraction of non-bonded silane B-III) bis (propyltriethoxysilyl) sulfide in the silane mixture: from added silanesⁱ⁾And silanes^f)Calculated (i.e. taking into account in silane)^f)S in (1)₁-silane B-III))

l) mole fraction of non-bonded silanes B-II) in the silane mixture:

m) mole fraction of non-bonded silanes B-IV) in the silane mixture:

n) polybutadiene: europrene Neocci BR 40, Polymer (Polimeri)

o)S L R-4601, Shengxi ao corporation (Trinseo)

As is evident from the table, the rubber mixtures according to the invention exhibit an improvement in the level of rolling resistance and wear characteristics compared with the prior art. The rubber mixtures according to the invention have the same or improved rolling resistance index, as is evident from the values of the hysteresis loss tan and the resilience at 70 ℃. At the same time, the rubber mixtures according to the invention are at a very good level of abrasion. Surprisingly, even replacement of silane a with silane B results in improved or at least unchanged wear. The rubber mixtures according to the invention also exhibit improved stiffness and thus improved handling.

Thus, the vulcanized rubber of the present invention and the vehicle tire of the present invention are characterized by optimal wear, handling and rolling resistance behavior.

TABLE 1

Composition (I)	Unit of	R1
			NR TSR	phr	10
BRⁿ⁾	phr	18
			SSBR^o)	phr	72
Silicon dioxide^a)	phr	95
			TDAE	phr	50
Other additives^b)	phr	9
			Silane (different)^d)	phf	Is different
Accelerator^c)	phr	4
			Sulfur	phr	2

TABLE 2

	Unit of	V1	V2	V3	V4	V5	V6	V7	V8
										Silane^f)	phf	7.2	7.2	-	-	-	-	-	-
Silaneⁱ⁾	phf	-	2.8	-	-	-	-	-	-
										Silane^g)	phf	-	-	7.2	7.2	7.2	7.2	7.2	-
Silane^h)	phf	-	-	-	2.2	3.3	-	-	-
										Silane^j)	phf	-	-	-	-	-	1.7	2.6	7.2
B-III)^k)Mol% of	Mol％	7	35	-	-	-	-	-	-
										B-II)^l)Mol% of	Mol％	-	-	0	17	23	-	-	-
B-IV)^m)Mol% of	Mol％	-	-	-	-	-	17	23	100

tan d max.55℃		0.19	0.19	0.18	0.17	0.17	0.24	0.24	0.28
										tan d 10％		0.17	0.17	0.18	0.17	0.17	0.21	0.22	0.22
Resilience at 70 ℃	％	44.0	46.2	45.1	47.5	49.1	38.6	38.4	32.0
										M200	MPa	4.5	5.0	4.5	4.7	4.9	1.8	1.8	1.1
Wear and tear	mm³	146	147	133	134	143	282	287	320

TABLE 3

	Unit of	V9	E1	E2	V10	E3	E4	E5	E6	V11
											Silane^e)	phf	7.2	7.2	7.2	-	7.2	7.2	7.2	7.2	-
Silaneⁱ⁾	phf	-	-	-	-	-	-	2.7	4.0	7.2
											Silane^h)	phf	-	3.4	5.1	8.5	-	-	-	-	-
Silane^j)	phf	-	-	-	-	2.7	4.0	-	-	-
											B-III)^k)Mol% of	Mol％	0	-	-	-	-	-	17	23	100
B-II)^l)Mol% of	Mol％	0	17	23	100	-	-	-	-	-
											B-IV)^m)Mol% of	Mol％	0	-	-	-	17	23	-	-	-

											tan d max.55℃		0.18	0.14	0.15	0.18	0.15	0.14	0.16	0.15	0.24
tan d 10％		0.18	0.14	0.14	0.19	0.15	0.14	0.15	0.14	0.21
											Resilience at 70 ℃	％	46.6	52.9	54.7	42.1	51.9	53.7	51.5	52.9	34.2
M200	MPa	4.4	5.9	6.3	2.5	7.1	7.6	6.1	6.4	1.4
											Wear and tear	mm³	99	81	86	196	67	76	72	85	234

TABLE 4

	Unit of	V12	V13	V14	V15	V16	V17	V18	V19
										Silane^f)	phf	7.2	4.3	-	-	-	-	-
Silaneⁱ⁾	phf	-	2.6	-	-	-	-	-
										Silane^g)	phf	-	-	11.1	6.6	4.4	6.6	4.4	-
Silane^h)	phf	-	-	-	3.4	5.1	-	-	-
										Silane^j)	phf	-	-	-	-	-	2.7	4.0	6.7
B-III)^k)Mol% of	Mol％	7	43	-	-	-	-	-	-
										B-II)^l)Mol% of	Mol％	-	-	0	25	43	-	-	-
B-IV)^m)Mol% of	Mol％	-	-	-	-	-	25	43	100

tan d 10％		0.18	0.18	0.16	0.17	0.18	0.21	0.22	0.22
										Resilience at 70 ℃	％	44.3	43.9	48.5	47.5	47.2	38.0	37.2	31.8
Wear and tear	mm³	145	147	128	112	145	273	322	319

TABLE 5

	Unit of	E7	E8	E9	E10	E11	E12	E13	V20
										Silane^e)	phf	4.3	2.9	4.3	2.9	5.8	4.3	2.9	-
Silaneⁱ⁾	phf	-	-	-	-	1.3	2.7	4.0	6.7
										Silane^h)	phf	3.4	5.1	-	-	-	-	-	-
Silane^j)	phf	-	-	2.7	4.0	-	-	-	-
										B-III)^k)Mol% of	Mol％	-	-	-	-	11	25	43	100
B-II)^l)Mol% of	Mol％	25	43	-	-	-	-	-	-
										B-IV)^m)Mol% of	Mol％	-	-	25	43	-	-	-	-

										tan d 10％		0.14	0.14	0.14	0.13	0.15	0.15	0.14	0.21
Resilience at 70 ℃	％	52.6	51.9	51.7	50.5	48.6	50.1	50.4	34.0
										Wear and tear	mm³	83	108	89	118	80	94	99	225

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