A functionalized polymer blend for a tire

TECHNICAL FIELD

The present invention relates to a polymer blend consisting of (a) from 60 to 96 percent by weight of a first elastomeric polymer having a high molecular weight, (b) from 4 to 35 percent by weight of a second polymer having a low molecular weight, and optionally (c) from 0 to 13 weight percent of at least one diluent oil. In particular the first elastomeric polymer, i.e. component (a), is obtained by (I) anionic polymerization of at least one bound diene monomer and optionally at least one αolefin monomer in the presence of a polymerization initiator in an organic solvent and optionally by (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one a modifying compound, as defined in claim 1 and the following part of the document. Similarly, a second polymer, that is component (b), is obtained by (i) anionic polymerization (i-1) of at least one bound diene monomer, (i-2) at least one bound diene monomer and at least one α-olefin monomer or (i-3) at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent and by (ii) modification of the polymer chain ends obtained by the method (i) by adding and reacting at least one modifying compound, as defined in claim 1 and the following part of the document.

The present invention also relates to a polymer composition comprising said polymer blend. In another embodiment, the present invention relates to a method of preparing a crosslinked elastomeric polymer, wherein said method consists of (1) producing said polymer blend or said polymer composition, (2) adding at least one filler and optionally at least one silicon hydride coupling agent and reacting such a mixture, and (3) adding at least one vulcanizing agent and optionally at least one vulcanizing accelerating agent to the mixture of step (2) and crosslinking such a mixture. The present invention further relates to a crosslinked elastomeric polymer obtained according to said method and an article comprising said polymer composition or said crosslinked elastomeric polymer. In addition, the use of said polymer blend, said polymer composition or said crosslinked elastomeric polymer for producing a tire, tire tread or sidewall of a tire is described, as well as a polymer kit comprising said polymer blend or said polymer composition.

BACKGROUND OF THE INVENTION

In recent years, there has been a growing need to develop polymer compositions for the production of tires for the automotive industry that would improve tire performance. In particular, environmental aspects such as reducing fuel consumption and / or carbon dioxide emissions as a result of reducing tire rolling resistance have become more important, as well as safety aspects such as improving driving stability due to increased grip and abrasion resistance.

A typical rubber tire formulation contains an aromatic vinyl bonded high molecular weight diene copolymer, e.g. styrene butadiene rubber (SBR), which, when mixed with many additives, such as silica filler and vulcanizing agent, and vulcanization (crosslinking), results in a tire tire with lower rolling resistance due to the use of a high molecular weight SBR component. Although obtaining a tire with better (lower) rolling resistance is beneficial, the use of an aromatic vinyl-bonded diene copolymer with a high molecular weight is associated with high viscosity, and thus results in less favorable processability at subsequent processing stages, such as compound preparation and vulcanization (crosslinking) ) suitable polymeric preparations.

Therefore, aromatic vinyl bonded high molecular weight diene copolymer is usually diluted with low molecular weight dilution oil to reduce the viscosity of the copolymer and to provide good mixing, incorporation and distribution parameters of the copolymer during the subsequent stages of blend preparation and / or crosslinking (vulcanization) of the rubber preparation . Typical diluting oils (or plasticizers) include mineral oils and processed mineral oils, such as e.g. DAE (Distillate Aromatic Extract), TDAE (Treated Distillate Aromatic Extract), MES (Mild Extraction Solvate), RAE (Residual Aromatic Extract) and naphthenic oils. However, there are some disadvantages to diluting the aromatic vinyl-bound diene copolymer with a low molecular weight dilution oil:

Because the molecular weight of the commonly used diluting oil is relatively low, e.g. about 450 g / mol (converted to polystyrene equivalents) in the case of TDAE oil, the increased processability of vinyl-bound aromatic diene copolymer with high molecular weight during the subsequent stages of preparation of the mix and vulcanization, as mentioned above, is associated with a significant increase in the amount of "volatile organic compounds "(Hereinafter referred to as VOC) in the final product, i.e. the tire. These VOC emissions become particularly important when using the tire at elevated temperatures.

Another disadvantage is that the glass transition temperature and compatibility of such dilution oils are more or less constant and cannot change. Therefore, factors such as compatibility and the resulting formation of diluent oil deposits on the surface of the vulcanizate during storage should be taken into account in the production of the diene copolymer bound by aromatic vinyl. In addition, the efficiency and scope of applications of vulcanizate (i.e. a crosslinked rubber formulation after vulcanization), which usually depend on the glass transition temperature, can only be adjusted by changing the composition of the diene copolymer bound by aromatic vinyl. An increase in the glass transition temperature of the aromatic vinyl diene copolymer results, however, in better adhesion and greater rolling resistance, and thus greater fuel consumption and increased carbon dioxide emissions. On the other hand, the reduction of the glass transition temperature of the aromatic vinyl diene copolymer results in improved rolling resistance of the resulting tire and lower fuel consumption, but unfortunately also leads to a reduction in wet grip.

Another disadvantage of using a low molecular weight dilution oil is that most of these oils have intense colors - from yellow to dark brown. Therefore, before changing the polymer grade, intensive cleaning of the production plant should be carried out, in particular if oil-diluted polymer is to be used during the next production cycle. However, such cleaning procedures are time consuming and expensive.

In addition, dilution of the vinyl aromatic high molecular weight diene copolymer with a commonly used low molecular weight dilution oil results in less favorable reduction of mechanical properties, especially modulus values, hardness relative to guidance stability (E 'at temp.

60 ° C), greater friction losses and reduced rebound elasticity at higher temperatures, which corresponds to a worsening of rolling resistance.

There is therefore a need to develop alternative diluents that are suitable substitutes or supplements to the dilution oils commonly used according to the current state of the art, and thus enabling the use of cross-linked (vulcanized) polymer preparations, which have acceptable or improved processability, at the same time ensuring less emission of VOC compounds and better balancing of dynamic properties of cross-linked polymer preparations and their strengthening, for example. lower hysteresis losses manifested by low temperature rise, high reflection flexibility at high temperatures and low tangent value δ at 60 ° C, as well as better reinforcement manifested by a higher module, especially at 300% elongation, and high abrasion resistance final products in the form of tires. The present invention enables this demand to be met.

SUMMARY OF THE INVENTION

In a first aspect, the present invention relates to a polymer blend consisting of (a) from 60 to 96 percent by weight of the first elastomeric polymer, (b) from 4 to 35 percent by weight of the second polymer, and optionally (c) from 0 to 13 percent by weight of at least one dilution oil, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and optionally at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent and optionally (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one modifying compound according to claim 1 and the description below, and the second polymer is obtained by (i) anionic polymerization in the presence of an organic solvent polymerization initiator (i-1) of at least one bound diene monomer or (i-2) at least one bound diene monomer and at least one α-olefin monomer or (i-3) at least one α-olefin monomer; and (ii) modification of the polymer chain ends obtained by method (i) by adding and reacting at least one compound represented by formula (1), pattern (3) or pattern (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a), (b) and (c) are based on the total weight of the polymer blend.

The polymerization initiator may be selected from the group consisting of n-BuLi, sec-BuLi, tert-BuLi, a compound represented by formulas (6) to (10) according to claim 4 or their adducts with Lewis base and / or mixtures thereof.

The component (b), i.e. the second polymer, may be an elastomeric polymer, preferably a styrene butadiene polymer or a butadiene polymer.

At least one bound diene monomer may be selected from 1,3-butadiene, 2-alkyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1, 3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene and / or 1, 3-cyclooctadiene. Preferred bound diene monomers are butadiene and / or isoprene.

At least one α-olefin monomer may be selected from the group consisting of styrene,

2-methylstyrene, 3-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, stylben, 2,4-diisopropylstyrene, 4-tert-butylstyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) ether dimethylaminoethyl, N, N-dimethylaminoethyl styrene, tert-butoxystyrene, vinylpyridine, divinylbenzene, a vinyl silane compound of formula (4) or formula (5) according to claim 5 and / or a mixture thereof. Preferred α-olefin monomers are styrene, divinylbenzene and vinylsilane compounds of formula (4) or formula (5).

In a second aspect, the present invention provides a polymer composition consisting of the polymer blend of the first aspect of the present invention.

The polymer composition of the present invention may also contain at least one filler and optionally at least one vulcanizing agent (or crosslinker). In addition, the polymer composition of the present invention may also contain up to 10 weight percent of at least one diluting oil based on the total weight of the polymer composition.

In a third aspect, the present invention provides a method for preparing a crosslinked elastomeric polymer, said method comprising the following steps:

(1) Preparation of the polymer blend according to the first aspect of the present invention or the polymer composition according to the second aspect of the present invention; (2) adding at least one filler and optionally at least one silicon hydride coupling agent and reacting said mixture, and (3) adding at least one vulcanizing agent and optionally at least one vulcanizing accelerating agent to the mixture of step (2) and crosslinking said mixture.

In a fourth aspect, the present invention provides a crosslinked elastomeric polymer obtainable according to the third aspect of the present invention.

In a fifth aspect, the present invention provides an article consisting of the polymer composition of the second aspect of the present invention or the crosslinked elastomeric polymer of the fourth aspect of the present invention.

Said article according to the invention may be a tire, a tire tread, a sidewall, a conveyor belt, a seal or a flexible hose.

In a sixth aspect, the present invention relates to the use of (I.1) the polymer blend according to the first aspect of the present invention, (I.2) the polymer composition according to the second aspect of the present invention or (I.3) the crosslinked elastomeric polymer according to the fourth aspect of the present invention for the preparation of tire tread or sidewall.

In a seventh aspect, the present invention relates to a polymer set consisting of (II.1) the polymer blend of the first aspect of the present invention or (II.2) the polymer composition of the second aspect of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

POLYMER MIXTURE

The polymer blend of the first aspect of the present invention consists only of the following components:

Component (a) - the first elastomeric polymer, characterized by high molecular weight

In a first embodiment, the component (a) of the polymer blend according to claim 1 is the first elastomeric polymer characterized by high molecular weight obtained by (I) anionic polymerization of at least one bound diene monomer and optionally at least one α-olefin monomer in the presence of a solvent polymerization initiator organic.

In an alternative embodiment, the component (a) of the polymer blend according to claim 1 is the first elastomeric polymer, characterized by high molecular weight, obtained by (I) anionic polymerization of at least one bound diene monomer and optionally at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent and (II) modification (or functionalization) of polymer chains obtained by method (I) by adding and reacting the modifying compound represented by formula (1), formula (2) and / or formula (3) set out below.

Specific monomers and anionic polymerization reaction conditions and modification reaction (if applicable) are described in more detail below.

General information, supplementary information in this disclosure, on polymerization technology using polymerization initiating compounds, polar coordination compounds and accelerating agents (to increase / change the initiator's reactivity, random distribution of aromatic vinyl monomers and / or random distribution and / or change in concentration of 1,2-polybutadiene or 1,2-polyisoprene or 3,4-polyisoprene units introduced into the polymer), the amounts of each compound, suitable monomers, and the appropriate conditions for carrying out the process are described in WO 2009/148932, which has been fully incorporated into this document by reference.

Related price monomers

Representative examples of bound diene monomers include 1,3-butadiene, 2-alkyl-1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene , 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4pentadiene, cyclopentadiene, 2,4-hexadiene and 1,3-cyclooctadiene, and combinations thereof. Preferred bound diene monomers include, but are not limited to, 1,3-butadiene, isoprene and combinations thereof.

G-olefin monomer

In addition to at least one bound diene monomer, at least one α-olefin monomer may optionally participate in the polymerization of component (a). Suitable examples of α-olefin monomers include, but are not limited to, styrene and its derivatives, including C1-4 alkyl substituted styrenes, such as 2-methylstyrene, 3metylostyren, α-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene. α-methylstyrene, stilbene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, winylobenzylodimetyloamina, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimetyloaminoetylostyren. N, N-bis (trialkilosilylo) aminostyrene. tert-butoxystyrene, vinyl pyridine, divinylbenzene, including 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene, a vinyl silane compound of formula (4) or a multivinylaminosilane of formula (5) as defined below and / or a mixture thereof.

<img file="PL3059256T3_D0001.tif" />

x₄ r^with (R ") with₄ (OSi (R_d)₃), pattern (4)

Y4 wherein the Rd element is independently selected from C1-C18 hydrocarbyl; the R element is selected from C1-C6 hydrocarbyl; the Ra element, Rb and Rc are independently selected from hydrogen, methyl ethyl and vinyl; the values ​​of x4 and y4 are independently selected from integers 1 and 2; the value of z4 is an integer selected from 0 and 1, and x4 + Y4 + z4 = 3; R 'is independently selected from C 1 -C 12 alkyl, C2-C12 alkenyl aryl C6-C18, C7-C18 alkylaryl and tri (C1-C6 alkyl, C6-C12 aryl or C7-C18 alkylaryl) silyl, where two R 'groups can be combined to form a ring, and the ring may contain in addition to the Si bonded nitrogen atom, one or more oxygen atoms, nitrogen atom a&gt; N (C 1 -C 6 alkyl) group and a sulfur atom, while one R 'group can be -Si (CRc = CRaRb) (OSi (Rd) 3) y4 (R ") z4, and Ra, Rb, rc rd, R " y4 and z4 are independently as defined above, and y4 + z4 = 2.

In preferred embodiments of the vinylsilane compound of formula (4), the parameters and substituents have the following values:

a) (Rd) 3 is (methyl, methyl, t-butyl) or (phenyl, phenyl, phenyl), or (t-butyl, phenyl, phenyl), or (hexyl, hexyl, hexyl); R 'is independently selected from methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, octyl and benzyl (bonded through a methyl group) or -NR'R' forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R "is methyl; Ra, Rb and Rc are hydrogen and x4 = y4 = z4 = 1;

b) (Rd) 3 is (methyl, methyl, t-butyl) or (hexyl, hexyl, hexyl); the R 'element is independently selected from methyl and ethyl or the -NR'R' element forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R "

is methyl; Ra, Rb and

Rc are hydrogen and x4 = 2, y4 = 1 and z4 = 0;

c) (Rd) 3 is (methyl, methyl, t-butyl) or (hexyl, hexyl, hexyl); the R 'element is independently selected from methyl and ethyl or the -NR'R' element forms a morpholine group, pyrrolidine group, piperidine group or oxazolidine group; R "is methyl; Ra and Rb are hydrogen, Rc is vinyl, and x4 = y4 = z4 = 1.

Preferred embodiments of the vinylsilane compound of formula (4) are (tert-butyldimethylsiloxy) methyl-4-morpholino (vinyl) silane, (tert-butyldimethylsiloxy) (dimethylamino) methyl (vinyl) silane, (tert-butyldimethylsiloxy) (diethylamino) methyl and / (tertbutylodimetylosiloksy) (dibutylamino) methyl (vinyl) silane.

In another preferred embodiment, the vinyl silane compound according to formula (4) is represented by the following formula (4a).

<img file="PL3059256T3_D0002.tif" />

where the R * element is independently selected from the group consisting of C1-C6 alkyl, C6-C12 aryl and C7-C18 alkylaryl, and the other groups and parameters are as defined for formula (4).

Preferable examples of the vinylsilane compound of formula (4a) are (tert-butyldimethylsiloxy) [(trimethylsilyl) propylamino] methyl (vinyl) silane, (Tertbutylodimetylosiloksy) [(trimethylsilyl) -methyl] methyl (vinyl) silane, (Tertbutylodimetylosiloksy) [(trimethylsilyl) ethylamino] methyl (vinyl) silane, (Tertbutylodimetylosiloksy) [(trimethylsilyl) butylamino] methyl (vinyl) silane, (Tertbutylodimetylosiloksy) [(dimetylofenylosilylo) propylamino] methyl (vinyl) silane, (tert-butyldimethylsiloxy) [(dimethylphenylsilyl) ethylamino] methyl (vinyl) silane and (tert-butyldimethylsiloxy) [(dimethylphenylsilyl) methylamino] methyl (vinyl) silane.

The vinyl silane compounds described above are disclosed in detail in Taiwanese (ROC) Patent Application No. 103128797, which is fully incorporated herein by reference.

The multivinylaminosilane compound of formula (5) is defined as follows:

(AND¹) -Bn1 formula (5), where element A¹ is an organic group having at least two amino groups; each element B is independently selected from the group -Si (R⁵¹) (R⁵²) (R⁵³), with elements R⁵¹, R⁵² and R⁵³ are independently selected from vinyl, butadienyl, methyl, ethyl, propyl, butyl and phenyl, provided that at least one of the R elements⁵¹, R⁵² and R⁵³ is selected from vinyl and butadienyl, each B group being a substituent of the A group amino group¹, at least two amino groups of group A¹ are substituted with at least one group B, while the value of n1 is an integer not less than 2, preferably an integer selected from the range of 2 to 6, and all amino groups in group A¹ are tertiary amine groups.

The multivinylaminosilane of formula (5) has at least two amino groups substituted with at least one ethylenically unsaturated B silyl group. The expression "group B is a substituent of the amino group" or "amino group substituted with the B group" as used herein means the bond of the group B to the nitrogen atom of the amino group, i.e.&gt; NSi (R⁵¹) (R⁵²) (R⁵³). Amine group of group A¹ can be substituted with 0, 1 or 2 groups B. All group A amino groups¹ are tertiary amino groups, i.e. groups that do not contain a hydrogen atom. Organic group¹ is preferably a group without polymerization hydrogen. The expression "polymerization hydrogen" is used in the context of the present invention to describe a hydrogen atom that is not inert, i.e. it will react during anionic polymerization of bound dienes, e.g., butadiene or isoprene. Organic group¹ is also preferably a group without electrophilic groups. The expression "electrophilic groups" is used in the context of the present invention to describe a group that will react with lithium n-butyl as a model initiator and / or a live chain during anionic polymerization of bound dienes, e.g. butadiene or isoprene. Electrophilic groups include: alkynes, (Carbo) cations. halogen atoms, Si-O, Si-S, Si-halogen groups, metal-C groups, nitrites, (Thio) -karboksylany. (thio) carboxylic esters, (Thio) anhydride, (Thio) ketones, (Thio) aldehydes, (Thio) cyanates, (Thio) isocyanates, alcohols, thiols, (Thio) sulfates, sulfonates, sulfamates, sulphones sulfoxides imine thioketals, thioacetals, oximes, karbazony, carbodiimides ureas, urethanes, diazonium salts, carbamates, amides, N-oxides, nitro groups nitrosamines, xanthates, phosphanes, phosphates, phosphine phosphonates, boronic acids, boron esters etc.

Even more preferably organic group A¹ is a group that does not contain polymerisation hydrogen or electrophilic groups.

In preferred embodiments, the multivinylaminosilane of formula (5) belongs to the group consisting of:

<img file="PL3059256T3_D0003.tif" />

where each R element is independently selected from B and C 1 -C 6 alkyl or benzyl and the same restrictions and provisions apply for group B as for formula (5).

<img file="PL3059256T3_D0004.tif" />

<img file="PL3059256T3_D0005.tif" />

<img file="PL3059256T3_D0006.tif" />

where each R element is a C 1 -C 6 alkyl group and the same restrictions and provisions apply for group B as for formula (5).

<img file="PL3059256T3_D0007.tif" />

<img file="PL3059256T3_D0008.tif" />

<img file="PL3059256T3_D0009.tif" />

<img file="PL3059256T3_D0010.tif" />

with the same restrictions and provisions for group B as for formula (5).

<img file="PL3059256T3_D0011.tif" />

<img file="PL3059256T3_D0012.tif" />

where each R element is independently selected from B, C 1 -C 4 alkyl and phenyl and the same restrictions and provisions for group B apply as for formula (5).

Most preferably, styrene, α-methylstyrene and / or divinylbenzene, including 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene are used as at least one α-olefin monomer according to claim 1.

Temperature

Typically, polymerization of the monomers, i.e. at least one bound diene monomer and optionally at least one α-olefin monomer described above is carried out at a temperature above 0 ° C. In a preferred embodiment, the polymerization temperature is in the range of 20 ° C to 110 ° C, more preferably in the range of 30 ° C to 95 ° C.

Solvent

An organic solvent may be suitably used in the polymerization reaction. In one embodiment, the solvent used for polymerization is selected from non-polar aromatic and non-aromatic solvents, such as e.g. butane, butene, pentane, cyclohexane, toluene, hexane, heptane and octane. In a preferred embodiment, the solvent is selected from butane, butene, cyclohexane, hexane, heptane, toluene or mixtures thereof.

Solids content in monomers

Preferably, the solids content of the polymerized monomers is from 5 to 35 percent by weight, more preferably from 10 to 30 percent by weight, and most preferably from 15 to 25 percent by weight, based on the total weight of the monomers and solvent. As used herein, the term "total solids content of monomers" (herein referred to as TSC), "solids content of monomers" or similar terms refer to a percentage of the total mass of monomers in relation to the total mass of solvent and monomers (e.g. . 1,3-butadiene and styrene).

Polymerization initiator

The polymerization initiator is a suitable lithium alkyl compound, e.g., lithium ethyl, lithium propyl, lithium n-butyl, lithium sec-butyl, lithium tert-butyl, lithium phenyl, lithium hexyl, 1,4-dilithio-n-butane, a compound represented by formulas below from (6) to (10) or their adducts with Lewis bases. Mixtures of these polymerization initiators may also be used.

<img file="PL3059256T3_D0013.tif" />

where element R^3a is independently selected from -N (R²⁸) R²⁹, C1-C18 alkyl, C6-C18 aryl and aralkyl (C7-C18); element R^4a is independently selected from -N (R^30a) R^31a, alkyl (C1-C18), aryl (C6-C18) and aralkyl (C7-C18); elements of R⁵ and R⁶ are independently selected from hydrogen, C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; element M² is lithium;

_{elements of R}¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ are independently selected from hydrogen, C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; elements of R²⁶, R²⁷, R²⁸, R²⁹, R^30a and R^31a are independently selected from C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; the value of q is selected from integers 1, 2, 3, 4 and 5; the value of r is selected from integers 1, 2 and 3, and the value of a1 is an integer equal to 0 or 1.

In a preferred embodiment, the R elements^3a, R^4a, R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are independently selected from (C 1 -C 18) alkyl; elements of R⁵, R⁶, R¹⁸, R¹⁹, R²⁰ and R²¹ are independently selected from hydrogen and alkyl (C1-C18); elements of R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷are independently selected from hydrogen and alkyl (C1-C6), and the other groups and parameters are as defined for formula (6) and formula (7) above.

Useful aminosilane polymerization initiators of formulas (6) and (7) include the following:

<img file="PL3059256T3_D0014.tif" />

<img file="PL3059256T3_D0015.tif" />

<img file="PL3059256T3_D0016.tif" />

<img file="PL3059256T3_D0017.tif" />

<img file="PL3059256T3_D0018.tif" />

<img file="PL3059256T3_D0019.tif" />

or Lewis base adducts thereof and / or mixtures thereof. The aminosilane polymerization initiators described above are disclosed in detail in WO 2014/040640, which is fully incorporated herein by reference.

Alternatively, the compound represented by the formula (8) can be used as the polymerization initiator.

R¹n

R _z1 (OSiR^1b3)_x1 /^S&lt;2b / (NO^2b2)_y1 / ¹ABOUT_mand formula (8) wherein each R ° element is independently selected from C1-C6 alkyl, C2-C6 alkenyl, C7-C10 alkylaryl and C6-C10 aryl, preferably independently selected from C1-C4 alkyl, C7 alkylaryl and C6 aryl; element R^{1 '} is an optionally substituted methylene group; each element of R^1b is independently selected from C1-C10 alkyl, C7-C10 alkylaryl and C6-C10 aryl, preferably selected independently from C1-C6 alkyl and C6-C10 aryl; each element of R^2b is independently selected from C1-C10 alkyl, C7-C10 alkylaryl and C6-C10 aryl, preferably selected independently from C1-C8 alkyl and C7-C8 alkylaryl, with the R groups^2b they can be joined together to form a ring together with the bonded Si nitrogen atom; elements of R^3b and R^4b are independently selected from hydrogen, methyl, ethyl, propyl, butyl and vinyl; each element of R^5b is independently selected from C1-C5 alkyl, C7-C12 alkylaryl and C6-C12 aryl, preferably selected independently from C1-C5 alkyl, C7-alkylaryl and C6-aryl, and more preferably selected independently from C1-C5 alkyl; element R^6b is selected from C1-C6 alkyl, phenyl and benzyl; M is lithium; a1&gt; 1; b1&gt; 0; a1 + b1 &lt;10; m1 = 0 or 1; n = 0 to 12; X1 = 0, 1 or 2; yx = 1, 2 or 3; z1 = 0, 1 or 2; x1 + y1 + z1 = 3; or x1 + y1 + z1 = 2 when the silicon atom of the aminosilyl group is double bonded to benzene rings via R groups^{1 '}or single bonds; provided that, when m1 = 1, then n1 = 1 to 12 and when m1 = 0, then n1 = 0 and x1 = 1 or 2; wherein the aminosilyl groups may be bonded to any of the two benzene rings, the individual ammonosilyl groups may be different from each other, and the R group (s)^5b may be associated with any of the two benzene rings.

In a preferred embodiment, each R ° element is independently selected from C1-C5 alkyl and C6 aryl; each element of R^1b is independently selected from C1C4 alkyl and C6 aryl; each element of R^2b is independently selected from C1-C8 alkyl and C7-C10 alkylaryl; elements of R^3b and R^4b are hydrogen; each element of R^5b is independently selected from C1-C4 alkyl; element R^6b is selected from methyl, ethyl, tert-butyl, n-butyl, sec-butyl, phenyl and benzyl; a1 = 1 or 2, b1 = 0 or 1, m1 = 0 and R¹'is methylene, and n1 = 1, 2 or 3, x1 = 0 or 1, y1 = 1 or 2 and z1 = 0 or 1, while the other groups and parameters are as defined for formula (8) above.

The preparation of the polymerization initiators described above of formula (8) is disclosed in detail in document PCT / EP2014 / 065027, which is fully incorporated herein by reference.

Alternatively, the compound of formula (9) may be used as the polymerization initiator.

<img file="PL3059256T3_D0020.tif" />

where each element M^1c is lithium; each element of R^1c is independently selected from C1-C100 alkyl and C2-C100 alkenyl, optionally substituted with at least one C6-C12 aryl group, and optionally bonded to carbon C via a maximum of 25 monomer units selected from bonded diene monomers and aromatic vinyl compounds, in particular butadiene , isoprene and styrene; each element of R^12c is independently selected from hydrogen, alkyl (C1-C10), aryl (C6-C12) and alkylaryl (C7-C18); each element of Y^1c is independently selected from nitrogen, sulfur and silicon; elements of R^3c, R^4c and R^5c are independently selected from alkyl (C1-C18), di (C1-C6) alkylamino (only when element Y^1c is a silicon atom), aryl (C6-C18), alkylaryl (C7-C18) and, when element Y^1c is not a silicon atom of the -SiR group^14cR^15cR^16c, with elements of R^14c, R^15c and R^16c are independently selected from alkyl (C1-C18), aryl (C6-C18) and alkylaryl (C7-C18); n3 and o3 are integers selected from 0 and 1; and in addition n3 + o3 = 1 when Y^1c= N, n3 = o3 = 0 when Y^1c= S and n3 + o3 = 2 when Y^1c= Si; m3 is an integer selected from 0, 1, 2 and 3; the K element is selected from nitrogen and&gt; CH; each element E³ is independently selected from alkyl (C1-C18), aryl (C6-C18), alkylaryl (C7-C18) and the group -Y^3c(R^9c) (R^10c) T3 (R^11c) u3, with the element Y^3c is selected from nitrogen, sulfur and silicon; elements of R^9c, R^10cand R^11c are independently selected from alkyl (C1-C18), di (C1-C6) alkylamino (only when element Y^3c is a silicon atom), aryl (C6-C18), alkylaryl (C7-C18) and, when element Y^3c is not a silicon atom of the -SiR group^20cR^21cR^22c, with elements of R^20c, R^21c and R^22c are independently selected from alkyl (C1-C18), aryl (C6-C18) and alkylaryl (C7-C18); t3 and u3 are integers selected from 0 and 1, while t3 + u3 = 1 when Y^3c= N, t3 = u3 = 0 when Y^3c= S and t3 + u3 = 2 when Y^3c= Si; s3 is an integer selected from 0, 1 and 2; every element of F³ is independently selected from alkyl (C1-C18), aryl (C6-C18), alkylaryl (C7-C18) and -Y^2c(R^6c) (R^7c) Q3 (R^8c) r3, with the element Y^2c is selected from nitrogen, sulfur and silicon; elements of R^6c, R^7c and R^8c are independently selected from alkyl (C1-C18), di (C1-C6) alkylamino (only when element Y^2cis a silicon atom), aryl (C6-C18), alkylaryl (C7-C18) and, when element Y^2c is not a silicon atom of the -SiR group^17cR^18cR^19c, with elements of R^17c, R^18c and R^19c are independently selected from alkyl (C1-C18), aryl (C6-C18) and alkylaryl (C7-C18); q3 and r3 are integers selected from 0 and 1, while q3 + r3 = 1 when Y^2c= N, q3 = q3 = r3 = 0 when Y^2c= S, and q3 + r3 = 2 when Y^2c= Si and p3 is an integer selected from 0, 1, 2 and 3.

In a preferred embodiment, each R element^1c is the same and selected from (C 1 -C 10) alkyl; each element of R^12c is independently selected from hydrogen and (C 1 -C 10) alkyl, preferably hydrogen; elements of R^3c, R^4c and R^5c are independently selected from alkyl (C1C18) and when the Y element^1c is not a silicon atom of the -SiR group^14cR^15cR^16c, with elements of R^14c, R^15c_{and R}^16c are independently selected from (C 1 -C 18) alkyl; each E3 element is independently selected from (C1-C18) alkyl; each F3 element is independently selected from the group -Y^2c(R^6c) (R^7c) Q3 (R^8c) r3, with elements R^6c, R^7c and R^8c are independently selected from alkyl (C1-C18) and when the Y element^2c is not a silicon atom, -SiR^17cR^18cR^19c, with elements of R^17c, R^18c and R^19c are independently selected from (C 1 -C 18) alkyl; p3 is an integer chosen from 1, 2 and 3, while the other groups and parameters are as defined for formula (9) above.

Polymerization initiators of formula (9) and their preparation are disclosed in the document

PCT / EP2013 / 065399, which has been fully incorporated into this document by reference.

Alternatively, the polymerization initiator of formula (10) can be used.

<img file="PL3059256T3_D0021.tif" />

where each element R³¹ is independently selected from hydrogen, alkyl (C1-C10), aryl (C6-C12) and aralkyl (C7-C18); each element of R³², R³³ and R³⁴ is independently selected from hydrogen, alkyl (C1-C18) and alkoxy (C1-C18); each element of R⁴¹ is independently selected from alkyl (C1-C100) and alkenyl (C2-C100), with each R element⁴¹ is optionally substituted with one to three aryl groups (C6-C12) and is optionally linked to the skeleton of formula (10) via an oligomer chain composed of a maximum of 25 monomer units selected from the group consisting of bound dienes, in particular 1,3 -butadiene and isoprene, and vinyl aromatic compounds, in particular styrene and divinylbenzene; element M² is lithium, and the values ​​of k, 1 and q are integers selected independently from 0, 1, 2 and 3.

In a preferred embodiment, the R element⁴¹ is selected from alkyl (C1-C10); each element of R³¹ is independently selected from hydrogen and (C1-C10) alkyl preferably from hydrogen; elements of R³² and R³⁴ are the same and are selected from hydrogen and alkyl (C1C18) and each R element³³ is independently selected from hydrogen and alkyl (C1-C18). The polymerization initiators of formula (10) described above are disclosed in detail in patent application EP 151 151 112.8, which has been fully incorporated herein by reference.

Most preferably, n-butyl lithium, sec-lithium n-butyl or a compound of formula (6) or formula (7) are used in particular

<img file="PL3059256T3_D0022.tif" />

. The above initiators can be used as initiators alone or in combination as a mixture of two or more types of compounds.

Modification

In one embodiment, component (a) is also functionalized with at least one compound of formula (1) to (3) or formula (11) to (15) as defined below.

(R *** O) x (R **) y Si-AS-SiR ** 3 formula (1), wherein each R ** element is independently selected from C 1 -C 16 alkyl or alkylaryl; the R *** element is independently selected from C 1 -C 4 alkyl; element A is selected from C6-C18 aryl, C7-C50 alkylaryl, C1-C50 alkyl and C2-C50 dialkylether and optional R ** elements, R *** or A may be independently substituted with at least one group selected from C 1 -C 4 alkyl, C1-C4 alkoxy, aryl C6-C12, C7-C16 alkylaryl, di (C1-C7 hydrocarbyl) amino group, bis (tri (C 1 -C 12 alkyl) silyl) amino group, tris (C1-C7 hydrocarbyl) silyl and C1-C12 thioalkyl; x is an integer selected from 1, 2 and 3; y is an integer selected from 0, 1 and 2, provided that x + y = 3.

Even more preferably, each of the elements R *** is independently selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl; each R ** element is independently selected from C 1 -C 6 alkyl, C 6 -C 12 aryl or C 7 -C 10 alkylaryl; and element A is - (CH2) N-, where N is an integer selected from 1, 2, 3, 4, 5 or 6. Preferred examples of compounds represented by formula (1) serving as modifying agents include, but are not limited to:

(MeO)₃Si- (CH₂)₃-S-SiMe₃, (EtO)₃Si- (CH₂)₃-S-SiMe₃, (PrO)₃Si- (CH₂)₃-S-SiMe₃, (BuO)₃Si- (CH₂)₃-S-SiMe₃(MeO)₃Si- (CH₂)₂-S-SiMe₃, (EtO)₃Si- (CH₂)₂-S-SiMe₃, (PrO)₃Si- (CH₂)₂-S-SiMe₃, (BuO)₃Si- (CH₂)₂-S-SiMe₃, (MeO)₃sich₂-S-SiMe₃, (EtO)₃Si-CH₂-S-SiMe₃, (PrO)₃Si-CH₂-S-SiMe₃, (BuO)₃Si-CH₂-S-SiMe₃, (MeO)₃Si-CH₂-CMe₂CH₂-S21

SiMe₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-SiMe₃, (PrO)₃Si-CH2-CMe2-CH2-S-SiMe₃, (BuO)₃Si-CH2-CMe2-CH2-S-SiMe₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (BuO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (MeO)₃Si- (CH₂)₃-S-Sietam₃, (EtO)₃Si- (CH₂)₃-S-Sietam₃, (PrO)₃Si- (CH₂)₃-S-Sietam₃, (BuO)₃Si- (CH₂)₃-S-Sietam₃, (MeO)₃Si- (CH₂)₂-S-Sietam₃, (EtO)₃Si- (CH₂)₂-S-Sietam₃, (PrO)₃Si- (CH₂)₂-S-Sietam₃, (BuO)₃Si- (CH₂)₂-S-Sietam₃, (MeO)₃Si-CH₂-S-Sietam₃, (EtO)₃Si-CH₂-S-Sietam₃, (PrO)₃Si-CH₂-S-Sietam₃, (BuO)₃Si-CH₂-S-Sietam₃, (MeO)₃Si-CH₂-CMe₂CH₂-S-Sietam₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-Sietam₃, (PrO)₃Si-CH₂-CMe₂CH₂-S-Sietam₃, (BuO)₃sich₂-CMe₂CH₂-S-Sietam₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (PrO)₃sich₂-C (H) Me-CH₂-S-Sietam₃ (BuO)₃Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (MeO)₃Si- (CH₂)₃-S-SiMe₂tBu, (EtO)₃Si- (CH₂)₃-SSiMe₂tBu, (PrO)₃Si- (CH₂)₃-S-SiMe₂tBu, (BuO)₃Si- (CH₂)₃-S-SiMe₂tBu, (MeO)₃Si- (CH₂)₂-S-SiMe₂tBu, (EtO)₃Si- (CH₂)₂-S-SiMe₂tBu, (PrO)₃Si- (CH₂)₂-S-SiMe₂tBu, (BuO)₃Si- (CH₂)₂-S-SiMe₂tBu, (MeO)₃Si-CH₂-S-SiMe₂tBu, (EtO)₃Si-CH₂-S-SiMe₂tBu, (PrO)₃Si-CH₂-S-SiMe₂tBu, (BuO)₃Si-CH₂-S-SiMe₂tBu, (MeO)₃Si-CH₂-CMe₂CH₂-SSiMe₂tBu, (EtO)₃Si-CH₂-CMe₂CH₂-S-SiMe₂tBu, (PrO)₃Si-CH₂-CMe₂CH₂-S-SiMe₂tBu, (BuO)₃Si-CH₂-CMe₂CH₂-SSiMe₂tBu, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, (PrO)₃Si-CH₂-C (H) MeCH₂-S-SiMe₂tBu, (BuO)₃Si-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, (MeO)₃MeSi- (CH₂)₃-S-SiMe₃, (EtO)₂MeSi- (CH₂)₃-SSiMe₃, (PrO)₂MeSi- (CH₂)₃-S-SiMe₃, (BuO)₂MeSi- (CH₂)₃-S-SiMe₃, (MeO)₂MeSi- (CH₂)₂-S-SiMe₃, (EtO)₂MeSi- (CH₂)₂-S-SiMe₃, (PrO)₂MeSi- (CH₂)₂-S-SiMe₃, (BuO)₂MeSi- (CH₂)₂-S-SiMe₃, (MeO)₂MESI-CH₂-S-SiMe₃, (EtO)₂MESI-CH₂-S-SiMe₃, (PrO)₂MESI-CH₂-S-SiMe₃, (BuO)₂MESI-CH₂-S-SiMe₃, (MeO)₂MESI-CH₂-CMe₂CH₂-SSiMe₃, (EtO)₂MESI-CH₂-CMe₂CH₂-S-SiMe₃, (PrO)₂MESI-CH₂-CMe₂CH₂-S-SiMe₃, (BuO)₂MESI-CH₂-CMe₂CH₂-SSiMe₃, (MeO)₂MESI-CH₂-C (H) Me-CH₂-S-SiMe₃, (EtO)₂MESI-CH₂-C (H) Me-CH₂-S-SiMe₃, (PrO)₂MESI-CH₂-C (H) MeCH₂-S-SiMe₃, (BuO)₂MESI-CH₂-C (H) Me-CH₂-S-SiMe₃, (MeO)₂MeSi- (CH₂)₃-S-Sietam₃, (EtO)₂MeSi- (CH₂)₃-S-Sietam₃, (PrO)₂MeSi- (CH₂)₃-S-Sietam₃, (BuO)₂MeSi- (CH₂)₃-S-Sietam₃, (MeO)₂MeSi- (CH₂)₂-S-Sietam₃, (EtO)₂MeSi- (CH₂)₂-S-Sietam₃, (PrO)₂MeSi- (CH₂)₂-S-Sietam₃, (BuO)₂MeSi- (CH₂)₂-S-Sietam₃, (MeO)₂MESI-CH₂-S-Sietam₃, (EtO)₂MESI-CH₂-S-Sietam₃, (PrO)₂MESI-CH₂-S-Sietam₃, (BuO)₂MESI-CH₂-S-Sietam₃, (MeO)₂MESI-CH₂-CMe₂CH₂-S-Sietam₃, (EtO)₂MeSiCH₂-CMe₂CH₂-S-Sietam₃, (PrO)₂MESI-CH₂-CMe₂CH₂-S-Sietam₃, (BuO)₂MESI-CH₂-CMe₂CH₂-S-Sietam₃, (MeO)₂MeSiCH₂-C (H) Me-CH₂-S-Sietam₃, (EtO)₂MESI-CH₂-C (H) Me-CH₂-S-Sietam₃, (PrO)₂MESI-CH₂-C (H) Me-CH₂-S-Sietam₃, (BuO)₂MESI-CH₂-C (H) Me-CH₂-S-Sietam₃, (MeO)₂MeSi- (CH₂)₃-S-SiMe₂tBu, (EtO)₂MeSi- (CH₂)₃-S-SiMe₂tBu, (PrO)₂MeSi- (CH₂)₃-S-SiMe₂tBu, (BuO)₂MeSi- (CH₂)₃-S-SiMe₂tBu, (MeO)₂MeSi- (CH₂)₂-S-SiMe₂tBu, (EtO)₂MeSi- (CH₂)₂-S-SiMe₂tBu, (PrO)₂MeSi- (CH₂)₂-S-SiMe₂tBu, (BuO)₂MeSi- (CH₂)₂-S-SiMe₂tBu, (MeO)₂MeSiCH₂-S-SiMe₂tBu, (EtO)₂MESI-CH₂-S-SiMe₂tBu, (PrO)₂MESI-CH₂-S-SiMe₂tBu, (BuO)₂MESI-CH₂-S-SiMe₂tBu, (MeO)₂MESI-CH₂-CMe₂CH₂-S-SiMe₂tBu, (EtO)₂MESI-CH₂-CMe₂CH₂-S-SiMe₂tBu, (PrO)₂MESI-CH₂-CMe₂CH₂-SSiMe₂tBu, (BuO)₂MESI-CH₂-CMe₂CH₂-S-SiMe₂tBu, (MeO)₂MESI-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, (EtO)₂MeSiCH₂-C (H) Me-CH₂-S-SiMe₂tBu, (PrO)₂MESI-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, (BuO)₂MESI-CH₂-C (H) Me-CH₂-SSiMe₂tBu, (MeO) Me₂Si- (CH₂)₃-S-SiMe₃, (EtO) Me₂Si- (CH₂)₃-S-SiMe₃, (PrO) Me₂Si- (CH₂)₃-S-SiMe₃, (BuO) Me₂Si- (CH₂)₃-S-SiMe₃, (MeO) Me₂Si- (CH₂)₂-S-SiMe₃, (EtO) Me₂Si- (CH₂)₂-S-SiMe₃, (PrO) Me₂Si- (CH₂)₂-SSiMe₃, (BuO) Me₂Si- (CH₂)₂-S-SiMe₃, (MeO) Me₂Si-CH₂-S-SiMe₃, (EtO) Me₂Si-CH₂-S-SiMe₃, (PrO) Me₂Si-CH₂-S-SiMe₃, (BuO) Me₂Si-CH₂-S-SiMe₃, (MeO) Me₂Si-CH₂-CMe₂CH₂-S-SiMe₃, (EtO) Me₂Si-CH₂-CMe₂CH₂-S-SiMe₃, (PrO) Me₂sich₂-CMe₂CH₂-S-SiMe₃, (BuO) M ©₂Si-CH₂© -cm₂CH₂-S-SiM ©₃, (M © O) M ©₂Si-CH₂-C (H) M © -CH₂-S-SiM ©₃, (EtO) Me₂Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (PrO) Me₂Si-CH₂-C (H) Me-CH₂-S-SiMe₃, (BuO) Me₂Si-CH₂-C (H) Me-CH₂-SSiMe₃, (MeO) Me₂Si- (CH₂)₃-S-Sietam₃, (EtO) Me₂Si- (CH₂)₃-S-Sietam₃, (PrO) Me₂Si- (CH₂)₃-S-Sietam₃, (BuO) Me₂Si- (CH₂)₃-SSiEt₃, (MeO) Me₂Si- (CH₂)₂-S-Sietam₃, (EtO) Me₂Si- (CH₂)₂-S-Sietam₃, (PrO) Me₂Si- (CH₂)₂-S-Sietam₃, (BuO) Me₂Si- (CH₂)₂-SSiEt₃, (MeO) Me₂Si-CH₂-S-Sietam₃, (EtO) Me₂Si-CH₂-S-Sietam₃, (PrO) Me₂Si-CH₂-S-Sietam₃, (BuO) Me₂Si-CH₂-S-Sietam₃, (MeO) Me₂Si-CH₂-CMe₂CH₂-S-Sietam₃, (EtO) Me₂Si-CH₂-CMe₂CH₂-S-Sietam₃, (PrO) Me₂Si-CH₂-CMe₂CH₂-S-Sietam₃, (BuO) Me₂Si-CH₂-CMe₂CH₂-S-Sietam₃, (MeO) Me₂Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (EtO) Me₂Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (PrO) Me₂Si-CH₂-C (H) Me-CH₂-S-SiEt3, (EtO) Me₂Si- (CH₂)₃-S-SiMe₂tBu, (MeO) Me₂Si- (CH₂)₂-S-SiMe₂tBu, (MeO) Me₂Si- (CH₂)₃-S-SiMe₂tBu, (BuO) Me₂Si- (CH₂)₃-S-SiMe₂tBu, (PrO) Me₂Si- (CH₂)₂-S-SiMe₂tBu, (BuO) Me₂Si-CH₂-C (H) Me-CH₂-S-Sietam₃, (PrO) Me₂Si- (CH₂)₃-S-SiMe₂tBu, (EtO) Me₂Si- (CH₂)₂-S-SiMe₂tBu, (BuO) Me₂Si- (CH₂)₂-S-SiMe₂tBu, (MeO) Me₂Si-CH₂-S-SiMe₂tBu, (EtO) Me₂Si-CH₂-S-SiMe₂tBu, (PrO) Me₂Si-CH₂-SSiMe₂tBu, (BuO) Me₂Si-CH₂-S-SiMe₂tBu, (MeO) Me₂Si-CH₂CMe₂CH₂-S-SiMe₂tBu, (EtO) Me₂Si-CH₂-CMe₂CH₂-SSiMe₂tBu, (PrO) Me₂Si-CH₂-CMe₂CH₂-S-SiMe₂tBu, (BuO) Me₂Si-CH₂-CMe₂CH₂-S-SiMe₂tBu, (MeO) Me₂sich₂-C (H) Me-CH₂-S-SiMe₂tBu, (EtO) Me₂Si-CH₂-C (H) Me-CH₂-S-SiMe₂tBu, SiMe₂tBu, (BuO) Me₂Si-CH₂-C (H) Me-CH₂-S-SiMe₂Bu.

(PrO) Me₂Si-CH₂-C (H) Me-CH₂- More preferably, the sulfanylsilane compound of formula (1) is selected from (MeO) 3Si- (CH2) 3-S-SiMe2tBu, (MeO) 2 (CH3) Si- (CH2) 3-S-SiMe2tBu, (MeO) ( Me) 2Si- (CH2) 3-S-SiMe2tBu and mixtures thereof.

Alternatively, a compound of formula (2) may be used.

((R¹O) x2, (R²) Y2, Si-R³-S) s2, M * (R⁴) t2, (X *) u2, formula (2), where the element M * is silicon or tin; x2 'is an integer selected from 1, 2 and 3; y2 'is an integer selected from 0, 1 and 2; wherein x2 '+ y2' = 3; the value of s2 'is an integer selected from 2, 3 and 4; t2 'is an integer selected from 0, 1 and 2; the value of u2 'is an integer selected from 0, 1 and 2; wherein s2 '+ t2' + u2 '= 4; element R¹ is independently selected from hydrogen and (C 1 -C 6) alkyl; element R² is independently selected from alkyl (C1-C16), alkylaryl (C7-C16) and arylalkyl (C7-C16); element R³ is divalent and is independently selected from alkyl (C1-C16), alkylarylalkyl (C8-C16), arylalkyl (C7-C16) and alkylaryl (C7-C16), and each group may be substituted with at least one of the following groups: tertiary amino, silyl, aralkyl (C7-C18) and aryl (C6-C18);

element R⁴ is independently selected from alkyl (C1-C16) and alkylaryl (C7-C16); X * is independently selected from chloride, bromide and -OR^{* 5}; with the R element^{* 5} is selected from alkyl (C1-C16) and arylalkyl (C7-C16).

In a preferred embodiment, the M * element is a silicon atom; element R³ is divalent and is alkyl (C1-C16); X * means -OR^{* 5}, with the element R^{* 5}is selected from alkyl (C1-C4); elements of R¹, R² and R⁴ are independently selected from (C 1 -C 4) alkyl; the values ​​of s2 'and t2' are 2 and the value of u2 'is 0; while the value of x2 'is 2 and the value of y2' is 1; while the other groups and parameters are consistent with the definition given for formula (2).

Specific preferred types of the silane sulfide modifier according to the present invention include the following compounds and their corresponding Lewis base adducts:

(MeO)₃Si- (CH₂)₃-S-Si (Me)₂-S- (CH₂)₃-Si (OMe) 3, (MeO)₃Si- (CH₂)₃-S-Si (Et)₂-S- (CH₂) 3-Si (OMe)₃, (MeO)₃Si- (CH₂)₃-S-Si (Bu)₂-S- (CH₂)₃-Si (OMe)₃, (EtO)₃Si- (CH₂)₃-S-Si (Me)₂-S- (CH₂)₃-Si (OEt)₃, (EtO)₃Si- (CH₂)₃-SSi (Et)₂-S- (CH₂)₃-Si (OEt)₃.

Si (Me)₂-S- (CH₂)₃-Si (OPr)

Si (Bu)₂-S- (CH₂)₃-Si (OPr)₃.

Si (Et)₂-S- (CH₂)₂-Si (OMe)₃.

Si (Me)₂-S- (CH₂)₂-Si (OEt)₃.

Si (Bu)₂-S- (CH₂)₂-Si (OEt)₃.

Si (Et)₂-S- (CH₂)₂-Si (OPr)₃, (PrO)₃Si- (CH₂)₃-S (PrO)₃Si- (CH₂)₃-S (MeO)₃Si- (CH₂)₂-S (EtO)₃Si- (CH₂)₂S (EtO)₃Si- (CH₂)₂-S (PrO)₃Si- (CH₂)₂-S (EtO)₃Si- (CH₂)₃-S-Si (Bu)₂-S- (CH₂)₃-Si (OEt)₃, (PrO)₃Si- (CH₂)₃-S-Si (Et)₂-S- (CH₂)₃-Si (OPr)₃, (MeO)₃Si- (CH₂)₂-S-Si (Me)₂-S - (- CH₂)₂-Si (OMe)₃, (MeO)₃Si- (CH₂)₂-S-Si (Bu)₂-S- (CH₂)₂-Si (OMe)₃, (EtO)₃Si- (CH₂)₂-S-Si (Et)₂-S- (CH₂)₂-Si (OEt)₃, (PrO)₃Si- (CH₂)₂-S-Si (Me)₂-S- (CH₂)₂-Si (OPr)₃, (PrO)₃Si- (CH₂)₂-S-Si (Bu)₂-S- (CH₂)₂-Si (OPr)₃, (MeO)₃Si-CH₂-S-Si (Me)₂-SCH₂-Si (OMe)₃, (MeO)₃Si-CH₂-S-Si (Et)₂-S-CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-S-Si (Bu)₂-S-CH₂-Si (OMe)₃, (EtO)₃sich₂-S-Si (Me)₂-S-CH₂-Si (OEt)₃(EtO)₃Si-CH₂-S-Si (Et)₂-S-CH₂-Si (OEt)₃(EtO)₃Si-CH₂-S-Si (Bu)₂-S-CH₂-Si (OEt)₃, (PrO)₃Si-CH₂-S-Si (Me)₂-S-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-S-Si (Et)₂-S-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-S-Si (Bu)₂-SCH₂-Si (OPr)₃, (MeO)₃Si-CH₂-CMe₂CH₂-S-Si (Me)₂-S-CH₂-CMe₂CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-CMe₂CH₂-SSi (Et)₂-S-CH₂-CMe₂CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OMe)₃, (EtO)₃sich₂-CMe₂CH₂-S-Si (Me)₂-S-CH₂-CMe₂CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-Si (Et)₂-SCH₂-CMe₂CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OEt)₃, (PrO)₃sich₂-CMe₂CH₂-S-Si (Me)₂-S-CH₂-CMe₂CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-CMe₂CH₂-S-Si (Et)₂-SCH₂-CMe₂CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OPr)₃, (MeO)₃sich₂-C (H) Me-CH₂-S-Si (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-Si (Et)₂-SCH₂-C (H) Me-CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-Si (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₃, (EtO)₃sich₂-C (H) Me-CH₂-S-Si (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-Si (Et)₂-S-CH₂-C (H) MeCH₂-Si (OEt)₃, (EtO)₃Si-CH₂- (H) Me-CH₂-S-Si (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-SSi (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-S-Si (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-S-Si (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₃, (MeO)₂ (Me) Si- (CH₂)₃-SSi (Me)₂-S- (CH₂)₃-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₃-S-Si (Et)₂-S- (CH₂)₃-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₃-S-Si (Bu)₂-S- (CH₂)₃-Si (OMe)₂(Me), (EtO)₂(Me) Si- (CH₂)₃-S-Si (Me)₂-S- (CH₂)₃-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₃-S-Si (Et)₂-S- (CH₂)₃-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂) 3-S-Si (Bu)₂-S- (CH₂)₃-Si (OEt)₂(Me), (PrO)₂(Me) Si- (CH₂)₃-S-Si (Me)₂-S- (CH₂)₃-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₃-S-Si (Et)₂-S- (CH₂)₃-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₃-S-Si (Bu)₂-S- (CH₂)₃-Si (OPr)₂(Me), (MeO)₂(Me) Si- (CH₂)₂-S-Si (Me)₂-S- (CH₂)₂-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₂-S-Si (Et) 2-S- (CH₂)₂-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH2)₂-SSi (Bu)₂-S- (CH₂)₂-Si (OMe)₂(Me), (EtO)₂(Me) Si- (CH₂)₂-S-Si (Me)₂-S- (CH₂)₂-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₂-SSi (Et)₂-S- (CH₂)₂-Si (OEt)₂(Me), (EtO) 2 (Me) Si- (CH₂)₂-S-Si (Bu)₂-S- (CH₂)₂-Si (OEt)₂(Me), (PrO)₂(Me) Si- (CH₂)₂-SSi (Me)₂-S- (CH₂)₂-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₂-S-Si (Et)₂-S- (CH₂)₂-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₂-SSi (Bu)₂-S- (CH₂)₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-S-Si (Me)₂-S-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-SSi (Et)₂-S-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-S-Si (Bu)₂-S-CH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-SSi (Me)₂-S-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-S-Si (Et)₂-S-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-S-Si (Bu)₂-SCH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-S-Si (Me)₂-S-CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-S-Si (Et)₂-SCH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-S-Si (Bu)₂-S-CH₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-CMe₂CH₂-SSi (Me)₂-S-CH₂-CMe₂CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Et)₂-SCH₂-CMe₂CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Me)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Et)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Me)₂-S-CH₂-CMe₂CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Et) ₂-S-CH₂-CMe₂CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Si (Bu)₂-S-CH₂-CMe₂CH₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) MeCH₂-S-Si (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Bu)₂-S-CH₂-C (H) MeCH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) sich₂-C (H) Me-CH₂-S-Si (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Bu)₂-SCH₂-C (H) Me-CH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Si (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-C (H) Me-CH₂-SSi (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me), (MeO)₃Si- (CH₂) 3-S-Sn (Me)₂-S- (CH₂)₃-Si (OMe) 3, (MeO)₃Si- (CH₂)₃-SSn (Et)₂-S- (CH₂)₃-Si (OMe)₃.

Sn (Me)₂-S- (CH₂)₃-Si (OEt)₃.

Sn (Bu)₂-S- (CH₂)₃-Si (OEt)₃.

Sn (Et)₂-S- (CH₂)₃Si (get drunk₃.

Sn (Me)₂-S- (CH₂)₂-Si (OMe)₃.

Sn (Bu)₂-S- (CH₂)₂-Si (OMe)₃.

Sn (Et)₂-S- (CH₂)₂-Si (OEt)₃.

Sn (Me)₂-S- (CH₂)₂Si (get drunk₃.

Sn (Bu)₂-S- (CH₂)₂-Si (OPr)₃, (EtO)₃Si- (CH₂)₃-S (EtO)₃Si- (CH₂)₃-S (PrO)₃Si (CN₂)₃-S (MeO)₃Si- (CH₂)₂-S (MeO)₃Si- (CH₂)₂-S (EtO)₃Si- (CH₂)₂-S (PrO)₃Si- (CH₂)₂-S (PrO)₃Si- (CH₂)₂-S (MeO)₃Si-CH₂-S-Sn (Et)₂-S (MeO)₃Si- (CH₂)₃-S-Sn (Bu)₂-S- (CH₂)₃-Si (OMe)₃, (EtO)₃Si- (CH₂)₃-S-Sn (Et)₂-S- (CH₂)₃-Si (OEt)₃, (PrO)₃Si- (CH₂)₃-S-Sn (Me)₂-S- (CH₂)₃-Si (OPr), (PrO)₃Si- (CH₂)₃-S-Sn (Bu)₂-S- (CH₂)₃Si (get drunk₃(MeO)₃Si- (CH₂)₂-S-Sn (Et)₂-S- (CH₂)₂-Si (OMe)₃, (EtO)₃Si- (CH₂)₂-S-Sn (Me)₂-S- (CH₂)₂-Si (OEt)₃, (EtO)₃Si- (CH₂)₂-S-Sn (Bu)₂-S- (CH₂)₂-Si (OEt)₃, (PrO)₃Si- (CH₂)₂-S-Sn (Et)₂-S- (CH₂)₂-Si (OPr)₃, (MeO)₃Si-CH₂-S-Sn (Me)₂-S-CH₂-Si (OMe)₃.

CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-S-Sn (Bu)₂-S-CH₂-Si (OMe)₃, (EtO)₃Si-CH₂-S-Sn (Me)₂-S-CH₂-Si (OEt)₃, (EtO)₃sich₂-S-Sn (Et)₂-S-CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-S-Sn (Bu)₂-S-CH₂-Si (OEt)₃, (PrO)₃Si-CH₂-S-Sn (Me)₂-SCH₂-Si (OPr)₃, (PrO)₃Si-CH₂-S-Sn (Et)₂-S-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-S-Sn (Bu)₂-S-CH₂-Si (OPr)₃, (MeO)₃sich₂-CMe₂CH₂-S-Sn (Me)₂-S-CH₂-CMe₂CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-CMe₂CH₂-S-Sn (Et)₂-SCH₂-CMe₂CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-CMe₂CH₂-S-Sn (Bu)₂-S-CH₂-CMe₂CH₂-Si (OMe)₃, (EtO)₃sich₂-CMe₂CH₂-S-Sn (Me)₂-S-CH₂-CMe₂CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-Sn (Et)₂-SCH₂-CMe₂CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-CMe₂CH₂-S-Sn (Bu)₂-S-CH₂-CMe₂CH₂-Si (OEt)₃, (PrO)₃sich₂-CMe₂CH₂-S-Sn (Me)₂-S-CH₂-CMe₂CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-CMe₂CH₂-S-Sn (Et)₂-SCH₂-CMe₂CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-CMe₂CH₂-S-Sn (Bu)₂-S-CH₂-CMe₂CH₂-Si (OPr)₃, (MeO)₃sich₂-C (H) Me-CH₂-S-Sn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Et)₂-SCH₂-C (H) Me-CH₂-Si (OMe)₃, (MeO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₃, (EtO)₃sich₂-C (H) Me-CH₂-S-Sn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Et)₂-SCH₂-C (H) Me-CH₂-Si (OEt)₃, (EtO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₃, (PrO)₃sich₂-C (H) Me-CH₂-S-Sn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Et)₂-SCH₂-C (H) Me-CH₂-Si (OPr)₃, (PrO)₃Si-CH₂-C (H) Me-CH₂-S-Sn (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₃, (MeO)₂(Me) Si- (CH₂)₃-S-Sn (Me)₂-S- (CH₂)₃-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₃-SSn (Et)₂-S- (CH₂)₃-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₃-S-Sn (Bu)₂S- (N₂)₃-Si (OMe)₂(Me), (EtO)₂(Me) Si- (CH₂)₃-SSn (Me)₂-S- (CH₂)₃-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₃-S-Sn (Et)₂-S- (CN₂)₃-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₃-SSn (Bu)₂-S- (CH₂)₃-Si (OEt)₂(Me), (PrO)₂(Me) Si- (CH₂)₃-S-Sn (Me)₂-S- (CH₂)₃-Si (OPr)₂(Me) (PrO)₂(Me) Si- (CH₂)₃-SSn (Et)₂-S- (CH₂)₃-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₃-S-Sn (Bu)₂-S- (CH₂)₃Si (get drunk₂(Me), (MeO)₂(Me) Si- (CH₂)₂-SSn (Me)₂-S- (CH₂)₂-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₂-S-Sn (Et)₂-S- (CH₂)₂-Si (OMe)₂(Me), (MeO)₂(Me) Si- (CH₂)₂-S-Sn (Bu)₂-S- (CH₂)₂-Si (OMe)₂(Me), (EtO)₂(Me) Si- (CH₂)₂-SSn (Me)₂-S- (CH₂)₂-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₂-S-Sn (Et)₂-S- (CH₂)₂-Si (OEt)₂(Me), (EtO)₂(Me) Si- (CH₂)₂-SSn (Bu)₂-S- (CH₂)₂-Si (OEt)₂(Me), (PrO)₂(Me) Si- (CH₂)₂-S-Sn (Me) 2-S- (CH₂)₂-Si (OPr) 2 (Me), (PrO)₂(Me) Si- (CH₂)₂-SSn (Et)₂-S- (CH₂)₂-Si (OPr)₂(Me), (PrO)₂(Me) Si- (CH₂)₂-S-Sn (Bu)₂-S- (CH₂)₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-SSn (Me)₂-S-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-S-Sn (Et)₂-S-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-SSn (Bu)₂-S-CH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-S-Sn (Me)₂-S-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-SSn (Et)₂-S-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-S-Sn (Bu)₂-S-CH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-S-Sn (Me)₂-SCH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-S-Sn (Et)₂-S-CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-S-Sn (Bu)₂-SCH₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Me)₂-S-CH₂-CMe₂CH₂-Si (OMe)₂(Me), (MeO)₂(Me) sich₂-CMe₂CH₂-S-Sn (Et)₂-S-CH₂-CMe₂CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Bu)₂-SCH₂-CMe₂CH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Me)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Et)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-CMe₂CH₂-SSn (Bu)₂-S-CH₂-CMe₂CH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Me)₂-SCH₂-CMe₂CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Et)₂-S-CH₂-CMe₂CH₂-Si (OPr)₂(Me), (PrO)₂(Me) Si-CH₂-CMe₂CH₂-S-Sn (Bu)₂-S-CH₂-CMe₂CH₂-Si (OPr)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) Me-CH₂-SSn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Sn (Et)₂-S-CH₂-C (H) MeCH₂-Si (OMe)₂(Me), (MeO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Sn (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OMe)₂(Me), (EtO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Sn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-C (H) MeCH₂-S-Sn (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OEt)₂(Me), (EtO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Sn (Bu)₂-S-CH₂-C (H) Me25

CH₂-Si (OEt)₂(Me), (PrO)₂(Me) Si-CH₂-C (H) Me-CH₂-S-Sn (Me)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me), (PrO)₂(Me) sich₂-C (H) Me-CH₂-S-Sn (Et)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me), and / or (PrO)₂(Me) Si-CH₂-C (H) Me-CH₂-SSn (Bu)₂-S-CH₂-C (H) Me-CH₂-Si (OPr)₂(Me).

The modified compounds of formula (2) described above are disclosed in detail in WO2014 / 040639, which has been fully incorporated herein by reference.

In another embodiment, the compound of formula (3) can be used in the modification (II) step.

(RIO) x1 '(RII) y1'Si-RIV-SE formula (3), where the RI and RII elements are independently selected from C1-C8 alkyl or C1-C4 alkoxy, provided that at least one of the RI and RII elements is C1-C4 alkoxy; x1 'is an integer selected from 1, 2 and 3; y1 'is an integer selected from 0, 1 and 2; the RIV element is selected from C1-C8 alkyl, and the E element is an RV group or has the formula (3a):

s

-CSR_v formula (3a) where the RV element is C1-C6 alkyl, C6-C12 aryl, C7-C16 alkylaryl or arylalkyl

C7-C16.

Preferably in formula (3) each of RI and RII is independently C1-C4 alkoxy; the RIV element is selected from C1-C4 alkyl, and the E element has the formula (3a).

The compounds of formula (3) described above are disclosed in detail in EP document 2596 963 B1, which is fully incorporated herein by reference.

In an alternative embodiment, at least one compound of formula (11) to (15) as defined below can be used in the modification (II) step.

(OR^1d)_r4

Si_R3d__s__withd

<img file="PL3059256T3_D0023.tif" />

formula (11) where each element R^1d is independently selected from (C 1 -C 16) alkyl; each element of R^2d is independently selected from alkyl (C1-C16), aryl (C6-C18) and alkylaryl (C7C18); each element of R^3d is independently selected from divalent alkyl (C126

C16), divalent aryl (C6-C18), divalent alkylaryl (C7-C18) and -R^4dOR^5d-, with elements of R^4d and R^5d are independently selected from divalent (C1-C6) alkyl; element Z^d is independently selected from alkyl (C1-C16), aryl (C6-C18), alkylaryl (C7-C18), (C = S) -SR^6d, with the element R^6d is selected from alkyl (C1C16), aryl (C6-C18) and alkylaryl (C7-C18), as well as -M^1d(R^7d) C4 (R^8d) d4, with the element M^1d is silicon or tin, each element R^7d is independently selected from alkyl (C1-C16), aryl (C6-C18) and alkylaryl (C7-C18); each element of R^8d is independently selected from -SR^3d-Si (OR^1d) R 4 (R^2d) s4, with elements R^1d, R^2d and R^3d are as defined above, r4 is an integer selected independently from 1, 2 and 3, and s4 is an integer selected independently from 0, 1 and 2, with r4 + s4 = 3; c4 is an integer selected independently from 2 and 3; d4 is an integer selected independently from 0 and 1, while c4 + d4 = 3;

<img file="PL3059256T3_D0024.tif" />

where elements R^9e, R^10e, R^11e and R^12e are independently selected from hydrogen, alkyl (C 1 -C 16), aryl (C 6 -C 16) and aralkyl (C 7 -C 16), preferably N-methyl pyrrolidone;

(0R^13a)_t1_R16a

Si15a_i

N, (R^14a)_u1

17a formula (13) (0R^18a)_v^{3) 2}

Si-R^20a—L / (CR^23a2)₂ formula (14) where each element R^13a, R^14a, R^18a and R^19a is independently selected from alkyl (C1-C16), R elements^15a and R^20a are independently selected from divalent alkyl (C1-C16), divalent aryl (C6-C18), divalent aralkyl (C7-C18) and -R^24a-OR^25a- where elements R^24a and R^25a are independently selected from divalent (C1-C6) alkyl; elements of R^16a and R^17a are independently selected from (C 1 -C 16) alkyl and -SiR^26aR^27aR^28awhere _{elements of R}^26a, R^27a_{and R}^28a are independently selected from alkyl (C1-C16), aryl (C6-C18) and alkylaryl (C7-C18); each element of R^21a and R^22a is independently selected from alkyl (C1-C16), aryl (C6-C18) and alkylaryl (C7-C18); each element of R^23a is independently selected from hydrogen and (C 1 -C 6) alkyl; t1 and u1 are integers independently selected from 1, 2 and 3, v and v are integers independently selected from 0, 1 and 2, and t1 + u1 = 3 and v + w = ​​3;

<img file="PL3059256T3_D0025.tif" />

where each element R²⁹ and R^thirty is independently selected from alkyl (C1-C16), aryl (C6C18), alkylaryl (C7-C18) and vinyl, and the value x10 is an integer from 1 to 6.

Modification conditions

At the modification stage (II) in the process of producing component (a), at least the modifying compound of formula (1) to (3) or formula (11) to (15) as defined above can be added to the live polymer in an amount such that the ratio the molar content was at least 0.05, more preferably at least 0.1, and most preferably at least 0.15.

Modifying compounds represented by any one of formulas (1) to (3) or formulas (11) to (15) are preferably added with almost complete or complete conversion of the polymerized monomers, preferably with an anionic polymerization conversion index higher than 85 weight percent relative to to the amount of monomers supplied. The phrase "amount of monomers supplied", "amount of monomers introduced" or similar terms as used herein refers to the amount of monomers supplied as part of the polymerization process. In a preferred embodiment, the conversion rate is at least 92.0 weight percent, preferably over 94.0 weight percent, based on the amount of monomers supplied. The term "monomer conversion" as used herein refers to a particular monomer conversion (e.g. combined conversion of styrene and 1,3-butadiene), e.g. at the outlet of a specific polymerization reactor.

Preferably, a significant number of living polymer chain ends are not inactivated prior to reaction with the modifying compound, i.e. living polymer chain ends are present and can react with a modifying compound represented by any of formulas (1) to (3) and formulas (11) to (15) during a polymer chain end modification reaction. Before introducing modifying compounds, it may be beneficial to change the ends of the polymer chains to the ends of the dienyl chains by adding small amounts of bound diene monomer, e.g. 1,3-butadiene. During the modification reaction, at least one polymer chain may react with said modifying compounds.

In this way, the modification reaction using a compound represented by any of formulas (1) to (3) or formulas (11) to (15) as defined above results in obtaining modified or functionalized elastomeric polymers. In one embodiment, such elastomeric polymers are characterized by a degree of modification (molar percentage of modified chain ends relative to the total number of macromolecules produced) at a level of at least 20%, preferably at least 50%, and most preferably at least 80%.

The modifying compound represented by any of formulas (1) to (3) or formulas (11) to (15) can be added directly to the polymer solution without dilution. However, it may be advantageous to add compounds represented by any one of formulas (1) to (3) or formulas (11) to (15) in a solution based on an inert solvent, e.g. the solvent described above.

Basically, it should be understood that the terms "modification" and "functionalization" can be used interchangeably.

randomizers

Randomizers, conventionally known in the art (also called polar coordination compounds) can optionally be added to the monomer mixture or to the polymerization reaction to adjust the microstructure (i.e. the content of vinyl bonds) of the bound diene polymer portion and / or to adjust the distribution of α-olefin monomer in the polymer chain. It is also possible to use a combination of two or more randomizers.

Examples of randomizers useful in the present invention are generally Lewis base compounds. Examples of Lewis bases suitable for use in the present invention are, inter alia, ether compounds, such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, 2- (2-ethoxyethoxy) -2-methylpropane, (C1-C8 alkyl) tetrahydrofuryl ethers (such as methyl tetrahydrofuryl ether, etylotetrahydrofuryloeter, propylotetrahydrofuryloeter, butylotetrahydrofuryloeter, heksylotetrahydrofuryloeter, oktylotetrahydrofuryloeter) tetrahydrofuran, 2,2- (bistetrahydrofurfurylo) propane, bistetrahydrofurfuryloformal, tetrahydrofurfuryl alcohol methyl ether, tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol butyl ether, αmetoksytetrahydrofuran, dimethoxybenzene and dimethoxyethane and tertiary amines, such as triethylamine, pyridine, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine dipiperydynoetan, N, N-diethylethanolamine methyl ether, Ν, Ν-diethylethanolamine ethyl ether, N, N-diethylethanolamine and dimethyl Ν, Ν-tetrahydrofurfurylamine. Examples of preferred randomizers are listed in WO 2009/148932, which is incorporated by reference in its entirety.

In addition, potassium compounds can also be used as randomizers to achieve a specific incorporation of α-olefin (vinyl) monomer in the polymer chain. Suitable potassium compounds can be selected from the group containing potassium alkoxides, potassium sulfonates and potassium carboxylates. Examples include potassium t-butoxide, potassium t-amylate, potassium nonylphenolate, potassium 3,7-dimethyl-3-octylate, potassium dodecylbenzene sulfonate, potassium naphthalene sulfonate, potassium stearate, potassium decanoate and / or potassium naphthoate. The randomizer is usually added in a molar ratio of randomizer to initiator from 0.012: 1 to 10: 1, preferably from 0.1: 1 to 8: 1, and more preferably from 0.25: 1 to about 6: 1.

stabilizers

After the polymerization process, one or more stabilizers ("antioxidants") can optionally be added to the polymer to prevent degradation of the first elastomeric polymer by molecular oxygen. Antioxidants based on sterically protected phenols are usually used, such as 2,6-di-tert-butyl-4-methylphenol, 6,6'metylenobis (2-tert-butyl-4-methylphenol), iso-octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexamethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isotridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-etylidenobis- (4,6-di-tert-butylphenol), tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate and 2-tert-butyl acrylate

6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl and thioester-based antioxidants such as 4,6-bis (octylthiomethyl) o-cresol and tetrakis (3laurylthiopropionate) pentaerythritol. Other examples of suitable stabilizers can be found in F. Rothemeyer, F. Sommer, Kautschuk Technologie, 2nd ed. (Hanser Verlag, 2006) pp. 340-344 and in the publications cited therein.

Structure of the first elastomeric polymer

In one embodiment, the first elastomeric polymer (a) is a homopolymer obtained by (I) anionic polymerization of bound dienes, preferably 1,3-butadiene or isoprene.

In another embodiment, the first elastomeric polymer is (a) a random or block co-polymer obtained by (I) anionic polymerization of at least one bound diene, preferably 1,3-butadiene or isoprene, with at least one α-olefin monomer, preferably with styrene and / or divinylbenzene.

For this reason, the first elastomeric polymer (a) in the polymer blend is preferably a butadiene polymer, a butadiene divinylbenzene copolymer, a styrene butadiene copolymer (hereinafter referred to as SBR) or a styrene-divinylbenzenebutadiene terpolymer.

In one alternative embodiment, the first elastomeric polymer (a) is therefore a homopolymer obtained by (I) anionic polymerization of bound dienes, preferably 1,3-butadiene or isoprene, and (II) modification of the homopolymer chains obtained in step (I) by adding and reacting at least one compound represented by any one of formulas (1) to (3) and formulas (11) to (15) as defined above.

In another alternative embodiment, the first elastomeric polymer (a) is a random or block co-polymer obtained by (i) anionic polymerization of at least one bound diene, preferably 1,3-butadiene or isoprene, with at least one α-olefin monomer, preferably with styrene and / or divinylbenzene and (II) modification of random or block copolymer or terpolymer chains obtained in step (i) by adding and reacting at least one compound represented by any one of formulas (1) to (3) and formulas ( 11) to (15) as above.

Most preferably the first elastomeric polymer (a) is a styrene butadiene copolymer (hereinafter referred to as SBR), a (homo) butadiene polymer (hereinafter referred to as BR) or a modified SBR or BR polymer as described above.

The first elastomeric polymer (a), e.g. a styrene butadiene copolymer or modified SBR polymer, has a number average molecular weight (here referred to as Mn) in the range from 400,000 to 2,000,000 g / mol, more preferably in the range from 450 1,000 to 1,500,000 g / mol, and most preferably in the range of 500,000 to 800,000 g / mol, measured by size exclusion chromatography (hereby recorded as SEC) and converted to polystyrene equivalents.

The first elastomeric polymer (a), e.g. a styrene butadiene copolymer or modified SBR polymer, has a mass average molecular weight (here referred to as Mw) in the range from 400,000 to 3,000,000 g / mol, more preferably in the range from 600,000 up to 1,500,000 g / mol, and most preferably in the range from 800,000 to 1,100,000 g / mol, measured by size exclusion chromatography (hereby recorded as SEC) and converted to polystyrene equivalents.

Mn and Mw values ​​falling below the indicated ranges lead to less favorable Mooney viscosity, greater cold flow and greater rolling resistance after forming and vulcanization of the polymer blend according to the claims. On the other hand, Mn and Mw values ​​falling within the ranges indicated above result in poorer processability of the elastomeric polymer (a) and the polymer blend according to claim 1 and the above description.

In other words, the first elastomeric polymer (a), e.g. a styrene butadiene copolymer or a modified BR or SBR polymer is a high molecular weight component as defined above.

The weight ratio of α-olefin, e.g. styrene, relative to diene, e.g. 1,3-butadiene or isoprene, in the first elastomeric polymer (a) as defined above is preferably below 50 weight percent, preferably below 48 weight percent, and most preferably below 45 weight percent.

In one embodiment, the α-olefin content, e.g. styrene, in the first elastomeric polymer (a) as defined above is in the range of 0 to 30 weight percent. In another embodiment, the α-olefin content, e.g. styrene, in the elastomeric polymer (a) as defined above is in the range of 30 to 45 percent by weight. The term "α-olefin content" or "styrene content" as used herein refers to the percentage by mass of α-olefin or styrene in the first elastomeric polymer (a) relative to the total weight of the first elastomeric polymer.

In one embodiment, the vinyl content of the first elastomeric polymer (a) is preferably in the range of 5 to 80 percent by weight. The term "vinyl content" as used herein refers to the percentage by mass of at least one diene, e.g. 1,3-butadiene and / or isoprene, introduced into the polymer chain of the elastomeric polymer (a) in the 1,2- position and 1,2- or 3,4- position, respectively, and is determined on the basis of the diene part, e.g. butadiene and / or isoprene (total amount of polymerized diene) in the elastomeric polymer. In a more preferred embodiment, the vinyl content is in the range of 8 to 65 weight percent.

The amount of component (a) in the polymer blend of claim 1 is in the range of 60 to 96 weight percent, preferably in the range of 70 to 90 weight percent, based on the total weight of the polymer blend.

In addition, it is preferred that the first elastomeric polymer (a) in the polymer blend of the present invention has a glass transition temperature (in this document recorded as Tg) in the range from -95 ° C to 5 ° C as measured by DSC (see measurement methods below).

Component (b) - a second polymer, characterized by low molecular weight

In the first embodiment, component (b) of the polymer blend as defined in claim 1 is a second polymer, characterized by low molecular weight, obtained by (i-1) anionic polymerization of at least one bound diene monomer, preferably 1,3-butadiene or isoprene, in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-1) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the value x, x1 ' r4, t1 and v are selected from numbers 1 and 2.

The second polymer (b) in the polymer blend of the present invention is therefore preferably a modified butadiene copolymer (hereinafter referred to as BR).

In a second embodiment, component (b) of the polymer blend as defined in claim 1 is a second polymer, characterized by low molecular weight, obtained by (i-2) anionic polymerization of at least one bound diene monomer, preferably 1,3-butadiene or isoprene, and at least one α-olefin monomer, preferably styrene, α-methylstyrene or divinylbenzene, in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-2) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the value x, x1 ' r4, t1 and v are selected from numbers 1 and 2.

Alternatively, the second polymer (b) in the polymer blend of the present invention is therefore preferably a styrene butadiene polymer (SBR).

In a third embodiment, component (b) of the polymer blend as defined in claim 1 is a second polymer, characterized by low molecular weight, obtained by (i-3) anionic polymerization of at least one α-olefin monomer, preferably styrene, α-methylstyrene or divinylbenzene, in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-3) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) as defined above and claim 1, provided that in the appropriate formula, the value x, x1 ' r4, t1 and v are selected from numbers 1 and 2.

Alternatively, the second polymer (b) in the polymer blend of the present invention is therefore preferably a modified polystyrene polymer.

Description of the appropriate reaction conditions for the anionic polymerization (i), including relevant bound diene monomers, α-olefin monomers, polymerization initiators, solvents, temperatures and reaction conditions of the modification (ii), including appropriate modifying agents, relating to the preparation of component (b) corresponds to the above description of the polymerization reaction (I) and the optional modification reaction (II) for the preparation of component (a). The monomers and conditions used to prepare component (b) are therefore generally the same as those disclosed above for the first elastomeric polymer, i.e. component (a), provided that the conditions set out in the first, second and third embodiments for component ( b) as described above.

In the first to third embodiments described above, the polymerization initiator for the anionic polymerization reaction is preferably selected from lithium n-butyl, lithium sec-butyl or a compound of formula (6) or formula (7), which in particular

Me

<img file="PL3059256T3_D0026.tif" />

Me can be used alone or in combination.

Additionally, in a preferred embodiment, the second polymer (b) is an elastomeric polymer, e.g., styrene butadiene or butadiene polymer.

Component (b) of the polymer blend according to claim 1 is a second polymer characterized by low molecular weight. The amount of component (b) in the polymer blend of claim 1 is in the range of 4 to 35 weight percent, preferably in the range of 10 to 30 weight percent, and most preferably in the range of 13 to 25 weight percent, based on the total weight of the polymer blend .

The second polymer (b) has a number average molecular weight (hereinafter referred to as Mn) in the range from 500 to 80,000 g / mol, more preferably in the range from 1000 to 50,000 g / mol, and most preferably in the range from 2,000 to 25,000 g / mol, measured by size exclusion chromatography (hereby recorded as SEC) and converted to polystyrene equivalents.

The second polymer (b) has a weight average molecular weight (here recorded as Mw) in the range from 500 to 100,000 g / mol, more preferably in the range from 1000 to 50,000 g / mol, as measured by size exclusion chromatography (here recorded as SEC) and converted into polystyrene equivalents.

In other words, the second polymer (b) is a low molecular weight compound as defined above.

In one embodiment, the vinyl content of the second polymer (b), in the case of the butadiene or isoprene (b) homopolymer, is preferably from 5 to 80 percent by weight, and the content of styrene or divinylbenzene is less than 1 percent by weight.

In one embodiment, the vinyl content of the second polymer (b), in the case of styrene butadiene copolymer (b), is preferably from 5 to 75 percent by weight, and the styrene content of the second polymer (b) is preferably from 1 to 70 percent by weight, more preferably from 5 to 60 weight percent, and most preferably from 10 to 50 weight percent.

In one embodiment, the styrene content of the second polymer (b), in the case of a styrene homopolymer, is preferably greater than 90 weight percent, more preferably greater than 95 weight percent, and most preferably greater than 98 weight percent. In addition, it is preferred that the second polymer (b) in the polymer blend of the present invention has a glass transition temperature (hereinafter referred to as Tg) in the range from -95 ° C to 30 ° C as measured by DSC (see measurement methods below) .

Ingredient (c) - optional (conventional) low molecular weight dilution oil

Component (c) of the polymer blend according to claim 1 is optional and corresponds to at least one dilution oil, which is also called plasticizer.

The amount of component (c) in the polymer blend (if present) may range from 0 to 13 percent by weight, based on the total weight of the polymer blend. If a larger amount of component (c) is used, the parameters of the crosslinked vulcanizates containing the polymer blend as defined in this publication, and in particular the abrasion resistance and adhesion of the polymer blend / composition, will deteriorate.

References to examples of typical dilution oils and their classification are found in International Patent Application No. PCT / US09 / 045553 and United States Patent Application No. 2005/0159513, which are fully incorporated herein by reference. Typical dilution oils include MES (Mild Extraction Solvate), TDAE (Treated Distillate Aromatic Extract), RAE (Residual Aromatic Extract), including T-RAE and S-RAE, DAE, including T-DAE and NAP (light and heavy naphthenic oils) , including but not limited to Nytex 4700, Nytex 8450, Nytex 5450, Nytex 832, Tufflo 2000 and Tufflo 1200. In addition, native oils can be used as diluents, including vegetable oils. Typical oils are also functionalized variants of the oils mentioned above, in particular epoxy and hydroxylated oils. These dilution oils contain different concentrations of polycyclic aromatic, paraffinic, naphthenic and aromatic compounds, and also have different glass transition temperatures. The types of oils mentioned above have been described in the publication "Kautschuk Gummi Kunststoffe", volume 52, p. 799-805. In preferred embodiments, MES, RAE and / or TDAE agents are used as (conventional) diluting oils.

Preparation of the mix. polymer

The polymer blend of the present invention is prepared in solution by in situ polymerization of both compounds (a) and (b), i.e. the first elastomeric polymer (a) and the second polymer (b) as described above, during one process or by mixing the appropriate polymer solutions obtained after the polymerization reaction (including the modification reaction, if done) of the relevant components, i.e. the first elastomeric polymer (a) and the second polymer (b) as described above. Optional diluent oils (c) are then added and mixed to the resulting polymer solution containing the first elastomeric polymer (a) and the second polymer (b) (if any). The amounts of individual ingredients are specified in claim 1.

The polymer blend is then recovered from the polymer blend solution in accordance with methods commonly known and used in the rubber industry, e.g. by steam stripping at an elevated temperature, preferably around 100 ° C, followed by typical dewatering and drying at elevated temperatures.

Specific polymer blends of the present invention

The following alternative embodiments relate to specific polymer blends of the present invention:

In a first embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-1) of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i1) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a second embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-1) of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-1) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a third embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of an organic solvent polymerization initiator and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any from formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-1) of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-1) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a fourth embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any one of formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-1) of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-1) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of from 400,000 to

000 000 g / mol and weight average molecular weight (Mw) of 500,000 to

000 000 g / mol and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 80

100 000 g / mol and wherein the amounts of components (a) and (b) are based on the total weight of the polymer blend.

In a fifth embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-2) of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i- 2) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of from 400,000 to

000 000 g / mol and weight average molecular weight (Mw) of 500,000 to

000 000 g / mol, and the second polymer (b) number average molecular weight (Mn) between 500 and 80,000 g / mol and weight average molecular weight (Mw) between 500 and 100,000 g / mol and the amounts ( a) and (b) are based on the total weight of the polymer blend.

In a sixth embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-2) of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i- 2) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a seventh embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of an organic solvent polymerization initiator and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any from formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-2) of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i- 2) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of from 500,000 to

000 000 g / mol and weight average molecular weight (Mw) from 400,000 to

000 000 g / mol, and the second polymer (b) number average molecular weight (Mn) between 500 and 80,000 g / mol and weight average molecular weight (Mw) between 500 and 100,000 g / mol and the amounts ( a) and (b) are based on the total weight of the polymer blend.

In an eighth embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any one of formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-2) of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i- 2) by adding and reacting at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a ninth embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-3) of at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i3) by adding and reacting at least one the relationship represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a tenth embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and the second polymer is obtained by (i) anionic polymerization (i-3) of at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-3) by adding and reacting with at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of from 400,000 to

000 000 g / mol and weight average molecular weight (Mw) of 500,000 to

000 000 g / mol, and the second polymer (b) number average molecular weight (Mn) between 500 and 80,000 g / mol and weight average molecular weight (Mw) between 500 and 100,000 g / mol and the amounts ( a) and (b) are based on the total weight of the polymer blend.

In an eleventh embodiment, the polymer blend of the present invention consists of (a) from 60 to 96 percent by weight of the first elastomeric polymer and (b) from 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer in the presence of an organic solvent polymerization initiator and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any from formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-3) of at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (ii) modification of the polymer chain ends obtained by method (i-3) by adding and reacting at least one the relationship represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 400,000 to 2,000,000 g / mol and a weight average molecular weight (Mw) of 500,000 to 3,000,000 g / mol, and the second polymer (b) has a number average molecular weight (Mn) of 500 to 80,000 g / mol and a weight average molecular weight (Mw) of 500 to 100,000 g / mol and the amounts of components (a) and (b ) are based on the total weight of the polymer blend.

In a twelfth embodiment, the polymer blend of the present invention consists of (a) 60 to 96 percent by weight of the first elastomeric polymer and (b) 4 to 35 percent by weight of the second polymer, wherein the first elastomeric polymer is obtained by (I) anionic polymerization of at least one bound diene monomer and at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent, and (II) modification of the polymer chain ends obtained by method (I) by adding and reacting at least one compound represented by any one of formulas (1) to (3) or formulas (11) to (15) according to claim 1, and the second polymer is obtained by (i) anionic polymerization (i-3) of at least one α-olefin monomer in the presence of a polymerization initiator in an organic solvent and (ii) modification of the polymer chain ends obtained by method (i-3) by adding and reacting with at least one compound represented by any of the formulas (1), (3) or formulas (11) to (15) according to claim 1, provided that in the appropriate formula, the entries x, x1 ' r4, t1 and v are selected from values ​​1 and 2, wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of from 400,000 to

000 000 g / mol and weight average molecular weight (Mw) of 500,000 to

000 000 g / mol, and the second polymer (b) number average molecular weight (Mn) between 500 and 80,000 g / mol and weight average molecular weight (Mw) between 500 and 100,000 g / mol and the amounts ( a) and (b) are based on the total weight of the polymer blend.

In addition, the polymer blends of the present invention described in the above twelve embodiments may also contain from 0 to 13 weight percent of at least one diluent oil.

Polymer composition

The present invention also relates to a polymer composition comprising a polymer blend according to the first aspect of the present invention described above.

In one embodiment, the polymer composition of the present invention may also contain at least one filler to serve as a reinforcing agent. Examples of suitable fillers include soot (including electrically conductive soot), carbon nanotubes (CNTs) (including single CNTs, hollow carbon fibers (HCF) and modified CNT containing at least one functional group, such as a hydroxyl group, carboxyl and carbonyl), graphite, graphene (including individual graphene flakes), silica, carbon-silica two-phase filler, clays, including layered silicates, calcium carbonate, magnesium carbonate, lignin, amorphous fillers, such as fillers based on glass particles, starch-based fillers and combinations thereof. Additional examples of suitable fillers are described in WO 2009/148932, which is fully incorporated herein by reference. Examples of suitable soot include carbon black produced by a conventional method using an oven, for example, with a nitrogen specific adsorption surface of 50-200 m²/ g and DBP oil adsorption of 80-200 ml / 100 grams, such as carbon black FEF, HAF, ISAF or SAF, and electrically conductive carbon black. In some embodiments, high agglomeration carbon black is used. Carbon black is usually used in an amount of from 2 to 100 parts by weight or from 5 to 100 parts by weight, or from 10 to 100 parts by weight, or from 10 to 95 parts by weight per 100 parts by weight of all polymer.

Examples of suitable silica fillers include, but are not limited to, wet process silica, dry process silica, and synthetic silicate type silica. Silica with a small particle diameter and large specific surface has a highly reinforcing effect. Silica with small particle diameter and high agglomeration (i.e. characterized by a large specific surface area and high oil absorption), it has the unique ability to form suspensions in polymer compositions, making it better processable. The average diameter of the silica particle, in terms of primary particle diameter, may be from 5 to 60 nm, and more preferably from 10 to 35 nm. The specific surface area of ​​silica particles (measured by the BET method) can be from 35 to 300 m²/ G. Silica is usually used in an amount of from 10 to 150 parts by weight or from 30 to 130 parts by weight, or from 50 to 130 parts by weight per 100 parts by weight of all polymer.

Siliceous fillers can be used together with other fillers, including carbon black, carbon nanotubes, two-phase carbon-silica filler, graphene, graphite, clay, calcium carbonate, magnesium carbonate and combinations thereof. Soot and silica may be added together, in which case the total amount of carbon black and silica added is from 30 to 150 parts by weight or from 50 to 150 parts by weight per 100 parts by weight of all polymer.

Two-phase carbon-silica filler is so-called silica coated carbon black, produced by coating the surface of soot with silica, commercially available under the trademark CRX2000, CRX2002 or CRX2006 (manufacturer: Cabot Co.).

The carbon-silica two-phase filler is added in the same amounts as specified above for silica.

In another embodiment, the polymer composition comprising the polymer blend of the present invention may optionally contain at least one vulcanizing agent (or crosslinker). The terms "vulcanizing agent" and "crosslinking agent" (or "vulcanization" and "crosslinking" respectively) as used herein are used interchangeably.

Sulfur, sulfur-containing compounds that act as sulfur donors, sulfur accelerating systems and peroxides are the most common vulcanizing agents. Examples of sulfur-containing compounds that act as sulfur donors include dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD) and dipentamethylene thiuram tetrasulfide (DPTT). Examples of sulfur accelerators include amine derivatives, guanidine derivatives, aldehyde liquefaction products, thiazoles, thiuram sulfides, dithiocarbamates and thiophosphates. Examples of peroxides used as vulcanizing agents include di-tert.-butyl peroxides, di- (tert.-butyl-peroxy-trimethylcyclohexane), di- (tert.butyl-peroxyisopropyl-) benzene, dichlorobenzoyl peroxide, dicumyl peroxides, tert-butyl-cumyl peroxide, dimethyl-di (tert.-butyl-peroxy) hexane and dimethyl di (tert.-butyl-peroxy) hexine and butyl-di (tert.-butyl-peroxy) valerate (Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000) . Further examples and additional information about vulcanizing agents can be found in KirkOthmer, Encyclopedia of Chemical technology, ed. 3., (Wiley Interscience, NY 1982), volume 20, p. 365-468 (in particular, the entry 'Vulcanizing Agents and Auxiliary Materials', p. 390-402).

In addition, the polymer composition containing the polymer blend of the present invention may also contain up to 10 weight percent of at least one diluting oil based on the total weight of the polymer composition. Thinning oils have been described above.

If desired, sulfuramide, sulfenguanidine or sulfentiuram type accelerating vulcanization agents may be used together with a vulcanizing agent. Optionally, other additives can be used, such as zinc white, vulcanization auxiliaries, anti-aging agents, supplementary agents used in the process, etc. The vulcanizing agent is usually added to the polymer composition in an amount of 0.5 to 10 parts by weight, and in some preferred embodiments in an amount of 1 to 6 parts by weight per 100 parts by weight of all elastomeric polymer. Examples of vulcanization accelerating agents and their amounts added relative to the total polymer weight are given in International Patent Publication No. WO 2009/148932. Sulfur accelerating systems may or may not contain zinc oxide. Preferably zinc oxide is used as a component of the sulfur accelerator system.

In some embodiments, the silicon hydride coupling agent (used to polymerize fillers) can be added to a polymer composition comprising the polymer blend of the present invention and silica, layered silicate (such as magadyite), or a two-phase carbon silicate filler. A typical amount of silane coupling agent added is from about 1 to about 20 parts by weight, and in some embodiments from about 5 to about 15 parts by weight, per 100 parts by weight of the total amount of silica and / or carbon-silica biphasic filler.

Silicon coupling agents can be classified according to Fritz Rothemeyer, Franz Sommer: Kautschuk Technologie, (Carl Hanser Verlag 2006):

(A) as bifunctional silanes, including, among others, Si 230 (EtO) 3Si (CH2) 3Cl, Si 225 (EtO) 3SiCH = CH2, A189 (EtO) 3Si (CH2) 3SH, Si 69 [(EtO) 3Si (CH2) 3S2] 2, Si 264 (EtO) 3Si (CH2) 3SCN and Si 363 (EtO) Si ((CH2-CH2O) 5 (CH2) 12CH3) 2 (CH2) 3SH) (Evonic Industries AG); and (B) monofunctional silanes, including Si 203 (EtO) 3-Si-C3H7 and Si 208 (EtO) 3SiC8H17.

Further examples of silicon hydride coupling agents are given in International Patent Application No. PCT / US2009 / 045553 and include bis- (3-hydroxydimethylsilylpropyl) tetrasulphide, bis- (3-hydroxydimethylsilylpropyl) disulfide, bis- (2-hydroxydimethylsilylethyl) tetrasulphide, bis- (2-hydroxydimethylsilylethyl) disulfide, 3-hydroxymethylsiloxymethylsiloxymethoxymethylsulphosulfide

Preparation method of crosslinked elastomeric polymer

In a further aspect, the present invention relates to a method of preparing a crosslinked elastomeric polymer, wherein said method consists of the following stages: (1) Preparation of the polymer blend according to the first aspect of the present invention or the polymer composition according to the second aspect of the present invention; (2) adding at least one filler and optionally at least one silicon hydride coupling agent and reacting said mixture, and (3) adding a vulcanizing agent and optionally at least one vulcanizing accelerating agent to the mixture of step (2) and crosslinking said mixture.

Steps (1) to (3) relate to the preparation of a polymer blend or polymer composition containing the polymer blend of the present invention and vulcanization of the polymer composition containing the polymer blend and can be carried out using conventional mix preparation / crosslinking devices. Conventional fillers, silicon hydride coupling agents and vulcanization accelerating agents that can be used as part of the method of preparing the crosslinked elastomeric polymer have been described above. Crosslinked elastomeric polymer, article and set of polymers

The present invention further relates to crosslinked elastomeric polymers obtained by the method described above.

Furthermore, the present invention relates to articles comprising a polymer composition comprising the polymer blend of the present invention or said crosslinked elastomeric polymer obtainable as described above. In a preferred embodiment, the article of the present invention may be a tire, tire tread, sidewall, conveyor belt, seal, or hose.

Furthermore, the present invention relates to polymer sets comprising (II.1) the polymer blend of the present invention or (II.2) the polymer composition of the present invention.

DEFINITIONS

Alkyl groups as defined herein, alone or in combination with other groups such as alkylaryl or alkoxy, include straight chain alkyl groups such as methyl (Me), ethyl (Et), n-propyl (Pr), n-butyl (Bu), n-pentyl, nhexyl etc., branched alkyl groups such as isopropyl, tert- butyl etc. and cyclic alkyl groups such as cyclohexyl.

Alkoxy groups as defined in this document include methoxy (MeO), ethoxy (EtO), propoxy (PrO), butoxy (BuO), isopropoxy, isobutoxy, pentoxy etc. Aryl groups as defined herein include phenyl and biphenyl compounds. The aryl groups preferably contain only one aromatic ring, and most preferably contain a C6 aromatic ring, e.g. benzene.

Alkylaryl groups as defined herein are combinations of at least one aryl group bound to at least one alkyl group, for example in the form of alkylaryl, arylalkyl, alkylarylalkyl and arylalkylaryl. Alkylaryl groups preferably contain only one aromatic ring, and most preferably contain a C6 aromatic ring.

The homopolymer or copolymer as defined herein may contain a small amount of a second or third monomer, e.g. divinylbenzene, in the range of up to 1 weight percent based on the total weight of the polymer.

EXAMPLES

The following examples are presented to further illustrate the present invention, but are not intended to limit the scope of the present invention. Room temperature or ambient temperature refers to a temperature of about 20 ° C. All polymerizations were carried out under a nitrogen atmosphere after removal of moisture and oxygen.

Testing methods

Exclusion Chromatography

The molecular weight and molecular weight distribution of the polymer were measured by size exclusion chromatography (SEC) based on polystyrene standards. Each polymer sample (9 to 11 mg) was dissolved in tetrahydrofuran (10 mL) to form a solution. The solution was filtered using a 0.45 μm filter. A 100 μl sample was loaded onto a gel chromatography column (Hewlett Packard 1100 system equipped with 3 PLgel 10 μm MIXED-B columns). Refractometric detection was used to study the molecular weight. Molecular weight was calculated as for polystyrene based on calibration based on EasiCal PS1 polystyrene standards (Easy A and B) from Polymer Laboratories. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are given based on polystyrene standards. The molecular weight distribution is expressed in the form of dispersion D = Mw / Mn.

Analysis to measure monomer conversion

The monomer conversion was determined by measuring the solids concentration (TSC) in the polymer solution at the end of the polymerization process. The maximum solids content is obtained by converting 100 wt. of charged butadiene (mBd) and styrene (mSt) to the final polymer according to the TSC formula max = (mBd + mSt) / (mBd + mSt + m polar compound + mNBL + mcyclohexane) * 100%. A sample of the polymer solution weighing from about 1 g to about 10 g, depending on the expected monomer conversion, was taken from the reactor directly into a 200 ml Erlenmeyer flask filled with ethanol (50 ml). The weight of the filled Erlenmeyer flask was determined before sampling ("A") and after sampling ("B"). The precipitated polymer was separated from the ethanol by filtration using a weighted paper filter (glass microfiber paper with a diameter of 90 mm, from MUNKTELL, class "C" weight), dried at 140 ° C using a HR73 moisture analyzer (from MettlerToledo) until a weight loss of less than 1 mg is achieved in 140 seconds. Finally, a second drying phase was carried out using the exclusion criterion with a weight loss of less than 1 mg in 90 seconds to achieve the final weight "D" of the dry sample on the paper filter. The polymer content of the sample was calculated according to the formula: TSC = (DC) / (BA) * 100%. The final monomer conversion value was calculated according to the TSC / TSC max * 100% formula.

Glass transition temperature measurement Tg

The glass transition temperature was determined using a DSC Q2000 (TA Instruments) as described in ISO 11357-2 (1999) and under the following conditions:

Weight: approx. 10-12 mg;

Sample container: standard aluminum bowls;

Temperature range: (-140 to 80) ° C;

Heating rate: 20 K / min;

Cooling rate: free cooling;

Purge gas: 20 ml Ar / min;

Coolant: liquid nitrogen;

Assessment method: inflection method.

At least one measurement was carried out for each sample. Two heating cycles were carried out during the measurement. The 2nd heating cycle was used to determine the glass transition temperature.

¹H-NMR

The vinyl content and total styrene content were measured by spectroscopy ¹HNMR in accordance with ISO 21561-2005, using an IBRUKER Avance NMR spectrometer (400 MHz) and a 5 mm double probe. CDCl3 / TMS was used as the solvent in a weight ratio of 0.05%: 99.95%.

Measurement of VOC emissions

Emissions of volatile organic compounds (VOC) were compared using an RTG 220 apparatus. Each of the obtained samples was heated from room temperature to 800 ° C at a rate of 10 K / min in the presence of inert gas. Observed changes in mass and thermal effects were recorded.

The measurement of flows present

The flow was tested on a sample removed from the Mooney chamber after determining the Mooney viscosity for the rubber compound. Twenty-two grams of rubber compound was placed in a Mooney chamber. The chamber was closed and the measurement was carried out in accordance with ASTM D1646. The sample was removed from the chamber after the measurement was completed, cooled and placed between the paper and the film. The sample was then loaded with a 2 kg weight and stored for several months at room temperature. Each month the paper contact surface was visually checked.

Measurement of rheological properties

The rheological properties of non-vulcanized samples were measured in accordance with ASTM D 5289-95 using a non-rotating shear rheometer (MDR 2000 E) to determine curing characteristics, in particular cure time (t95). The "t95" values ​​mean the time needed to reach a 95% vulcanization conversion.

Properties of vulcanizate

Samples were vulcanized to t95 at 160 ° C to measure DIN abrasion, tensile strength and tangent δ.

Tensile strength and modules

Tensile strength and modules were measured according to ASTM D 412 in a Zwick Z010 device.

attrition

The abrasion resistance test was carried out in accordance with DIN 53516 (01.06.1987). A higher index meant lower abrasion resistance.

Shore A hardness and flexibility. on reflection

Shore A hardness (ASTM D 2240) and reflection flexibility (ISO 4662) were measured at 0 ° C, room and 60 ° C.

Loss factor - tangent δ

The tangent value δ (also called "tan d") for the loss factor was measured at 0 ° C and 60 ° C using an Eplexor 150N / 500N dynamic spectrometer manufactured by Gabo Qualimeter Testanlagen GmbH (Germany), using dynamic tensile stress of 1% by frequency 2 Hz.

Preparation of polymers

Polymer A with a high molecular weight

Four batches were made according to the following procedure. Dried cyclohexane (mcyclohexane = 20642 g) was added to the deaerated, nitrogen flushed 40-liter stainless steel reactor. 1,3-butadiene (mBd = 677 g), styrene (mst = 941 g) and TMEDA (polar compound, 4.72 mmol) were fed to the reactor (TMEDA / active lithium butyl, mol / mol = 1.12). The mixture was mixed and heated to 55 ° C. Impurities in the system were titrated by the gradual addition of lithium n-butyl. After recognition of the endpoint, the polymerization process was started by adding lithium n-butyl (15% solution in cyclohexane) in an amount corresponding to the target molecular weight of 540 kg / mol (lithium NBL n-butyl butyl, 4.19 mmol) using a pump within 2 minutes . Then the polymerization process began. The temperature in the reactor was increased to 30 ° C for 30 minutes and then kept constant. 15 minutes after adding lithium n-butyl to the reaction mixture, butadiene (677 g) was added for 60 minutes. thirty minutes later tetramethoxysilane was added as a coupling agent. The remaining living polymer chains were removed after 20 minutes by the addition of methanol. As antioxidant, 4,6-bis (octylthiomethyl) o-cresol was added commercially available under the trade name IRGANOX 1520 (Ciba, 0.2 phr). Four batches were mixed and the resulting polymer was subjected to gel permeation chromatography (GPC) analysis: Mn = 659617, Mw = 1004402, D = 1.52. The microstructure and content of styrene blocks was measured by 1H NMR spectroscopy. The following results were obtained: styrene = 39.6%, vinyl (1,2-polybutadiene, calculated in the butadiene fraction) = 24.2%, part of the styrene blocks below 5% of the total styrene content. The Tg value was found to be -31 ° C.

High molecular weight K polymer

Dried cyclohexane (19 628 g) was added to a vented, nitrogen flushed 40-liter stainless steel reactor. 1,3-butadiene (2269 g), styrene (617 g), tetramethylethylenediamine (TMEDA) (32.44 mmol) and divinylbenzene (DVB) (1.644 mmol) were introduced into the reactor. The mixture was mixed and heated to 40 ° C. Impurities in the system were titrated by the gradual addition of lithium n-butyl. After recognition of the endpoint, the polymerization process was started by adding lithium n-butyl (0.119 mol / kg solution in cyclohexane) in an amount corresponding to the target molecular weight of 350 kg / mol (lithium n-butyl butler, 8.34 mmol) using a pump over 2 minutes. Then the polymerization process began. The temperature in the reactor was increased to 60 ° C for 60 minutes and then kept constant. 115 minutes later, 3-tert-butyldimethylsilylthiopropyltrimethoxysilane (2.19 mmol) was added as a coupling agent. After 30 minutes, butadiene (46.7 g) was added and the remaining living polymer chains were modified by the addition of 3-tert-butyldimethylsilylthiopropyl dimethoxymethylsilane (5.89 mmol). After 30 minutes, methanol (41 g) was added and 4,6-bis (octythiomethyl) -o-cresol commercially available under the trade name IRGANOX 1520 (Ciba, 0.2 phr) was added as an antioxidant. The resulting polymer was analyzed by GPC: Mn = 581830, Mw = 892501, D = 1.53. The microstructure and content of styrene blocks was measured by 1H NMR spectroscopy. The following results were obtained: styrene = 21.3%, vinyl (1,2-polybutadiene, calculated in the butadiene fraction) = 64.3%, part of the styrene blocks below 1%. The Tg value was found to be -20.3 ° C.

Low molecular weight B polymer

5112 g cyclohexane, 1.6 g 2,2-ditetrahydrofuryl ether (DTHFP, polar compound) and 55.3 g lithium n-butyl (3.154 mmol / g) were charged into a 10 L reactor, heated to a temperature of 40 ° C. Then, within 30 minutes, 697 g of butadiene was introduced into the reactor according to a target molecular weight of 4 kg / mol. The temperature of the polymerization mixture increased to 45 ° C in 45 minutes due to the heat of polymerization. Living polymer chains were deactivated with methanol and stabilized by the addition of 0.25 phr 4,6-bis (octythiomethyl) o-cresol commercially available under the trade name IRGANOX 1520. The polymer chains were not functionalized. The molecular weight expressed as polystyrene equivalents was determined at the Mn level of 7540 g / mol. The composition was found to contain 30% vinyl and 70% 1,4-butadiene. The Tg value was found to be -80.9 ° C.

Low molecular weight C polymer

A polymer was prepared as described above for polymer B with the exception that a modifying compound (C), (MeO) (Me) 2Si- (CH2) 3-SSiMe2C (Me) 3 was introduced instead of methanol to functionalize the polymer chain ends. After 60 minutes of reaction, the remaining living polymer chains were inactivated with methanol, and then the polymer was stabilized by adding 0.25 phr of Irganox 1520.

Low molecular weight D polymer

A polymer was prepared as described above for polymer C except that the modifying compound (B), (MeO) 2 (Me) Si- (CH2) 3-S-SiMe2C (Me) 3 was introduced in place of the modifying agent (C) for the functionalization of polymer chain ends.

Low molecular weight E polymer

5192 g of cyclohexane, 24.72 g of TMEDA and 44.3 g of lithium n-butyl (3.154 mmol / g) were charged into a 5 L reactor heated to a temperature of 40 ° C. Then, 504 g of butadiene and 176 g of styrene were introduced in parallel into the reactor within 30 minutes according to a target molecular weight of 5 kg / mol. The temperature of the polymerization mixture increased at the same time to 60 ° C due to the heat of polymerization. After 30 minutes, living polymers were deactivated with methanol as termination agent. The polymer chains were not functionalized. The molecular weight of polymer E expressed as polystyrene equivalents was determined at the Mn level of 8383 g / mol. The composition was found to contain 26.6% styrene and 65% vinyl. The Tg value was found to be -17.8 ° C.

Low molecular weight F polymer

A polymer was prepared as described above for polymer E with the exception that a modifying compound (B), (MeO) 2 (Me) Si- (CH2) 3-SSiMe2C (Me) 3 was introduced instead of methanol to functionalize the polymer chain ends. The mixture was stirred for 60 minutes to carry out the modification reaction. The remaining living polymer chains were inactivated with methanol and then stabilized by the addition of 0.25 phr of Irganox 1520.

Low molecular weight G polymer

A polymer was prepared as described above for polymer F with the following exceptions. As a polymerization initiator, instead of lithium n-butyl, the modifying compound (D), Li- (CH2) (Me) 2SiN- (C2H5) 2 * (CH3) 2N-CH2CH2-N (CH3) 2 was used, and instead of the modifying agent ( B) a modifying agent (C), (MeO) (Me) 2Si- (CH2) 3S-SiMe2C (Me) 3 was introduced to functionalize the other chain end.

Low molecular weight H polymer

A polymer was prepared as described above for polymer C with the exception that a modifying agent (E), n-methylpyrrolidone, was introduced instead of the modifying agent (C) to functionalize the ends of the polymer chains.

Low molecular weight polymer I

4525 g cyclohexane, 57.84 g 2,2-ditetrahydrofuryl ether (DTHFP, polar compound) and 97.77 g lithium n-butyl (3.154 mmol / g) were charged into a 10 L reactor, heated to a temperature of 25 ° C. Then, within 60 minutes, 618 g of styrene was introduced into the reactor according to the target molecular weight of 2 kg / mol. The temperature of the polymerization mixture increased to 30 ° C in 30 minutes due to the heat of polymerization. After 60 minutes, 2724 g of the polymer solution was discharged, inactivated with methanol, and the resulting polymer (I1) was stabilized by the addition of 0.25 phr of 4,6-bis (octylthiomethyl) o-cresol. The remaining living polymer chains were functionalized by adding 53.24 g of the modifying compound (B), (MeO) 2 (Me) Si- (CH2) 3-S-SiMe2C (Me) 3. After 60 minutes of reaction, the remaining living polymer chains were inactivated with methanol and then the polymer (I2) was stabilized by adding 0.25 phr of Irganox 1520. The molecular weight expressed as polystyrene equivalents was determined at the Mn level of 2263 g / mol. The Tg value was found to be 11.5 ° C.

Preparation of polymer mixtures

The polymer blends of the present invention were prepared using the polymer solutions described above.

SSBR 1 (comparative)

Polymer A solution was mixed with TDAE oil to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of TDAE oil. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 2 (comparatively)

The polymer B solution was mixed with the polymer A solution to obtain a polymer consisting of 77 percent by weight polymer A and 23 percent by weight polymer B. Then the polymer was recovered in the solution by steam stripping at 100 ° C, ground to fine particles and dried in air circulation oven at temperature

70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below

0.75%.

SSBR 3

The polymer C solution was mixed with the polymer A solution to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of polymer C. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 4

The polymer D solution was mixed with the polymer A solution to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of polymer D. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 5 (comparative)

The polymer A solution was mixed with the polymer E solution to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of polymer E. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 6

The polymer F solution was mixed with the polymer A solution to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of polymer F. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 7

The polymer G solution was mixed with the polymer A solution to obtain a polymer consisting of 77 weight percent of polymer A and 23 weight percent of polymer G. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 8 (comparative)

The polymer K solution was mixed with TDAE oil to obtain a polymer consisting of 77 percent by weight polymer K and 23 percent by weight TDAE oil. The polymer was then recovered in solution by steam stripping at 100 ° C, ground to fine particles and dried in a circulating oven at 70 ° C for 30 minutes. The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

SSBR 9

The polymer K solution was mixed with the polymer G solution to obtain a polymer consisting of 77 percent by weight polymer A and 23 percent by weight polymer G. Then the polymer was recovered in the solution by steam stripping at 100 ° C, ground to fine particles and dried in air-circulating oven at 70 ° C for 30 minutes.

The polymer particles were dried under ambient conditions, in an air atmosphere, until the content of residual volatile compounds reached a value below 0.75%.

Preparation of polymer compositions and appropriate vulcanizates by means of

2-stage mixture preparation / crosslinking process

The polymer compositions of the present invention were prepared using the styrene butadiene polymer solution (SSBR) described above. Polymer compositions were prepared by kneading according to the formulas shown in Table 1 as part of a standard two-step procedure for preparing a compound with silica as a filler using an internal laboratory mixer with a Banbury type rotor with a total chamber capacity of 370 cm³.

The reagents used are described in Table 1.

The first mixing stage was performed with a fill factor of 72% at an initial temperature of 50 ° C. After addition of the polymer composition, filler and other ingredients described in the formulas for step 1, the internal mixer rotor speed was controlled to obtain a temperature in the range of 145 ° C to 160 ° C for a maximum of 4 minutes so that the silanization reaction could take place. The total mixing time during the first stage was 7 min. After discharge of the compound, the mixture was cooled and allowed to relax before adding hardener during the second mixing step.

Table 1: Compound preparations.

<td></td><td colspan="2">Preparation</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>Mixing:</td><td colspan="2">Comparison / example</td><td>tied</td><td>tied</td><td>glue</td><td>glue</td><td>tied</td><td>tied</td><td>glue</td><td>glue</td><td>tied</td><td>example</td>

<td>Stage</td><td>land</td><td></td><td>k 1</td><td>k 2</td><td>d 1</td><td>d 2</td><td>k 1</td><td>k 3</td><td>d 3</td><td>d 4</td><td>k 4</td><td>order 5</td>

<td>1</td><td>SSBR.</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>^Typ^:</td><td></td><td>SSBR1</td><td>SSBR2</td><td>SSBR3</td><td>SSBR4</td><td>SSBR1</td><td>SSBR5</td><td>SSBR6</td><td>SSBR7</td><td>SSBR8</td><td>SSB</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>R9</td>

<td></td><td>Quantity^(and)</td><td>phr</td><td>81.3</td><td>81.3</td><td>81.3</td><td>81.3</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td>

<td></td><td>Buna® cis 132-</td><td>phr</td><td>18.7</td><td>18.7</td><td>18.7</td><td>18.7</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td></td><td>Schkopau¹</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Silica</td><td>phr</td><td>76.6</td><td>76.6</td><td>76.6</td><td>76.6</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td><td>80</td>

<td></td><td>(Ultrasil 7000GR)²</td><td>_*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>silane</td><td>phr</td><td>6.6</td><td>6.6</td><td>6.6</td><td>6.6</td><td>6.9</td><td>6.9</td><td>6.9</td><td>6.9</td><td>6.9</td><td>6.9</td>

<td></td><td>(Si 75®)³</td><td>_*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Acid</td><td>phr</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td>

<td></td><td>stearic⁴</td><td>_*</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Zinc oxide⁵</td><td>phr_*</td><td>2.4</td><td>2.4</td><td>2.4</td><td>2.4</td><td>2.5</td><td>2.5</td><td>2.5</td><td>2.5</td><td>2.5</td><td>2.5</td>

<img file="PL3059256T3_D0027.tif" />

⁴ Cognis GmbH;

Grillo-Zinkoxid GmbH

N- (1,3-dimethylbutyl) -N'-phenyl-1,4-benzenediamine, Duslo as

Protective wax against light and ozone, Rhein Chemie Rheinau GmbH

Solvay AG

N-tert-butyl-2-benzothiazyl-sulfenamide; Rhein Chemie Rheinau GmbH

Diphenylguanidine, Vulkacit DZ / EG-C, Lanxess AG

The second mixing step was carried out in the same device with a 69% duty cycle at an initial temperature of 50 ° C. The compound from the first mixing step, sulfur as the vulcanizing agent and DPG and TBBS accelerators were added and mixed for a total of 3 minutes.

The obtained vulcanizates were tested for their performance parameters.

RESULTS

Emission of VOC compounds by polymer blends:

The results of the VOC emissions test are summarized in Table 2 below. The polymer blends of the present invention show significantly improved emission of VOC compounds, i.e. a higher initial temperature for weight loss and lower weight loss up to 300 ° C.

Table 2: Emission of VOCs by polymer blends.

<td></td><td>Initial temperature for weight loss</td><td colspan="2">Weight loss [%] from temp. initial to temp.</td>

<td></td><td>T, initial [° C]</td><td>300 ° C</td><td>350 ° C</td>

<td>SSBR 1 (relationship 1)</td><td>150</td><td>7.8</td><td>17.4</td>

<td>SSBR 4</td><td>250</td><td>0.2</td><td>1.6</td>

<td>SSBR 6</td><td>250</td><td>0.2</td><td>1.8</td>

<td>SSBR 7</td><td>250</td><td>0.2</td><td>1.9</td>

outflow:

For all new SSBR samples, no leakage was found regardless of the compatibility of the polymer oil and high molecular weight SSBR rubber.

Parameters of cross-linked polymer compositions (vulcanizates):

Next, key performance parameters of cross-linked polymer compositions (vulcanizates) according to the present invention were analyzed. The results of the tests used are shown in Table 3.

According to Table 3 below, it was found that the polymer composition containing the polymer blend of the present invention (example 1, i.e., SSBR3; example 2, i.e., SSBR4;

Example 3, i.e. SSBR6; example 4, i.e. SSBR7; example 5, i.e. SSBR9) is characterized by much higher modules (M300 and M300-M100) in combination with a significantly improved tangent value d at 60 ° C (i.e. lower value) and flexibility in reflection at 60 ° C (i.e. higher value) (these parameters are laboratory determinants of tire rolling resistance) with similar friction losses (i.e. within the measurement error of the method according to DIN) and a comparable temperature increase (HBU) in relation to the polymer composition containing styrene butadiene copolymer diluted with TDAE oil without component (b) of low molecular weight (comparison 1, i.e. SSBR1, comparison 4, i.e. SSBR8) or styrene butadiene copolymer, which is diluted only with a non-functionalized low molecular weight polymer (comparison 2, i.e. SSBR2 or comparison 3, i.e. SSBR5).

Color:

In addition, the polymer blends and / or polymer compositions of the present invention have a translucent or white color, i.e. after the production of the polymer blends and / or polymer compositions of the present invention there is no need for intensive cleaning.

Table 3: Key performance parameters of crosslinked polymer compositions.

<td>Preparation</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>Comparison / example</td><td>Relationship 1</td><td>Relationship 2</td><td>Example 1</td><td>Example 2</td><td>Relationship 1</td><td>Relationship 3</td><td>Example 3</td><td>Example 4</td><td>Relationship 4</td><td>Example 5</td>

<td>Module 100 [MPa]</td><td>2.30</td><td>2.30</td><td>2.50</td><td>3.00</td><td>2.20</td><td>1.90</td><td>2.60</td><td>3.90</td><td>2.20</td><td>3.5</td>

<td>Module 300 [MPa]</td><td>10.40</td><td>11.20</td><td>13.30</td><td>14.90</td><td>10.20</td><td>9.50</td><td>12.90</td><td>18.50</td><td>11</td><td>19.7</td>

<td>Mod300 - Mod100 [MPa]</td><td>8.10</td><td>8.90</td><td>10,80</td><td>11.90</td><td>8.00</td><td>7.60</td><td>10.30</td><td>14.60</td><td>8.8</td><td>16.2</td>

<td>Abrasion according to DIN standards [cm³]</td><td>117</td><td>105</td><td>113</td><td>127</td><td>123</td><td>123</td><td>139</td><td>108</td><td>131</td><td>119</td>

<td>HBU sample [° C]</td><td>116</td><td>115</td><td>115</td><td>103</td><td>115</td><td>120</td><td>117</td><td>110</td><td>108</td><td>109</td>

<td>Flexibility with reflection at 60 ° C [%]</td><td>60.6</td><td>56.5</td><td>61.6</td><td>68.1</td><td>58.20</td><td>52.30</td><td>53,40</td><td>66.20</td><td>61.1</td><td>67.0</td>

<td>tan dw at 60 ° C</td><td>.1536</td><td>.1513</td><td>.1290</td><td>.0829</td><td>0.1466</td><td>.1719</td><td>.1428</td><td>0.0997</td><td>0.121</td><td>0.092</td>

<td>tan dmax</td><td>.9353</td><td>.7577</td><td>.8724</td><td>.9344</td><td>.8907</td><td>.9548</td><td>.8349</td><td>.8989</td><td>0.890</td><td>0.887</td>

<td>T at tan dmax [° C]</td><td>-21</td><td>-25</td><td>-27</td><td>-24</td><td>-24</td><td>-20</td><td>-19</td><td>-20</td><td>-19</td><td>-14</td>