Sulfur functionalized polymer, polymer composition comprising the polymer and methods for preparing the same

Abstract

The present invention relates to a polymer that comprises the reaction product of a living polymer chain and a sulfur functionalizer and has a sulfur content of 70 ppm or more, an AFC of 90 to 125, and a NF slope of 0.20 to 0.70. The present invention further relates to a process for preparing the polymer, non-vulcanized and vulcanized polymer compositions comprising the polymer, a method of preparing the same and articles comprising at least one component formed from the vulcanized polymer composition.

Description

[0001] SULFUR FUNCTIONALIZED POLYMER, POLYMER COMPOSITION COMPRISING THE POLYMER AND METHODS FOR PREPARING THE SAME FIELD OF THE INVENTION

[0002] The present invention relates to novel polymers, comprising the reaction product of a living polymer chain and a sulfur functionalizer, which can be useful in the manufacture of rubber articles. The present invention further relates to a process for preparing the polymer, nonvulcanized and vulcanized polymer compositions comprising the polymer, a method of preparing the same and articles comprising at least one component formed from the vulcanized polymer composition.

[0003] BACKGROUND OF THE INVENTION

[0004] Polymers for ultra-high-performance (UHP) tire applications are desired to simultaneously show excellent dynamic properties (measured as tan 6 60°C and tan 6 0°C), polymer compound manufacture processing characteristics and feasibility for commercial production. The latter requires good polymer finishing properties in state-of-the-art polymer production plants. In particular, polymers for UHP tire tread applications used in compound mixtures comprising a filler such as silica / carbon black should preferably exhibit tailored properties to allow for both low rolling resistance and high run rates in tire production. Excellent polymer manufacture processing characteristics therefore needs to be associated with a good polymer and filler rubber composition processability, the latter typically based on a reasonably low viscosity of the fillercomprising rubber compounds. On the other hand, polymers with a high slope in the Newtonian flow region (dlogG" / dloga>) are susceptible to excessive polymer cold flow, which negatively impacts polymer manufacturing processability and production efficiency.

[0005] While dynamic properties of an article comprising a vulcanized polymer may be adjusted by choosing suitable functionalization and polymer architecture, the viscosity of silica-containing rubber compounds tends to increase with increasing functionalization degree, which is due to stronger polymer-filler interactions and highly interconnected polymer-filler aggregates, as well as with increasing weight-average molecular weight (Mw) of specific polymer architectures. Increased viscosities, however, negatively affect production throughput, rubber sheet quality, and extrusion characteristics of rubber compositions.Traditional approaches to addressing these issues, particularly the one of high (non-cured) rubber composition viscosity, involve measures such as reducing the polymer Mw, incorporating processing aids such as mineral oil into polymers and into rubber compositions, using in rubber compositions polymers without any filler-active polymer functionalization or reducing the concentration of filler-active functionalities in polymers. Unfortunately, these measures come at the cost of increased hysteresis loss, leading to deteriorated dynamic properties, which when preparing an article such as a tire or part of it is an undesirable trade-off for fuel efficiency and overall performance. The interplay between polymer architecture, processability of both polymers and corresponding filler-comprising rubber compositions, and dynamic properties of cured filler-comprising rubber compositions is a key challenge.

[0006] Known polymers, such as in EP 3045495 Bl do not provide a good balance between compound viscosity and tan 6 60°C, therefore either the processability of the polymer in the rubber formulation or the dynamic property of a cured rubber formulation is negatively impacted. Thus, there remains a need to improve the balance to enhance both processing performance and dynamic property. Several prior art disclosures, such as US 3,281,383, US 3,244,664 and US 3,692,874, indicate that solution styrene-butadiene rubber (SSBR) polymers without any filleractive polymer functionalization are relatively easy to process, but also suffer from deteriorated hysteresis properties compared to silica-modified SSBR. Furthermore, as shown in WO 2007 / 047943 A2 non-modified polymers exhibit deteriorated hysteresis properties, as evidenced by higher tan 6 values at 60°C, compared to chain end modified polymers.

[0007] Therefore, there remains a need to identify polymers meeting advanced architecture requirements, which meet the desired performance profile.

[0008] SUMMARY OF THE INVENTION

[0009] The present invention is based on the finding that the above objects can be solved by adjusting an architecture functionalization coefficient (AFC) and a slope in the region of Newtonian flow (slope dlogG" / dloga>), which may hereinafter also be referred to as NF slope, of a polymer having a sulfur content of 70 ppm or more to specific ranges.

[0010] Thus, in a first aspect, the present invention provides a polymer, comprising the reaction product of a living polymer chain and a sulfur functionalizer, having a sulfur content of 70 ppm or more, based on the total amount of monomer applied in polymerization, an AFC of 90 to 125, and a NF slope of 0.20 to 0.70.In a second aspect, the present invention provides a process for preparing the polymer of the first aspect, the process comprising the steps of: a) reacting monomers in the presence of one or more initiator or catalyst compounds in a polymerization process to form a living polymer chain, b) optionally reacting the living polymer chain with an in-chain functionalizer, c) optionally reacting the living polymer chain with a modifier, and d) reacting the remaining living chain ends with a chain-end functionalizer.

[0011] In a third aspect, the present invention provides a non-vulcanized polymer composition comprising the polymer of the first aspect and one or more additives.

[0012] In a fourth aspect, the present invention provides a vulcanized polymer composition which is obtainable by vulcanizing the polymer composition of the third aspect.

[0013] In a fifth aspect, the present invention provides a method of making a vulcanized polymer composition that comprises a step of vulcanizing the polymer composition of the third aspect.

[0014] In a sixth aspect, the present invention provides an article comprising at least one component formed from the vulcanized polymer composition of the fifth aspect.

[0015] It has surprisingly been found that by using the specific functionalized polymer of the present invention, a particularly beneficial interplay of characteristics can be achieved. First, the polymer has a slope in the region of Newtonian flow (slope dlogG" / dloga>), which may hereinafter also be referred to as NF slope, that assures cold flow stability and contributes to a good polymer manufacturing characteristic. Second, by using a functionalized polymer having an AFC, described in further detail below, within a specific range in accordance with the present invention, in a polymer composition both good dynamic properties and good processability of rubber compounds comprising a filler are achieved. The dynamic properties are anticipated to correspond with hysteresis properties and are measured as tan 6 60°C and tan 6 0°C, leading to an excellent rolling resistance and / or wet grip.

[0016] The present invention is based on the finding that the good processing performance of the functionalized polymer and the corresponding filler-comprising polymer composition as well the balance between good rolling resistance and grip results from unique polymer architecture features. The inventive AFC, determined as described in the experimental section below, takes into account the fraction of modified polymer, the architecture of the polymer, such as for example star-shaped, branched or linear polymer macromolecules, and the functionalizationdensity of a filler active functional group. The inventive range of the AFC corresponds to a functionalized polymer with well-balance polymer-filler interactions for optimized dynamic properties. AFCs below inventive range revealed deteriorated dynamic performance, while AFCs above the inventive range caused deteriorated processing of filler comprising compounds. In combination with NF slopes in inventive range, a production with good cold flow stability and manufacture run rates is enabled. It thus enables the manufacture of new functionalized polymers with an ideal combination of selected functional groups, functionalization density and polymer architecture. Functionalization density is defined by the number of functional groups, e.g. sulfur comprising moieties per kg rubber.

[0017] As a result, the present invention is addressing the requirements described herein, fulfilling them by an architecture functionalization coefficient not considered in the present field before together with a specific NF slope. By this way, the present invention has been achieved.

[0018] DEFINITIONS

[0019] In the present disclosure, the following definitions are applicable. The chemical definitions of substituents or specific moieties, as well as abbreviations as used herein generally correspond to the meaning known in the art.

[0020] Hydrocarbyl groups as used herein refer to univalent groups formed by removing a hydrogen atom from a hydrocarbon, such as methyl or phenyl. Hydrocarbon groups from which the hydrocarbyl groups are obtained include an alkyl group, an alkenyl group or an alkynyl group, that may be linear, branched or cyclic as well as an aryl group, an aralkyl group, or an alkylaryl group. To give an example, a C3 hydrocarbyl may be a propyl group, a 1-methylethyl group, a propenyl group, a propynyl group, or a cyclopropyl group. Likewise, e.g., a C6hydrocarbyl may be a 1-hexyl group, a 2-hexyl group, a 3-hexyl group, a methylpent-l-yl etc., a cyclohexyl group or a phenyl group.

[0021] Hydrocarbylene groups as used herein refer to divalent groups formed by removing two hydrogen atoms from a hydrocarbon, the free valencies of which are not engaged in a double bond, such as methylene or phenylene. Hydrocarbon groups from which the hydrocarbylene groups are obtained include an alkylene group, an alkenylene group or an alkynylene group, that may be linear, branched or cyclic as well as an arylene group, an aralkylene group, or an alkylarylene group.Alkyl groups as used herein and unless specifically defined otherwise, whether as such or in association with other groups, such as aralkyl or alkylaryl, include both straight linear alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, octyl etc., branched alkyl groups, such as isopropyl, tert-butyl, etc., and cyclic alkyl groups, such as cyclohexyl. An alkenyl group and an alkynyl group as used herein differ from an alkyl group in that they are unsaturated, i.e. an alkenyl group is characterised by containing a carbon-carbon double bond and an alkynyl group is characterised by containing a carbon-carbon triple bond. In accordance with the above definition of hydrocarbyl / -ene groups, alkylene, alkenylene and alkynylene groups differ from alkyl, alkenyl and alkynyl groups in that a second hydrogen atom is removed, resulting in divalent groups.

[0022] Aryl groups as used herein and unless specifically defined otherwise refers to a carbocyclic ring system comprising at least one aromatic ring. The aryl group may comprise one, two or three aromatic rings. Preferably, the aryl group is a monocyclic or bicyclic ring system. Aryl groups as used herein include, but are not limited to, phenyl, biphenyl and other benzenoid compounds. Aryl groups preferably contain only one aromatic ring and most preferably contain a Cg aromatic ring, that is a benzene ring. In accordance with the above definition of hydrocarbyl / -ene groups, an arylene group as used herein differs from an aryl group in that a second hydrogen atom is removed, resulting in a divalent group.

[0023] Aralkyl groups as used herein refer to an alkyl group that is substituted by one or more aryl groups. Aralkyl groups preferably contain only one aromatic ring and most preferably contain a Cg aromatic ring. Preferred aralkyl groups are benzyl and phenethyl. In accordance with the above definition of hydrocarbyl / -ene groups, an aralkylene group as used herein differs from an aralkyl group in that a second hydrogen atom is removed, resulting in a divalent group.

[0024] Alkylaryl groups as used herein refer to an aryl group that is substituted by one or more alkyl groups. Alkylaryl groups preferably contain only one aromatic ring and most preferably contain a Cg aromatic ring. Preferred alkylaryl groups are methylphenyl and ethylphenyl. In accordance with the above definition of hydrocarbyl / -ene groups, an alkylarylene group as used herein differs from an alkylaryl group in that a second hydrogen atom is removed, resulting in a divalent group.

[0025] Where the present description refers to "preferred" embodiments / features, combinations of these preferred embodiments / features shall also be deemed as disclosed as long as this combination is technically meaningful and obvious for the person skilled in the art.Hereinafter, the use of the terms "comprising", "containing" and "including" should be understood as disclosing in a non-limited way, that is to say that additional components or steps can be present or implemented, as long as this is technically meaningful.

[0026] DETAILED DESCRIPTION

[0027] In the following, the embodiments of the invention as set out in the appended claims will be explained in detail.

[0028] Functionalized Polymer

[0029] The polymer according to the first aspect of the invention comprises the reaction product of a living polymer chain and a sulfur functionalizer. Preferably, the polymer is obtained by the polymerization process described in further detail below.

[0030] The functionalized polymer of the present invention has a sulfur content of 70 ppm or more, preferably of 300 ppm or less, more preferably of 150 ppm or less. That is, the sulfur content of the functionalized polymer may preferably be 70 ppm or more and 300 ppm or less, and more preferably 70 ppm or more and 150 ppm or less. Preferably, the polymer comprises the reaction product of a living polymer chain and a sulfur functionalizer to give above sulfur content. The sulfur content in the functionalized polymer of the invention is based on the total amount of monomer applied in polymerization and may for example be determined by GC according to the method described in the experimental section below. Since the sulfur content is adjusted to meet the above range, dynamic properties of an article comprising a vulcanized composition of the polymer are excellent.

[0031] The functionalized polymer has an architecture functionalization coefficient (AFC) of 90 to 125, determined by GPC according to the method described in the experimental section below. As mentioned above, the AFC takes into account the fraction of modified polymer, the architecture of the polymer and the functionalization density of a filler active functional group. For example, the AFC increases with decreasing modified polymer fraction, with decreasing branched polymer structure (i.e. fewer arms), and with increasing functionalization density of a filler active functional group. The inventive range of the AFC corresponds to a functionalized polymer with well balance polymer-filler interactions for optimized dynamic properties. AFCs below inventive range revealed deteriorated dynamic performance, while AFCs above the inventive range caused deteriorated processing of filler comprising compounds. By adjusting the AFC to be within the above range, the present invention enables the manufacture of new functionalized polymers withan ideal combination of selected functional groups, functionalization density and polymer architecture.

[0032] Furthermore, the functionalized polymer of the invention has a NF slope, i.e. a slope in the region of Newtonian flow (slope dlogG" / dloga>) of 0.20 to 0.70, preferably of 0.25 to 0.65, determined according to a method as described in the experimental section below. Since the NF slope is adjusted in the above range, cold flow stability is assured and a good polymer manufacturing characteristics are obtained.

[0033] Surprisingly, it has been found that when the specific ranges of NF slope and AFC are combined in accordance with the present invention, functionalized polymers with above sulfur content are obtained that meet advanced architectural requirements, resulting in a performance profile desired for UHP applications.

[0034] In a preferred embodiment of the first aspect, the functionalized polymer of the invention has a glass transition temperature (Tg) of -95 °C to -20 °C, preferably -95 °C to -35 °C, and most preferably -90 °C to -50 °C, determined in accordance with ISO 11357-2 (1999).

[0035] In preferred embodiments, the polymer of the invention exhibits a peak molecular weight (measured by GPC as described below) in the range of 100.000 to 1,000,000 g / mol, preferably 150.000 to 800,000 g / mol, most preferably 200.000 to 500,000 g / mol.

[0036] The sulfur functionalizer that is reacted with the living polymer chain to give the functionalized polymer is not particularly limited. The sulfur functionalizer may be chosen to adjust the sulfur content in the functionalized polymer to the above range. Furthermore, the sulfur functionalizer may be an in-chain functionalizer or a chain-end functionalizer. Preferably, the sulfur functionalizer of the first inventive aspect is a sulfanylsilane compound. An example of a chainend functionalizer is the sulfanylsilane compound of the following Formula (I).

[0037] (RO)x(R)ySi — Rl— S — SiR3Formula (I)

[0038] In Formula (I), Si is silicon, S is sulfur and O is oxygen. Furthermore, x is an integer selected from 3-y, with y being an integer selected from 0, 1, and 2. In other words, if y is 0, then x is 3-0 = 3; if y is 1, then x is 3-1 = 2; and if y is 2, then x is 3-2 = 1. Preferably y is an integer selected from 0 and 1. Furthermore, R in Formula (I) is each independently selected from C1-C16alkyl; C6-C18aryl, and C7-C18aralkyl. That is two or more of the groups R in Formula (I) may be the same or all of groups R may be different from each other. More preferably, R in Formula (I) is each independently C1-C16alkyl. As regards Rlin Formula (I), this group is selected from C1-C16aryl, C1-C16alkylaryl, or C1-C16alkyl. More preferably Rlis C1-C16alkyl. In an even more preferred embodiment, groups R and Rlare each independently selected from C1-C5alkyl.

[0039] According to another preferred embodiment of the first aspect, the polymer optionally further comprises the reaction product of a living polymer chain and a functionalizer selected from a compound of the following Formulae (II), (III), (IV) or a combination thereof.

[0040]

[0041] [Formula (II)]

[0042] (OSiRIV3)n

[0043] RIII-Si-(X)m

[0044] (RV)3-m-n[Formula (III)]

[0045]

[0046] [Formula (IV)]

[0047] In Formula (II), Si is silicon. Furthermore, o is an integer selected from 0, 1, and 2, whereas p is an integer selected from 3-o. In other words, if o is 0, then p is 3-0 = 3; if o is 1, then p is 3-1 = 2; and if o is 2, then p is 3-2 = 1. R" in Formula (II) is each independently selected from C1-C30 hydrocarbyl, preferably C1-C12 hydrocarbyl. As regards group A in Formula (II), this is each independently an amino group selected from the following Formulae (A-i) to (A-v), i.e. two or more of A may be the same or all the groups A present in Formula (II), depending on the integer of p, may be different from each other.

[0048]

[0049] [Formula (A-i)]

[0050]

[0051] ormu a -v

[0052] In Formulae (A-i) to (A-v), N is nitrogen.

[0053] Furthermore, R1and R2in Formula (A-i) are same or different and are each independently selected from C1-C8alkyl, C6-C12aryl, C7-C15aralkyl, allyl, and -(CH2)q-Y-(CH2)r-CH3. In the formula -(CH2)q-Y-(CH2)r-CH3, the group Y is selected from -O- and -S-, i.e. divalent oxygen and sulfur groups, q is an integer from 1 to 12 and r is an integer from 0 to 12.

[0054] In Formula (A-ii), R3, R4, R5, R6are same or different and are each independently selected from H, and C1-C8alkyl. That is, two or more of R3, R4, R5, R6may be the same or all of R3, R4, R5, R6may be different from each other. The group Z in Formula (A-ii) is selected from -O-, -S-, -NR7-, -CH2-and -CH2CH2-. In the formula -NR7-, the group R7is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl and benzyl.

[0055] In Formula (A-iii), C is carbon and F is flour, in Formula (A-iv), R8is each independently selected from H and C1-C8alkyl, and in Formula (A-v), R9is selected from C1-C8alkyl.

[0056] In Formula (III), Si is silicon and O is oxygen. Furthermore, m and n are each independently 1 or 2, with m + n being 2 or 3. R1" in Formula (III) is vinyl optionally substituted with one or moresubstituents selected from methyl, ethyl and vinyl. In other words, RIIImay be selected from ethenyl, methylethenyl, ethylethenyl, or 1,3-butadienyl. As regards RIVand RV, these groups are each independently selected from C1-C18hydrocarbyl, and preferably C1-C8hydrocarbyl. Turning to group X in Formula (III), this is each independently a group selected from the following Formulae (X-i) to (X-iv):

[0057] |— R10-G

[0058] Formula (X-i)

[0059]

[0060] In Formulae (X-i) to (X-v), R10is selected from a Ci-Cig hydrocarbylene. The group G is each independently -NR11R12, with R11and R12being each independently selected from C1-C8alkyl, C6-C12aryl, C7-C15aralkyl, SiR133or C2-C8alkyl-O-SiR133, wherein R13is each independently selected from C1-C6alkyl, C6-C12aryl and C7-C18alkylaryl, and R11may optionally be connected with R10or R12to form a ring and the ring may contain, further to the R10-bonded nitrogen atom, one or more selected from an oxygen atom, a nitrogen atom and a sulfur atom, with the proviso that, in case R11and R12are both SiR133, two R13may be connected with each other to form a ring together with the Si-atoms to which they are bonded. The groups RIII, RIVand RVin Formulae (X-i) to (X-v) are as defined above for Formula (III). Furthermore, s and t are each independently 1 or 2. As regards G1in Formulae (X-iii) and (X-iv), this group is each independently a cyclic diaminediyl group such as piperazinyl; or G1is an amino group selected from the following Formula (X-G1):

[0061]

[0062] [Formula (X- G1)]

[0063] In Formula (X-GI), R14is selected from C1-C8alkyl, C6-C12aryl, C7-C15aralkyl, SiR133, or -R10G. G, R10and R13in group R14are as defined above for Formulae (X-i) to (X-v). That is, G is -NR11R12with R11and R12being each independently selected from C1-C8alkyl, C6-C12aryl, C7-C15aralkyl, SiR133or C2-C8alkyl-O-SiR133, R10is selected from C1-C18hydrocarbylene, and R13is selected from C1-C6alkyl, C6-C12aryl and C7-C18alkylaryl.

[0064] The above Formula (IV) corresponds to styrene including group X as a substituent at the benzene group that may be in ortho, meta or para position to the vinyl group. Preferably, X is a substituent at the benzene group that is in ortho- or para-position to the vinyl group. The group X in Formula (IV) is as defined above for Formula (III).

[0065] In a preferred embodiment, the polymer is an elastomeric polymer.

[0066] In preferred embodiments, the polymer is selected from the group consisting of solution styrenebutadiene rubber (SSBR), polybutadiene rubber (PBR), polyisocyanurate (PIR), solution styreneisoprene rubber (SSIR), solution styrene-isoprene-butadiene rubber (SSIBR) or combinations thereof. In more preferred embodiments, the polymer is selected from the group consisting of SSBR, PBR or a combination thereof, and most preferably the polymer is SSBR. Preferably, the SSBR has a vinyl content (vinyl content = the content of 1,2-butadiene fraction based on BR fraction of the polymer or copolymer) of 5-80 wt.%, for example 10-30 wt.%, 30-50 wt.% or 50-70 wt%, and a styrene content (depending on the specific application) of 40-70 wt.%, or 15-40 wt.%, or 2-15 wt.% based on butadiene copolymer fraction. In a most preferred embodiment, the SSBR has a vinyl content of 5-25 wt.% and a styrene content of 10-20 wt.%, each based on butadiene copolymer fraction. Preferably the PBR has a vinyl content of <15 wt.%; or 15-40 wt.%, or 40-80 wt.%.

[0067] Polymerization

[0068] In a second aspect, the present invention provides a process for preparing the polymer of the first aspect. The process comprises the following steps: a) reacting monomers in the presence of one or more initiator or catalyst compounds in a polymerization process to form a living polymer chain, b) optionally reacting the living polymer chain with an in-chain functionalizer, c) optionally reacting the living polymer chain with a modifier, and d) reacting the remaining living chain ends with a chain-end functionalizer. While the order of steps b) and c) may be interchanged, i.e. the process for preparing the polymer of the first aspect may be performed in the step order a)-c)-b)-d), the process of the second aspect of the present invention is preferably in the step order a)-b)-c)-d).The polymer can generally be prepared via anionic, radical or transition metal-catalyzed polymerization, preferably prepared by anionic polymerization.

[0069] The polymerization may be conducted in a solvent and may be carried out with one or more of inchain functionalizers, modifiers, chain end functionalizers, randomizer compounds and polymerization accelerator compounds as subsequently described.

[0070] Further to the following specific disclosure, generally applicable directions on polymerization technologies including polymerization initiator or catalyst compounds, polar coordinator compounds and accelerators (for increasing / changing the reactivity of the initiator or catalyst, for randomly arranging monomer units and / or changing their concentration); the amounts of each compound; monomer(s); and suitable process conditions are described in WO 2009 / 148932, the content of which is incorporated herein by reference in its entirety.

[0071] Monomers

[0072] In a preferred embodiment of the process according to the second aspect, the monomers may be selected from one or more conjugated diene monomers and optionally one or more aromatic vinyl monomers, in a case where the polymer of the first aspect is SSBR, PBR, SSIR, SSIBR or a combination thereof.

[0073] Exemplary conjugated diene monomers useful in the present invention include 1,3-butadiene, 2-(C1-5-alkyl)-1,3-butadiene such as isoprene (2-methyl-l,3-butadiene), 2,3-dimethyl-l,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, 1,3-cyclooctadiene, β-myrcene, terpinene, a-farnesene. A mixture of two or more conjugated dienes may be used. Preferred conjugated dienes include 1,3-butadiene and isoprene. In a preferred embodiment, the conjugated diene is 1.3-butadiene. The conjugated dienes may be used in a total amount of up to 99.99 wt.%, preferably 30 to 99.99 wt.%, based on the total weight of monomers used in the polymerization reaction.

[0074] The aromatic vinyl monomers are compounds having only one vinyl group attached to an aromatic group. Exemplary aromatic vinyl monomers include styrene, C1-4alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, a-methylstyrene, 2,4-diisopropylstyrene and 4-tert-butylstyrene, stilbene, vinyl benzyl dimethylamine, (4-vinylbenzyl)dimethyl aminoethyl ether, N, N-dimethylaminoethyl styrene, tert-butoxystyrene and vinylpyridine. Two or more aromatic vinyl monomers may beused in combination. A preferred aromatic monovinyl monomer is styrene. The aromatic vinyl monomer(s) may be used, depending on the application, in a total amount of up to 70 wt.%, especially 40-70 wt.% or 0-40 wt.%, for example 15-40 wt.% or 2-15 wt.%, based on the total weight of monomers used in the polymerization reaction. In a preferred embodiment, the conjugated diene is 1,3-butadiene, the aromatic vinyl monomer is styrene, and the SSBR thus obtained has a vinyl content of 5-25 wt.% in relation to the butadiene copolymer fraction of the SSBR and a styrene content is 10-20 wt.%.

[0075] Comonomers other than the conjugated diene monomer and the aromatic vinyl monomer, which may be used in preparing the polymer of the invention, include acrylic monomers such as acrylonitrile, acrylates, e.g., acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate, and methacrylates, e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. Comonomers also include aromatic di- or higher vinyl compounds which have two or more vinyl groups attached to an aromatic group, such as divinylbenzene, including 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene (which may be used as an isomeric mixture of 1, 2- / 1, 3- / 1, 4-divinylbenzene herein referred to as " DVB"). They may be used in total amounts of 1 wt.% or less (based on the total molar weight of the monomers used to make the polymer). In one preferred embodiment, 1,2-divinylbenzene is used in combination with styrene and butadiene or isoprene. Further monomers include, for example, vinyl aminosilanes as described in WO2015 / 055252, W02016 / 131590, WO2017 / 216344 and W02019 / 020752 or monomers as disclosed in W02008108377A or WO2019216645A1, the contents of which are incorporated herein by reference in its entirety.

[0076] Initiator / Catalysator Compounds

[0077] The polymerization process of the present invention is carried out in the presence of an initiator or catalyst compound, and two or more initiator or catalyst compounds may be used in combination.

[0078] Initiator compounds useful for preparing the SSBR, PBR, SSIR, SSIBR or a combination thereof, may be a monovalent or multivalent (divalent, trivalent, etc.) initiator compound, including dianionic initiators. Suitable initiator compounds include alkali metals, organoalkali metal compounds, a complex between an alkali metal and a polar compound, an oligomer containing an alkali metal, and Lewis acid-base complexes. Exemplary alkali metals include lithium, sodium, potassium, rubidium and cesium. Exemplary organoalkali metal compounds include ethyllithium, n-butyllithium, s-butyllithium, t-octyllithium, isopropyllithium, phenyllithium, cyclohexyllithium, 2-butyllithium, 4-phenylbutyllithium, t-butyldimethylsilyloxypropyllithium,dialkylaminopropyllithium, N-morpholinopropyllithium, lithiumdiisopropylamide, lithium piperidide, lithium pyrrolidide, dilithiated diphenylethylene compounds, multi-lithiated trivinyl benzene compounds, sodium biphenylide, sodium naphthalenide and potassium naphthalenide. Exemplary complexes between an alkali metal and a polar compound include a lithiumtetramethylethylenediamine complex, a lithium-tetrahydrofuran complex, a lithium-ditetrahydrofuranepropane complex, and the sodium and potassium analogues thereof. More preferably, the initiator compound is a mono- or dilithium alkyl, alkylaryl or aryl compound. Further useful initiators include the amino silane polymerization initiators described in WO 2014 / 040640 or / and the polymerization initiators described in WO 2015 / 010710, both incorporated herein by reference in its entirety. The total amount of the initiator(s), in particular the organolithium initiator(s), is adjusted depending on the monomer and target molecular weight. The total amount is typically from 0.05 to 5 mmol, preferably from 0.2 to 3 mmol per 100 grams of monomer.

[0079] Solvent

[0080] The polymerization can be conducted as a solution polymerization, wherein the formed polymer is substantially soluble in the reaction mixture, or as a suspension / slurry polymerization, wherein the formed polymer is substantially insoluble in the reaction medium. The terms "solution polymerization" and "suspension polymerization" or "slurry polymerization" are use with their conventional meaning in the art of polymerization. More preferably, the polymer is obtained in a solution polymerization. As the polymerization solvent, a hydrocarbon solvent is conventionally used, which does not deactivate the initiator, catalyst, active polymer chain or any further active entity or moiety. A combination of two or more solvents may also be used. Exemplary hydrocarbon solvents include aliphatic and aromatic solvents. Specific examples include (including all conceivable constitutional isomers): propane, butane, pentane, hexane, heptane, butene, propene, pentene, hexane, octane, benzene, toluene, ethylbenzene and xylene.

[0081] In-chain functionalizer

[0082] The in-chain functionalizer in the optional step b) may be added initially or intermittently (at regular or irregular intervals) or continuously during the polymerization of the process according to the second aspect of the present invention may be a compound of Formulae (II), (III), (IV) or a combination thereof as defined above with respect to the first aspect so that a detailed description is omitted here.Modifier

[0083] The modifier, in the optional step c) of the process according to the second aspect of the present invention may be one conventionally known in the art, such as a compound selected from the group consisting of SnCI4, SiCI4, CI3Si-SiCI3, CI3Si-O-SiCI3, CI3Sn-SnCI3, CI3Sn-O-SnCI3, Sn(OMe)4, Si(OMe)4, Sn(OEt)4, Si(OEt)4, (Ra)3SnCI, (Ra)2SnCI2, RaSnCI3, RaSiCI3, (Ra)2SiCI2and (Ra)3SiCI, with Rabeing each independently a hydrocarbyl group, preferably an alkyl group. Preferably, the modifier may be one or more selected from the group consisting of tin tetrachloride (SnCI4), tetrachloro silane (SiCI4), tetraethoxy silane (Si(OEt)4), tetramethoxy silane (Si(OMe)4) and hexachlorodisilane (HCDS, CI3Si-SiCI3). The total amount of modifier used influence the Mooney viscosity of the modified polymer and is typically in the range of 0.001 to 4.5 equivalents per mmol initiator, for example 0.01 to about 1.5 equivalents per mmol initiator. Preferably 0.02 to 1 equivalents, more preferably 0.03 to 0.5 equivalents of modifier per mmol initiator are used.

[0084] Chain-end functional izer

[0085] The chain-end functionalizer in step d) of the process of the second aspect may include one or more chain-end functionalizers conventionally known to further control polymer properties by reacting with the terminal ends of the polymer chains in the polymer of the invention. In general, chain-end functionalizers, such as those disclosed in WO 2014 / 040640 and WO 2015 / 010710 and the silane sulfide functionalizer described in WO 2014 / 040639, each of which is incorporated herein by reference in its entirety may be used.

[0086] In a preferred embodiment, the remaining living chain ends in step d) of the process of the second aspect are reacted with a chain-end functionalizer that is a sulfanylsilane compound of Formula (I) as defined above with respect to the first aspect so that a detailed description is omitted here.

[0087] The chain end functionalizers of step d) may be added intermittently (at regular or irregular intervals) or continuously during the polymerization but are preferably added at a conversion rate of the polymerization of more than 80 percent and more preferably at a conversion rate of more than 90 percent. Preferably, a substantial amount / number of the polymer chain ends is not terminated prior to the reaction with the chain end functionalizer; that is, living polymer chain ends are present and are capable of reacting with the chain end functionalizer.

[0088] Randomizer compounds

[0089] Randomizer compounds as conventionally known in the art (also known as polar coordinator compounds) may optionally be added either to the monomer mixture or polymerization reaction, in order to adjust the microstructure (i.e. the content of vinyl bonds) of the conjugated diene partof the polymer, or to adjust the composition distribution of any aromatic vinyl monomer and of the vinyl bonds in the polymer chain. A combination of two or more randomizer compounds may be used. Randomizer compounds useful for the invention are generally exemplified by Lewis base compounds. Suitable Lewis bases for use in the present invention are, for example, 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, (Ci-Cg alkyl)tetrahydrofurylethers (including methyltetrahydrofurylether, ethyltetrahydrofurylether, propyltetrahydrofurylether, butyltetrahydrofurylether, hexyltetrahydrofurylether and octyltetrahydrofurylether), tetrahydrofuran, 2,2-(bistetrahydrofuryl)propane (Randomizer 2), bistetrahydrofurfurylformal, methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, a-methoxytetrahydrofuran, dimethoxybenzene and dimethoxyethane, and tertiary amines such as triethylamine, pyridine, N, N, N', N'-tetramethyl ethylenediamine (randomizer 1), dipiperidinoethane, methyl ether of N, N-diethylethanolamine, ethyl ether of N, N-diethylethanolamine, N, N-diethylethanolamine and dimethyl N, N-tetrahydrofurfuryl amine. Examples of preferred randomizer compounds are identified in WO 2009 / 148932, incorporated herein by reference in its entirety. The randomizer compound is typically added at a molar ratio of randomizer compound to initiator compound of from 0.012:1 to 10:1, preferably from 0.1:1 to 8:1 and more preferably from 0.13:1 to about 6:1.

[0090] Accelerator compounds

[0091] The polymerization can optionally include accelerator compounds to increase the reactivity of the initiator (and, thus, to increase the polymerization rate), to randomly arrange aromatic vinyl monomers introduced into the polymer, or to provide a single chain of aromatic vinyl monomers, thus influencing the distribution of aromatic vinyl monomers in a living anionic copolymer. Examples of accelerators include sodium alkoxides or sodium phenoxides and potassium alkoxides or potassium phenoxides, preferably potassium alkoxides or potassium phenoxides, such as potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium n-heptyloxide, potassium benzyloxide, potassium phenoxide; potassium salts of carboxylic acids, such as isovaleric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linolenic acid, benzoic acid, phthalic acid and 2-ethyl hexanoic acid; potassium salts of organic sulfonic acids, such as dodecyl benzenesulfonic acid, tetradecyl benzenesulfonic acid, hexadecyl benzenesulfonic acid and octadecyl benzenesulfonic acid; and potassium salts of organic phosphorous acids, such as diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, and dilauryl phosphite. Such accelerator compounds may be added in a total amount of from 0.005 to 0.5 mol per 1.0 gram atom equivalent of initiator.Non-vulcanized polymer composition

[0092] The non-vulcanized polymer composition, also referred to as non-cured polymer composition, of the third aspect of the present invention comprises the above-described polymer according to the invention and one or more additives.

[0093] For example, the one or more additives are selected from extender oils, stabilizers and further polymers, including polymer oils (Mp(real) = 700 to 50,000 g / mol measured by GPC), (which are not the polymers of the invention). Such further polymers include what is conventionally referred in this field to as oligomers. Liquid polymers or polymer oils or oligomers are, e.g., homo- or copolymers of styrene, isoprene, butadiene or farnesene.

[0094] In one embodiment, the polymer composition comprises one or more fillers. In another embodiment, the polymer composition additionally comprises one or more vulcanizing agents. In a preferred embodiment, the polymer composition comprises one or more fillers and one or more vulcanizing agents.

[0095] The following components are conventionally added in non-vulcanized compositions used in tires: extender oils, stabilizers, fillers, further polymers including polymer oils (Mp(real) = 700 to 50,000 g / mol measured by GPC).

[0096] Plasticizers

[0097] It has surprisingly been found that by using the specific functionalized polymer of the present invention, a particularly beneficial interplay of characteristics can be achieved. As described above, the present invention successfully controls an increase of the viscosity of filler-containing rubber compounds. The addition of processing aids such as a mineral oil can therefore be reduced or completely omitted. In other words, in a preferred embodiment, the non-vulcanized polymer composition of the third aspect includes a total amount of less than 50 phr of one or more extender oils. That is, while the composition may include 0-25 phr or 25-40 phr or 40-70 phr of one or more extender oils. The composition preferably includes less than 1 phr of an extender oil, the extender oil excluding liquid polymers and resins.

[0098] In one embodiment, the polymer composition of the present invention comprises the polymer of the invention in combination with one or more oils, especially mineral oils or extender oils from natural (non-fossil) sources (such as sunflower oil, rapeseed oil, soy oil, tall oil or castor oil). For representative examples and classification of oils see, e.g., WO 2009 / 148932 and US 2005 / 0159513, each of which is incorporated herein by reference in its entirety.Such oils include, for instance, conventionally known extender oils such as aromatic, naphthenic and paraffinic extender oils, for example MES (mild extraction solvate), TDAE (treated distillate aromatic extract), rubber-to-liquid (RTL) oils, biomass-to-liquid (BTL) oils, factices, extender resins or liquid polymers (such as liquid BR) having a median molecular weight (determined via GPC according to BS ISO 11344:2004) of from 800 to 50,000 g / mol. When liquid polymers are used as extender oils in the polymer composition of the present invention, they are not taken into account when calculating the composition of the polymer matrix. When using a mineral oil as the extender oil, it is preferably one or more selected from DAE (Distillated Aromatic Extracts), RAE (Residual Aromatic Extract), TDAE, MES and naphthenic oils. The aforementioned oils comprise different concentrations of polycyclic aromatic compounds, paraffinics, naphthenics and aromatics, and have different glass transition temperatures. The above-mentioned types of oil have been characterized in " Kautschuk, Gummi, Kunststoffe", vol. 52, pages 799-805. In some embodiments, MES, RAE and TDAE are preferred extender oils for rubber.

[0099] The one or more oils can be added to the polymer prior to or after the termination of the polymerization process. When the extender oil is added to the polymer solution, the timing of addition should preferably be after modification of the polymer or termination of the polymerization, for example after the addition of the modifying agent or polymerization termination agent. After the addition of extender oil, the oil-extended polymer composition can be obtained by separating any polymerization solvent from the polymer by means of a direct drying method or steam stripping, drying the rubber using a vacuum dryer, hot-air dryer, roller and the like.

[0100] In another embodiment, the oil is added to the "solvent-free" polymer in a mechanical mixer together with preferably at least one filler, and at least one further polymer.

[0101] Stabilizers

[0102] One or more stabilizers (also referred to as "antioxidants") can optionally be added to the polymer or to the non-vulcanized polymer composition comprising the polymer of the first aspect as an additive to prevent the degradation of the polymer by molecular oxygen. In case one or more stabilizers are added to the polymer, they may be added prior to or after the termination of the polymerization process.

[0103] Antioxidants based on sterically hindered phenols, such as 2,6-di-tert-butyl-4-methylphenol, 6,6'-methylenebis(2-tert-butyl-4-methyl phenol), Iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hexamethylenebis[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'-ethylidenebis-(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-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, and antioxidants based on thio-esters, such as 4,6-bis(octylthiomethyl)-o-cresol and pentaerythrityl tetrakis(3-laurylthiopropionate), are typically used. Other stabilizers are phosphite based (e.g. tris[4-(l,l-dimethylpropyl)phenyl] phosphite, bis[2,4-bis(2-methylbutan-2-yl)phenyl] [4-(2-methylbutan-2-yl)phenyl] phosphite, bis[4-(2-methylbutan-2-yl)phenyl][2,4-bis(2-methylbutan-2-yl)phenyl] phosphite, tris[2,4-bis(2-methylbutan-2-yl)phenyl] phosphite octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate). Further examples of suitable stabilizers can be found in F. Röthemeyer, F. Sommer, Kautschuk Technologie, 2nded., (Hanser Verlag, 2006) pages 340-344, and references cited therein.

[0104] Further polymers

[0105] Apart from the polymer of the invention, extender oil(s), filler(s), etc., the polymer composition of the invention may additionally contain further polymers, especially further elastomeric polymers. Further polymers may be added in the form of a solution to a solution of the polymer of the invention prior to work up of the polymer blend or may be added during a mechanical mixing process. Further polymers as referred to herein are polymers which are not in accordance with the polymer of the invention. Such further polymers include what is conventionally referred to as oligomers in this field.

[0106] Fillers

[0107] The polymer composition of the present invention, which optionally comprises one or more extender oils as defined above, may further comprise one or more fillers. One or more fillers can be added after the termination of the polymerization process. Examples of suitable fillers include carbon black (including electroconductive carbon black), carbon nanotubes (CNT) (including discrete CNT, hollow carbon fibers (HCF) and modified CNT carrying one or more functional groups, such as hydroxyl, carboxyl and carbonyl groups), graphite, graphene (including discrete graphene platelets), silica, carbon-silica dual-phase filler, clays (layered silicates, including exfoliated nanoclay and organoclay), calcium carbonate, magnesium carbonate, magnesium oxide, titanium dioxide, rubber gels, lignin, amorphous fillers, such as glass particle-based fillers, starch-based fillers, and combinations thereof. Further examples of suitable fillers are described in WO 2009 / 148932, which is fully incorporated herein by reference.In the polymer composition of the present invention, the one or more fillers are preferably selected from carbon black, carbon nanotubes, graphite, graphene, silica, carbon-silica dual-phase filler, clays calcium carbonate, magnesium carbonate, lignin, glass particle-based fillers and starch-based fillers, preferably the filler is carbon black or silica or may be a combination thereof. More preferably, the filler is silica.

[0108] As the carbon black, any type of carbon black conventionally known to a person of skill in the art may be used. In one embodiment, the carbon black has an iodine number according to ASTM D 1510 of 20 to 250 mg / g, preferably 30 to 180 mg / g, more preferably 40 to 180 mg / g, and even more preferably 40 to 130 mg / g, and a DBP number according to ASTM D 2414 of 80 to 200 ml / 100 g, preferably 100 to 200 ml / 100 g, more preferably 115 to 200 ml / 100 g (the DBP number determines the specific absorption volume of carbon black or of any bright filler by means of dibutyl phthalate).

[0109] Any type of silica conventionally known to a person of skill in the art and suitable as filler for tire rubber blends may be used. It is particularly preferred to use highly dispersed, precipitated silica having an nitrogen surface area (BET surface area; according to DIN ISO 9277 and DIN 66132) of 35 to 350 m² / g, preferably 35 to 260 m² / g, more preferably 100 to 260 m² / g and even more preferably 130 to 235 m² / g, and having a CTAB surface area (according to ASTM D 3765) of 30 to 400 m² / g, preferably 30 to 250 m² / g, more preferably 100 to 250 m² / g and even more preferably 125 to 230 m² / g. Such silica results, e.g. in rubber blends for tire treads, in particularly beneficial physical properties of the vulcanizates. In addition, it may bring about advantages in the processing of the blend, namely by reducing the time required for blending, while maintaining product properties, thus improving productivity. Useful silicas include those of the type Ultrasil® VN3 (trademark of Evonik Industries) as well as highly dispersed types, so-called HD silicas (e.g. Zeosil® 1165 MP of Rhodia).

[0110] Vulcanizing agents and vulcanizing accelerators

[0111] The polymer composition of the present invention may optionally further comprise one or more vulcanizing agents. Any vulcanizing agent conventionally used in the manufacture of rubber products can be used in the invention, and a combination of two or more vulcanizing agents may be used.

[0112] Sulfur, sulfur-containing compounds acting as sulfur donors such as dithiols, sulfur accelerator systems and peroxides are the most common vulcanizing agents. Examples of sulfur-containingcompounds acting as sulfur donors include dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethyl thiuram disulfide (TETD) and dipentamethylene thiuram tetrasulfide (DPTT). Examples of sulfur accelerators include amine derivates, guanidine derivates, aldehydeamine condensation products, thiazoles, xanthogenates, thiuram sulfides, dithiocarbamates and thiophosphates. It is preferably to use one or more sulfonamide accelerators selected from N-cyclohexyl 2-benzothiazol sulfenamide (CBS), N, N-dicyclohexyl benzothiazole 2-sulfenamide (DCBS), benzothiazyl 2-sulfenemorpholide (MBS) and N-tert-butyl 2-benzothiazyl sulfenamide (TBBS). Further crosslinking systems such as available under the trade names Vulkuren® (1,6-bis(N, N-dibenzyl thiocarbamoyldithio)-hexane; Lanxess), Duralink® or Perkalink® (1,3-bis(citraconimidomethyl)benzene; Lanxess) or disclosed in WO 2010 / 049261 may be added to the polymer composition. Examples of peroxides include di-tert-butyl-peroxides, di-(tert-butyl-peroxy-trimethyl-cyclohexane), di-(tert-butyl-peroxy-isopropyl-)benzene, dichlorobenzoylperoxide, dicumylperoxides, tert-butyl-cumyl-peroxide, dimethyl-di(tert-butyl-peroxy)hexane, dimethyl-di(ter-butyl-peroxy)hexine and butyl-di(tert-butyl-peroxy)valerate (Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000). A vulcanizing accelerator of the sulfene amide-type, guanidine-type or thiuram-type can be used together with a vulcanizing agent as required.

[0113] In addition, the polymer composition of the invention may contain conventional additives and vulcanization auxiliaries in proportions conventionally used. Such additives include:

[0114] a) aging inhibitors such as N-phenyl N'-(l,3-dimethylbutyl)-p-phenylenediamine (6PPD), N, N'- diphenyl-p-phenylenediamine (DPPD), N, N'-ditolyl-p-phenylenediamine (DTPD), N-isopropyl N'-phenyl-p-phenylenediamine (IPPD), 2,2,4-trimethyl 1,2-dihydrochinolin (TMQ), b) activators such as zinc oxide and fatty acids (e.g. stearic acid), wherein zinc oxide (zinc white) is preferably used as a component of the sulfur accelerator system;

[0115] c) waxes;

[0116] d) resins, especially adhesive resins;

[0117] e) mastication additives such as 2,2'-dibenzamidodiphenyldisulfide (DBD); and

[0118] f) processing additives such as zinc soaps and fatty acid esters and their derivatives.

[0119] Vulcanizing agents are typically added to the polymer composition in a total amount of from 0.5 to 10 parts by weight or, in some embodiments, 1 to 6 parts by weight per 100 parts by weight of the polymer. Examples of vulcanizing accelerators and amounts thereof relative to the polymer are given in WO 2009 / 148932, which is incorporated herein by reference in its entirety.Vulcanized polymer composition

[0120] The vulcanized polymer composition of the fourth aspect of the present invention is obtainable by vulcanizing the polymer composition of the invention comprising one or more vulcanizing agents. The method of making the vulcanized polymer composition of the fifth aspect of the present invention comprises a step of vulcanizing the polymer composition of the invention that comprises one or more vulcanizing agents under conditions and with machinery conventionally known in the art.

[0121] Article

[0122] The article of the sixth aspect of the present invention comprises at least one component formed from the vulcanized polymer composition of the invention, wherein the article preferably is a rubber-comprising article. The article may be, for instance, tire tread, a tire side wall, a tire carcass, a belt, a gasket, a seal, a hose, a vibration damper, an automotive part, a footwear component such as a shoe sole, a golf ball or a tire. Preferably, the article is a tire, more preferably the article is a summer, winter, all-weather passenger car tire or truck tires.

[0123] EXAMPLES

[0124] The present invention is explained in more detail by way of following examples, which are not intended to be limiting the present invention as set out in the appended claims.

[0125] Chemicals

[0126] • Solvent

[0127] Cyclohexane

[0128] • Monomer

[0129] Butadiene

[0130] Styrene

[0131] • Randomizer

[0132] TMEDA (N, N, N', N'-tetramethyl ethylenediamine)

[0133] Initiator

[0134] NB (n-Butyllithium solution in cyclohexane)In-Chain Functionalizer

[0135] ICF-1 (1-(ethenyldimethylsilyl)-4-ethylpiperazine; purity: > 97%)

[0136] 1H NMR (400 MHz, 20°C, C6D6): δ [ppm] = 6.14 (dd, J = 20.4 Hz, J = 14.8 Hz, 1H), 5.94 (dd, J = 14.8 Hz, J = 4.0 Hz, 1H), 5.72 (dd, J = 20.4 Hz, J = 4.0 Hz, 1H), 2.90 (t, J = 5.2 Hz, 4 H), 2.24 (q, J = 7.2 Hz, 2H), 2.21-2.17 (m, 4H), 1.00 (t, J = 7.2 Hz, 3H), 0.13 (s, 6H).13C NMR (100 MHz, 20°C, C6D6): δ [ppm] = 139.3, 132.2, 57.2, 53.3, 45.8, 12.3, -2.3.

[0137] ICF-2 (3,3'-[3-(1,1-dimethylethyl)-1-ethenyl-3,3-dimethyl-1-disiloxanyl]-bis[N, N-dimethyl-1-propanamine]; purity: > 97%)

[0138] 1H NMR (400 MHz, 20°C, C6D6): δ [ppm] = 6.16 (dd, J = 20.4 Hz, J = 15.2 Hz, 1 H), 5.96 (dd, J = 15.2 Hz, J = 4.0 Hz, 1 H), 5.82 (dd, J = 20.4 Hz, J = 4.0 Hz, 1 H), 2.22 (t, J = 7.2 Hz, 4 H), 2.13 (s, 12 H), 1.66-1.58 (m, 4 H), 0.96 (s, 9 H), 0.76-0.72 (m, 4 H), 0.11 (s, 6 H).13C NMR (100 MHz, 20°C, C6D6): δ [ppm] = 138.0, 132.7, 63.3, 45.6, 26.0, 21.9, 18.4, 13.4, - 2.5.

[0139] ICF-3 (Isomer mixture of 1-[2-(4-ethenylphenyl)ethyl]-pyrrolidine and 1-[2-(3-ethenylphenyl)ethyl]-pyrrolidine; purity: > 83%; residuals are corresponding 1-[2-(4-ethylphenyl)ethyl]-pyrrolidine and 1-[2-(3-ethylphenyl)ethyl]-pyrrolidine)

[0140] 1H NMR (400 MHz, 20°C, CDCl3): δ [ppm] = 7.32 - 7.04 (bm, 4H), 6.66 (dd, J = 17.6 Hz, 10.9 Hz, 1H), 5.76 (dd, 1H), 5.24 (dd, 1H), 2.81 (t, J = 5.1 Hz, 2H), 2.71 (t, J = 5.2 Hz, 2H), 2.57 (t, J = 4.8 Hz, 4H), 1.80 (m, 4H).13C NMR (100 MHz, 20°C, CDCl3): δ [ppm] = 144.3, 140.8, 137.7, 136.9, 128.5, 128.2, 126.6, 126.2, 125.90, 125.5, 123.9, 113.7, 113.1, 58.4, 54.3, 35.8, 23.5. GC): [%] = 11.2 (1,3-ethyl isomer), 5.8 (1,4-ethyl isomer), 65.8 (1,3-vinyl isomer), 17.2 (1,4-vinyl isomer), isomers verified via GC-MS coupling.

[0141] Chain-End Functionalizer

[0142] CEF (3-methoxy-3,8,8,9,9-pentamethyl-2-oxa-7-thia-3,8-disiladecane; purity: > 96%)1H NMR (400 MHz, 20°C, CDCl3): δ [ppm] = 3.51 (s, 6H), 2.52 (t, J = 7.2 Hz, 2H), 1.67 (dt, J = 16.4, 7.5 Hz, 2H), 0.96 (s, 9H), 0.79 - 0.70 (m, 2H), 0.26 (s, 6H), 0.12 (s, 3H).13C NMR (100 MHz, 20°C, CDCl3): δ [ppm] = 77.3, 77.0, 76.7, 50.2, 29.7, 26.6, 26.3, 18.9, 12.7, -3.6, -5.8.

[0143] Modifier

[0144] HCDS (1,1,1,2,2,2-hexachlorodisilane)

[0145] TMOS (tetramethoxysilane)

[0146] SnCI4(tin tetrachloride)Polymer Samples

[0147] The polymers samples of Examples El to E6 and Comparative Examples CE1 to CE7 were obtained according to the following general description. Details on the chemicals used and their amounts are summarized in Table 1 below.

[0148] Cyclohexane, butadiene-initial and styrene were charged to an air free 20 L reactor, and the stirred mixture was heated up to 56.5 °C. Then TMEDA and optionally an in-chain functionalizer were added and NB was charged dropwise to react the impurities until the color of the reaction mixture changed to yellowish (titration).

[0149] After that the required amount of NB was charged immediately to initiate the polymerization. The charge of the initiator was used as the start time of the polymerization. Parallel the temperature was increased by heating or cooling in the wall of the reactors beginning with the charge of the initiator to the final polymerization temperature of 85 °C with 2.7 °C / min.

[0150] After 12 min butadiene-incremental was charged over 80 min and the mixture was stirred further for 25 min. Then, if used, a modifier was added. After 20 min of stirring (just in case of Modifier HCDS stirring time was increased to 30 min), a chain-end functionalizer was added to the reactor and the reaction was stirred for further 18 min. The reaction was terminated with charge of methanol.

[0151] The polymer solution was stabilized with Irganox 1520D (0.2 phm), the polymer recovered by steam stripping and dried until a content of residual volatiles < 0.6% was obtained. The Mark-Houwink parameters for linear reference Comparative Example 1 were determined according to GPC methods as described in test method section to a = 0.618 and logK = -3.057 (K in [dL / g]). Characteristics of samples El to E6 and CE1 to CE7 are summarized in Table 2 below.Table 1: Polymerization Chemicals

[0152]

[0153] Table 2: Polymer Characteristics

[0154]

[0155] Polymer Compositions

[0156] After workup of the polymers, the samples were compounded in a Brabender 350S internal mixer by applying a two-step mixing process with the following conditions:

[0157] 1stmixing stage: Initial rotor speed: 50 rpm

[0158] Chamber temperature: 50°C

[0159] Total mixing time: 10 min

[0160] 2ndmixing stage: Initial rotor speed: 50 rpm

[0161] Chamber temperature: 50°C

[0162] Total mixing time: 5 min

[0163] The used mixing recipe including further additives is listed in Table 3 with the amounts of the formulation ingredients given in phr ("parts per hundred rubber") for each mixing step.

[0164] Table 3: Mixing Recipe

[0165] Mixing stage Formulation Amount / phr

[0166] 1stmixing step Polymer sample 80.0

[0167] SYNTECA® Ni45[1]20.0

[0168] Silica BET 160 m2 / g[2]80.0

[0169] Silane TESPD[3]6.9

[0170] Stearic acid 2.0

[0171] 6PPD[4]2.0

[0172] Zinc oxide 2.5

[0173] Wax[5]1.5

[0174] DPG[6]2.0

[0175] PEG-1500[7]4.0

[0176] TDAE[8]45.0

[0177] 2ndmixing step Sulfur 1.4

[0178] TBBS91.7

[0179] [1]min 94 % cis structures content (Synthos Schkopau GmbH)

[0180] [2]Ultrasil® 7000 GR, BET 160 m2 / g2(Evonik Industries)

[0181] [3]Bis(triethoxysilylpropyl)disulfide; Si 266® (Evonik Industries)

[0182] [4]N-l,3-dimethylbutyl-N'-phenyl-p-phenylenediamine; Dusantox® 6PPD (Duslo)

[0183] [5]Antisun and antiozonant wax; Antilux® 654 (Lanxess)

[0184] [6]1,3-diphenylguanidine

[0185] [7]Polyethylene glycol, Mw = 1.4 to 1.6 kg / mol (Avokal)

[0186] [8]Treated distilled aromatic extract; extender oil (Hansen & Rosenthal)

[0187] [9]N-tert-butyl-2-benzothiazole sulfenamideThe performance properties summarized in Table 4 obtained from raw polymer mixtures after the 2ndmixing step and from vulcanized rubber samples were determined by applying testing methods described below.

[0188] Table 4: Composition Characteristics’*

[0189]

[0190] xvalues >100 in line 3 represent improved rolling resistance predictive values, while values >100 in line 4 represent improved tensile strength values

[0191] Compared to the comparative samples CE1 to CE7, the inventive samples El to E6 show processible compound Mooney viscosities (CML) and improved rolling resistance indicators (tan 8 60°C). Mechanical properties such as tensile strength (TS) listed in Table 4, are for the inventive and comparative samples on a similar level.

[0192] Results

[0193] The obtained polymer characteristics 1) AFC, 2) sulfur content and 3) cold flow storage stability (NF slope) as well as the compound characteristics 4) CML and 5) rolling resistance indicator (tan 8 60°C) are summarized in Table 5 and grouped by the investigated modifiers and functionalization technologies.Table 5: Polymers grouped by modificationx

[0194]

[0195] xvalues >100 in column 6 represent improved rolling resistance predictive values

[0196] In comparison to comparative sample CE1 containing no sulfur and no modification, the functionalized, sulfur containing comparative sample CE3 without modification is characterized by an AFC of 122 and shows an 28% improved rolling resistance indicator tan 8 60°C. However, CEB has a NF slope higher than the beneficial upper-range value of 0.70 and thus unfavourable low cold flow storage stability. In contrast, comparative sample CE2 with increased in-chain functionalization show an AFC higher than the beneficial upper-range value of more than 125 causing deteriorated processible compound Mooney viscosities (CML).

[0197] In comparison to the HCDS modified comparative sample CE4 containing no sulfur, the HCDS modified inventive sample El containing sulfur is characterized by an increased AFC of 107 and shows a good cold flow storage stability determined by a low NF slope, a good processible CML and a 27 % improved rolling resistance indicator tan 8 60°C. An unfavorable low AFC of 55 was found for comparative sample CE5, which is modified with 0.56 mmol HCDS and contains sulfur in inventive range. As a result a worse processability indicated by a CML of 72 MU was found.

[0198] In comparison to the SnCI4modified comparative sample CE6 containing no sulfur, the sulfur containing inventive sample E3 modified with SnCI4is characterized by an AFC of 113 and shows agood cold flow storage stability determined by an intermediate NF slope, a good processible CML and a 29 % improved rolling resistance indicator (tan 860°C).

[0199] In comparison to the TMOS modified comparative sample CE7 containing no sulfur, the sulfur containing inventive samples E6 and E4 modified with TMOS are characterized by an increased AFC of up to 119 and show good cold flow storage stabilities determined by low NF slope, a good processible CML. Inventive example E4 contains additionally functionalizer IFC-1 and shows an improved rolling resistance indicator (tan 860°C) by 34%.

[0200] The sulfur containing inventive examples E2 and E5 are in-chain functionalized additionally with ICF-1 and ICF-2. Comparing inventive examples E2 and E5 with non- modified comparative sample CE1 and the HCDS modified comparative sample CE4 both containing no sulfur; E2 and E5 are characterized by a levelled AFC and show good cold flow storage stabilities determined by low NF slope, a good processible CML and a up to 20 % improved rolling resistance indicator tan 860°C.

[0201] Test Methods

[0202] Various methods were used to test and measure the examples. A description of each technique is provided below.

[0203] NMR spectroscopy

[0204] NMR spectroscopy was performed on a BRUKER Avance II (400MHz) in a 5-mm dual probe. Vinyl and total styrene content were measured using1H-NMR spectroscopy according to ISO 21561-2005, wherein vinyl contents are reported as wt% per total butadiene. CDCU / TMS was used as solvent in a weight ratio of 0.05%: 99.95%.

[0205] Gel Permeation Chromatography (GPC)

[0206] Standard molecular weights and molecular weight distributions (MWD) of the polymers were measured via GPC using a refractive index detector and polystyrene standards for calibration. Reported peak molecular weight (Mp) values, number average molecular weight (Mn) or the weight average molecular weight (Mw) are given based on polystyrene standards. The molecular weight distribution is expressed as the polydispersity index (PDI) Đ = Mw / Mn.

[0207] • GPC instrument and software

[0208] Instrument: Agilent Technologies 1260 Infinity II

[0209] Detector: Refractive index detector Agilent 1260 RID Modell G1362AMeasurement / Analysis software: Agilent OpenLAB CDS Chemstation Edition / Cirrus

[0210] • GPC Measurement conditions

[0211] GPC column: 3x Agilent PLgel MIXED-B 300x7.5mm columns (Agilent Technologies Inc.) Mobile phase: Tetrahydrofuran (Fisher Scientific HPLC grade, stabilized with 0.025% BHT, water <0.03%) containing 10 mL triethylamine (Thermo Fisher, analytical grade 99.5%) per 1 L tetrahydrofuran

[0212] Flow rate: 1.0 mL / min

[0213] Column oven temperature: 40°C

[0214] Detector temperature: 40°C

[0215] Sample solution injection volume: 100 pL

[0216] Calibration: Conventional calibration using Rl detector by means of EasiCal PS-1 (EasiCal A and B) polystyrene standards (Agilent Technologies) in given molecular weight range (EasiCal A 6545000, 739 500, 128900, 29460, 3 320 g / mol and EasiCal B 2327000, 298600, 75050, 9310, 580 g / mol)

[0217] • GPC Sample preparation

[0218] 10 mg of polymer sample were added into a screw vial, sealed and dissolved in 10 mL tetrahydrofuran / triethylamine solution (10 mL triethylamine (Thermo Fisher, analytical grade 99.5%) per 1 L tetrahydrofuran (Fisher Scientific HPLC grade, stabilized with 0.025% BHT, water <0.03%) by means of a Heidolph platform shaker (Promax 2020) for 2 hours. Afterwards, filtration was performed via a 0.45 pm pore size PTFE Agilent Captiva Econofilter of 25 mm diameter.

[0219] Architecture Functionalization Coefficient (AFC)

[0220] The determination of the AFC was accomplished using Malvern GPCmax VE2002 equipped with a Malvern VISCOTEK 305 TDA triple detector. A universal calibration was applied using a narrow polystyrene standard.

[0221] • Instrument and software

[0222] Instrument: Malvern Panalytical Ltd. GPCmax VE2002

[0223] Detector: Malvern VISCOTEK 305 TDA triple detector

[0224] (refractive index, light scattering, viscosimeter)

[0225] Measurement and analysis software: OmniSec 5.10.461 (Malvern Panalytical Ltd.)

[0226] Measurement conditionsGPC column: 3x Agilent PLgel MIXED-B 300x7.5mm columns (Agilent Technologies Inc.) Mobile phase: Tetrahydrofuran (Fisher Scientific HPLC grade, stabilized with 0.025% BHT, water <0.03%) containing 10 mL triethylamine (Thermo Fisher, analytical grade 99.5%) per 1 L tetrahydrofuran

[0227] Flow rate: 0.5 mL / min

[0228] Column oven temperature: 40°C

[0229] Detector temperature: 40°C

[0230] Sample solution injection volume: 100 pL

[0231] Calibration: Universal calibration using narrow polystyrene standard (Agilent Technologies Inc) with Mw of 89 600 g / mol, PDI of 1.04 and an intrinsic viscosity of 0.3778 dL / g

[0232] Sample preparation

[0233] 10 mg of polymer sample were added into a screw vial, sealed and dissolved in 10 mL tetrahydrofuran / triethylamine solution (10 mL triethylamine (Thermo Fisher, analytical grade 99.5%) per 1 L tetrahydrofuran (Fisher Scientific HPLC grade, stabilized with 0.025% BHT, water <0.03%) by means of a Heidolph platform shaker (Promax 2020) for 2 hours. Afterwards, filtration was performed via a 0.45 pm pore size PTFE Agilent Captiva Econofilter of 25 mm diameter.

[0234] Calculation AFC

[0235] The calculation of AFCs was accomplished according to Equation 1 (Eq. 1) using the abovedescribed instrument and measurement conditions. For analysis of GPC chromatograms, each peak (x) was integrated separately determining weight average molecular weight via light scattering (MWx(sample)), intrinsic viscosity ([n]X(sampiej), and refractive index (RI) detector areas for all polymer samples. All polymer signals with distinct maximum were considered as individual peaks. An example is shown in Figure 1 below. However, the findings of present invention are not limited to the shown example or a specific number of peaks. The parameters (a_reference and K_reference were determined using reference linear Comparative Example 1 (CE1) under the above given measurement conditions.

[0236]

[0237] [η]x(sample) Measured intrinsic viscosity in dL / g corresponding to GPC peak x of polymer sampleReference Fit parameter K according to Equation 2 of reference linear CE1 in dL / g determined on same GPC system and conditions as investigated polymer sample

[0238] a_reference Fit parameter according to Equation 2 a of reference linear CE1 determined on same GPC system and conditions as investigated polymer sample MWx(sampie) Weight average molecular weight in g / mol determined via light scattering detection corresponding to peak x of polymer sample

[0239] (Rl area peak)xIntegrated area of refractive index detector signal in mVmL for individual peak x of polymer sample

[0240]

[0241]

[0242] logMw

[0243] Figure 1: Schematic example for GPC chromatogram of a polymer sample used for calculation of AFC. All polymer signals with distinct maximum were considered as individual peaks. However, the findings of present invention are not limited to shown example or specific number of peaks.

[0244] Parameters a and K were obtained fitting linearly the molecular weights vs intrinsic viscosities plot according to Equation 2 (Eq.2) obtained from triple detection GPC.

[0245] log[η] = logK + a logMwEq.2

[0246] [r|] Intrinsic viscosity in dL / g

[0247] MwWeight average molecular weight in g / mol

[0248] Example of GPC chromatogram shown in Figure 1. Noticeably, the method described herein can be used for any chosen number of GPC peaks. Moreover, the measurement of non-modified reference CE1 (o and K) and sample on same GPC instrument and setup in a time window of <10 days were considered as important to avoid inaccuracies by different measurement conditions like solvent purity (e.g. water content due to different storage / usage times), different columnhistories or deviations in detector accuracy. The AFC can also be applied to oil extended diene polymers after extracting extender oil according to common techniques such as, for example ASTM D5774.

[0249] Glass Transition Temperature (Tg)

[0250] The glass transition temperature Tgwas determined as described in ISO 11357-2 (1999) by using the DSC Q2000 under the following conditions:

[0251] Weight: ca. 10 to 12 mg

[0252] Sample container: Alu / S

[0253] Temperature range: (-150 to 100) °C

[0254] Heating rate: 20 K / min or 5 K / min

[0255] Cooling rate: free cooling

[0256] Purge gas: 20 ml He / min

[0257] Cooling agent: liquid nitrogen

[0258] Each sample was measured at least once. The measurements contain two heating runs. The 2ndheating run was used to determine the glass transition temperatures.

[0259] Mooney viscosities ML and CML

[0260] Mooney viscosity (ML) of the polymer samples and compound Mooney viscosity (CML) of the compound samples was measured according to ASTM D1646 with large rotor geometry at temperature of 100°C.

[0261] Slope in the region of Newtonian flow "dlogG" / dlogcD" (NF flow)

[0262] Determination of slope dlogG" / dloga> has been carried out using an ARES 2 Rheometer with heating chamber and plate-plate geometry. The heating chamber was flushed with nitrogen atmosphere to prevent any oxidative effects during measurement and achieved a temperature stability of + / - 0.5K during measurement. The samples have been applied as a 2 mm thick film onto the round shaped plane-parallel rotors with diameter of 25 mm. The rotors have been specifically designed as transparent rotors manufactured of quartz glass to ensure by optical inspection that no inclusions such as gas bubbles are present or evolved during testing.

[0263] Shear strain amplitude was applied at 1 %, well covering linear-viscoelastic response region of the samples. Isothermal frequency sweeps at temperatures starting from 25°C to 135°C in steps of 10K have been carried out, screening a frequency w range of 0.03-100 rad / s with a step width of 5frequency steps per logarithmic decade. Samples have been applied in the measuring device under constant normal force of 20 N and after each temperature step was reached, the annealing time of 10 min has been applied to ensure homogeneous heating of the sample.

[0264] According to time-temperature superposition principle applied, slope in the region of Newtonian flow dlogG" / dloga> has been determined at 135°C in a frequency range between 0.03-0.1 rad / s, showing linear behavior in logarithmic scale and representing Newtonian-like flow behavior at low frequencies when shifted to reference temperature of 25°C. This behavior is dependent by chain architecture, affected by modification or introduction of functional groups and is material specific. In case of increasing slope in the region of Newtonian flow dlogG" / dloga>, chain mobility is increased at low frequency and material exhibits increased cold flow / creep when instantaneous static load would be applied (co -> 0 rad / s).

[0265] Gas Chromatography (GC)

[0266] GC measurements were conducted on Agilent 7890 with autosampler and FID detector. As column HP-5 (30m x 0.32 mm x 0.25 pm) was applied. AS injection method SSL, 1 pL @ 260 °C with split ratio 10:1 was used. The temperature program started at 40 °C (1 Min) and then heated up in a first step from 40 °C a 110 °C with 8 K / Min as heating rate, in a second step heating rate was increased to 15 K / Min to increase temperature to 300 °C (hold time 4 Min) and in a last heating step increased to 320 °C with a heating rate of 15 K / Min (hold time 2 Min). The method was calibrated in a range from 30 to 150 ppm.

[0267] The reactor sample after functionalization of the polymer was diluted with cyclohexane in a ratio of 1:10 to 1:15 prior GC measurement.

[0268] The amount of sulfur content [ppm] in the polymer was referred to the amount of abovedescribed chain-end functionalizer CEF to the polymer chains. In a first step the amount of chainend functionalizer CEFattached to the polymer was calculated by the following equation:

[0269] Amount of CEF attached to the polymer [ppm] = (amount of CEF added to the polymer solution [ppm] - amount of CEF remaining in polymer solution upon completion of functionalization reaction monitored via the GC-measurement described above.

[0270] In a second step, the amount of sulfur was calculated via relation of CEF to the total amount of polymer solution and the sulfur content of CEFvia the following equation:Sulfur amount in polymer [g] = amount of CEF attached to the polymer [ppm] * total amount of polymer solution [g] / 1000000 * x * 32.065 [g / mol] / molecular weight of CEF [g / mol]. The x is number of sulfur per CEF.

[0271] The sulfur amount [g] in the polymer was then related to total amount of monomer (butadiene and styrene) applied in the polymerization to calculate the concentration by the following equation:

[0272] Sulfur content in polymer [ppm] = amount of sulfur bonded to polymer [g] / total amount of monomer applied in polymerization [g] * 1000000. The sulfur content for each example and comparative example can be found in Table 2.

[0273] Tensile test of vulcanized rubber

[0274] Tensile strength (TS) was measured according to ASTM D412 using a ZwickRoell Z010 with type C dumbbell test specimens. Three measurements of the thickness were made, whereby the median of the three measurements was used as the thickness in calculating the cross-sectional area. The transverse speed was 500 mm / min.

[0275] Dynamic-mechanical analysis of vulcanized rubber

[0276] The tangent of the phase angle (tan 8 60°C) as rolling resistance predictor was determined in tension mode using a Netzsch DMA Gabo EPLEXOR 150N with the following testing conditions:

[0277] Sample clamping length: 27 mm

[0278] Sample width: ca. 7.7 mm

[0279] Sample thickness: ca. 2.0 mm

[0280] Temperature: 60 °C

[0281] Frequency: 10 Hz

[0282] Static strain amplitude: 11 %

[0283] Dynamic strain amplitude for tan 860°C: 5 %

Claims

CLAIMS1. A polymer, comprising the reaction product of a living polymer chain and a sulfur functionalizer, having a sulfur content of 70 ppm or more, based on the total amount of monomer applied in polymerization and determined by the method described in the specification,wherein the polymer has:an architecture functionalization coefficient (AFC) of 90 to 125, determined by gel permeation chromatography (GPC) according to the method described in the specification, anda slope in the region of Newtonian flow (slope dlogG" / dloga>) of 0.20 to 0.70, determined according to method as described in the specification.

2. The polymer of claim 1, wherein the polymer has:a sulfur content of 70 ppm or more and 300 ppm or less, preferably 150 ppm or less; and / ora glass transition temperature (Tg) of -95 °C to -20 °C, preferably -95 °C to -35 °C, and most preferably -90 °C to -50 °C, determined in accordance with ISO 11357-2 (1999); and / ora slope in the region of Newtonian flow (slope dlogG" / dloga>) of 0.25 to 0.65.

3. The polymer of claim 1 or 2, wherein the functionalizer is a sulfanylsilane compound of the following Formula (I):[Formula (I)](RO)x(R)vSi — R1— S — SiR3wherein in Formula (I),x is an integer selected from 3-y;y is an integer selected from 0, 1, and 2, preferably y is an integer selected from 0 and 1; R is each independently selected from Ci-Cis alkyl; Cg-Cig aryl, and C7-Cig aralkyl; and R1is Ci-Cis aryl, Ci-Cis alkylaryl, or Ci-Cis alkyl, preferably R1is Ci-Cis alkyl.The polymer of claims 1 to 3, wherein the polymer optionally further comprises the reaction product of a living polymer chain, and a functionalizer selected from a compound of the following Formulae (II), (III), (IV) or a combination thereof:[Formula (II)]wherein in Formula (II),o is an integer selected from 0, 1, and 2;p is an integer selected from 3-o;R" is each independently selected from C1-C30 hydrocarbyl; andA is each independently an amino group selected from the following Formulae (A-i) to (A-v):[Formula (A-i)]wherein in Formula (A-i), R1and R2are same or different and are each independently selected from Ci-Cg alkyl, Cg-Cu aryl, C7-C15 aralkyl, allyl, and -(CI- Jq-Y-fCI- Jr-CHg, with Y being selected from -O- and -S-, q being an integer from 1 to 12 and r being an integer from 0 to 12;[Formula (A-ii)]wherein in Formula (A-ii), R3, R4, R5, R6are same or different and are each independently selected from H, and Ci-Cg alkyl and Z is selected from -O-, -S-, -NR7-, - CH2- and -CH2CH2- with R7is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl and benzyl;wherein in Formula (A-iv), R8is each independently selected from H and Ci-Cg alkyl;[Formula (A-v)]wherein in Formula (A-v), R9is selected from Ci-Cg alkyl;[Formula (III)](OSiRIV3)nR'"-Si- (X)m(RV)3-m-nwherein in Formula (III),m and n are each independently 1 or 2, with m + n being 2 or 3;R1" is vinyl optionally substituted with one or more substituents selected from methyl, ethyl and vinyl;RIVand Rvare each independently selected from Ci-Cig hydrocarbyl; andX is each independently a group selected from the following Formulae (X-i) to (X-iv):(X-i) (X-ii) (X-iii) (X-iv)wherein in Formulae (X-i) to (X-v),R10is a C1-C18 hydrocarbylene;G is each independently -NR11R12, with R11and R12being each independently selected from Ci-Cg alkyl, Cg-Cu aryl, C7-C15 aralkyl, SiR133 or C2-C8alkyl-O-SiR133, wherein R13is each independently selected from Ci-Cg alkyl, Cg-Cu aryl and C7-Cig alkylaryl, and R11may optionally be connected with R10or R12to form a ring and the ring may contain, further to the R10-bonded nitrogen atom, one or more selected from an oxygen atom, a nitrogen atom and a sulfur atom, with the proviso that, in case R11and R12are both SiR133, two R13may be connected with each other to form a ring together with the Si-atoms to which they are bonded;R1", RIVand Rvin Formulae (X-i) to (X-v) are as defined above for Formula (III);s and t are each independently 1 or 2; andG1is each independently a cyclic diaminediyl group such as piperazinyl or G1is an amino group selected from the following Formula (X-G1):[Formula (X- G1)]wherein in Formula (X-G1), R14is selected from Ci-Cg alkyl, Cg-Cu aryl, C7-C15 aralkyl, Si R133, or -R10G, with G, R10and R13being as defined above for Formulae (X-i) to (X-v);[Formula (IV)]wherein in Formula (IV), X is as defined above for Formula (III).

5. The polymer of claims 1 to 4, wherein the polymer is selected from the group consisting of solution styrene-butadiene rubber (SSBR), polybutadiene rubber (PBR), solution styrene-isoprene rubber (SSIR), solution styrene-isoprene-butadiene rubber (SSIBR) or combinations thereof, preferably the polymer is selected from the group consisting of SSBR, PBR or a combination thereof, and most preferably the polymer is SSBR.

6. A process for preparing the polymer as defined in claims 1 to 5, wherein the process comprises the following steps:a) reacting monomers in the presence of one or more initiator or catalyst compounds in a polymerization process to form a living polymer chain;b) optionally reacting the living polymer chain with an in-chain functionalizer;c) optionally reacting the living polymer chain with a modifier; andd) reacting the remaining living chain ends with a chain-end functionalizer.

7. The process of claim 6, wherein:the monomers are selected from one or more conjugated diene monomers and optionally one or more aromatic vinyl monomers; and / orthe polymerization process is an anionic or radical or transition metal-catalyzed polymerization, preferably an anionic polymerization; and / orthe chain-end functionalizer is a sulfanylsilane compound of Formula (I) as defined in claim 3; and / orthe in-chain functionalizer is a compound of Formulae (II), (III), (IV) or a combination thereof as defined in claim 4.

8. A non-vulcanized polymer composition comprising the polymer as defined in claims 1 to 5 and one or more additives.

9. The polymer composition according to claim 8, wherein the one or more additives are selected from plasticizers, stabilizers and further polymers.

10. The polymer composition according to claim 8 or 9, further comprising one or more fillers, preferably selected from carbon black, carbon nanotubes, graphite, graphene, silica,carbon-silica dual-phase filler, clays, calcium carbonate, magnesium carbonate, lignin, glass particle-based fillers and starch-based fillers, preferably the filler is silica.

11. The polymer composition according to any one of claims 8 to 10, further comprising one or more vulcanizing agents.

12. A vulcanized polymer composition obtainable by vulcanizing the polymer composition as defined in claim 11.

13. A method of making a vulcanized polymer composition, wherein the method comprises the step of vulcanizing the polymer composition as defined in claim 11.

14. An article comprising at least one component formed from the vulcanized polymer composition as defined in claim 12, wherein the article preferably is a rubber-comprising article.

15. The article according to claim 14, wherein the article is a tire tread, a tire side wall, a tire carcass, a belt, a gasket, a seal, a hose, a vibration damper, an automotive part, a footwear component, a golf ball or a tire, more preferably a summer, winter, all-weather passenger car tire or truck tire.

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