Anionic polymers coupled with siloxane oligomers

Abstract

Living polymers prepared by organolithium initiated polymerization of conjugated diene monomer or copolymerization of conjugated diene and vinyl aromatic monomers are efficiently coupled by using a functionalized siloxane oligomer blend as coupling agent. Diene rubber compositions partially coupled with functionalized siloxane oligomer blends exhibit broad molecular weight distribution, increased throughput in their industrial processing, as well as faster dissolution in recipes to produce rubber toughened plastics such as HIPS and ABS. Radial styrene-butadiene block copolymers as well as their corresponding hydrogenated block copolymers achieved excellent thermoplastic elastomer performance and can be used for hotmelt adhesives, sealants, asphalt modification, footwear; technical compounds, thermoplastic gels, films or elastic fibers.

Description

Attorney Docket No.: DYN-10-PCTAPPLICATION FOR PATENTTITLE: ANIONIC POLYMERS COUPLED WITH SILOXANE OLIGOMERSAPPLICANT: Dynasol Eiastomeros, S. A. de C. V.Carretera Tampico-Mante km. 28.5Col. Santa Am liaAltamira, Tamaulipas, Mexico 89602INVENTORS:Luis Antonio Rodnguez GuadarramaTitan 15, Floor 9thMadrid, Spain 28045Daniel Abraham Elizarraras MayaPrivada Encino 319 i nt. 67, Col. Presas del Arena!, Tampico, Tamaulipas, Mexico 89344Sergio Albert o Moctezu a Espiri cuetoBosque de Los Colorines 302, Residencial Los Encinos, Altamira, Tamaulipas, Mexico 89606Oscar German Sanchez MunizSor Juana Ines de la Cruz 108, Col. del Maestro,Ciudad Madero, Tamaulipas, Mexico 89550Attorney Docket No.: DYN-10-PCTANIONIC POLYMERS COUPLED WITH SILOXANE OLIGOMERSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U. S. Provisional Patent Application No. 637737,723 filed on 22 December 2024.BACKGROUND OF THE INVENTION1. FIELD OF THE INVENTION

[0002] The present invention relates to rubbers that are produced through organolithium initiated anionic solution polymerization of conjugated diene monomer, copolymerization of conjugated diene monomers and vinyl aromatic monomers, or block copolymerization of conjugated diene monomers and vinyl aromatic monomers, followed by a coupling step of living polymer chains with a blend of Siloxane oligomers. The invention also relates to high impact polystyrene (HIPS) and acrylonitrile-butadiehe-styrene (ABS) plastics produced with such rubbers. The rubbers described in the invention can also be used in hotmelt adhesives, sealants, asphalt modification, footwear, technical compounds, thermoplastic gels, films or elastic fibers.2. DESCRIPTION OF THE RELATED ART

[0003] Solution rubbers produced by organolithium initiated polymerization of conjugated diene monomers, or block copolymerization of conjugated diene and vinyl aromatic monomers are widely used in several industrial applications. Polybutadiene (BR), styrene-butadiene tapered block copolymers (S-SBR). and styrene-butadiene block copolymers (SBS) are recommended for toughening of styrenic plastics, whereas hydrogenated styrene-butadiene block copolymers (SEBS) are more suited for toughening polyolefins.

[0004] Two relevant rubber-toughened styrenic plastics are high impact polystyrene (HIPS) and acrylonitrile butadiene styrene (ABS) plastics. These plastics are produced by bulk free radical polymerization of Styrene dr copolymerization of styrene and acrylonitrile, respectively, in the presence of BR, S-SBR, or SBS, or their blends. The initial step of fully dissolving the rubber (BR,Attorney Docket No.: DYN-10-PCTS-SBR, SBS) in the monomers, styrene or a styrene / acrylonitrile mixture, is critical from the standpoint of process throughput and plastic performance. Certain grades of HIPS and ABB require polybutadiene rubbers with solution viscosities, between 40-250 cP at 5 wt.% in styrene. In such cases the initial step of dissolving the rubber in the monomer(s) becomes a limitation, therefore it is highly desirable that rubbers exhibit short dissolution times, It is also desirable that rubbers have certain Mooney viscosity (ML1+4 at 100 °C), most desirably above 30 but lower than TOO, to avoid cold flow of the rubber during its storage and transportation.

[0005] Polybutadienes with a balanced solution viscosity, Mooney viscosity, and cold flow are typically achieved by partially coupling the living polymer chains after complete butadiene polymerization. By employing this method, poly dispersity index of the molecular weight distribution of polybutadienes is increased. When a coupling agent with functionality higher than two is used the high molecular weight fraction comprises polymer molecules with radial topology, also called branched, or multi-arm structure. It is well known in the art that the presence of radial species effectively reduces cold flow of the polybutadiene and increases its Mooney to solution viscosity ratio.

[0006] Some of the coupling agents usually found in the prior art can be epoxidized soybean oil, diviny I benzene, tin halides, silicon halides functional ized tin compounds, functionalized silicon compound such as a silane compound and functionalized oligomeric compounds such as the ones listed in U. S. Patent No.7,517,934. Silicon tetrachloride, tin tetrachloride and divinylbehzene are specific examples of prior art coupling agents. The partial coupling is achieved by controlling the dosage of coupling agent to deviate the amount of its reactive coupling moieties from the stoichiometric amount of living anionic polymer chains.

[0007] In the synthesis of radial tetra-chain organolithium initiated anionic polymerization, silicon tetrachloride or tin tetrachloride are commonly used as coupling agents. These compounds are highly unstable, as they form hydrogen chloride upon contact with air, which is highly toxic and corrosive. Therefore, it is necessary to use containers and pumps specially designed for these compounds. An additional problem of chlorosilane compounds and tinAttorney Docket No.: DYN-10-PCTtetrachloride is their low thermal stability during storage. A safer option that produces less corrosive secondary compounds is the use of less reactive coupling agents such as alkoxy silane compounds.

[0008] Moreover, the use of efficient coupling agents such as silicon chloride compounds leads to disadvantages associated with the presence of chloride compounds in the final product, like high rubber color and gel issues. While in case of using less reactive coupling agents such as monomeric alkoxysilane compounds (tetramethoxysilane, tetraethpxysilane, vinyltriethoxysilane, methyltriethoxysilane, etc. leads to large quantities of alcohol byproduct due to the alkoxysilane hydrolysis during the stripping process. Remaining alkoxy moieties left attached on the coupling residue after coupling reaction of the living polymer with the coupling agent, if the alkoxy moieties are in excess or sterically hindered from the attack of active lithium in the polymerization, may cause silanol condensation reactions between the coupled polymer chains that ultimately could result in ah uncontrolled increase in Mooney viscosity, and may as well generate gel issues.

[0009] CN 109,503,746 A discloses production of a polybutadiene with bi modal molecular weight distribution by coupling, wherein each peak in the molecular weight distribution has a polydispersity index (Mw / Mh) lower-than or equal to 1.10, its polymerization is carried out batchwise in the presence of a polar modifier, such as tetra hy rofuran, the coupling reaction is performed using a silicon halide such as SiCh, termination of polymer anions is performed by aqueous solution of CO2, it is recovered a polybutadiene whose solution viscosity at 5 wt.% in styrene at 25 °C is from 40 to 190 cP, and Mooney viscosity (ML1+4 at 100 ’C) is from 40 to 65. Likewise, CN 109,503,747 A discloses production of a polybutadiene with also a polydispersity index lower than or equal to 1.10 in each of its individual coupled and uncoupled fractions, using same means Of production, but where molecular weight and coupling level are adjusted to recover a polybutadiene whose solution viscosity at 5 wt.% in styrene at 25bC is from 80 to 120 cP. In both documents, advantages are shown on reduction of polybutadiene color by CO2 termination, comparing against termination step with Isopropanol, and on improvement on impact strength of a HIPS, in this case theAttorney Docket No.: DYN-10-PCTimprovement is relative to comparative examples that only deviate from the claimed range of solution viscosity.

[0010] U. S. Patent No. 8,481,644 discloses production of polybutadienes coupled with a tetraalkoxysjlane. Polybutadienes described in the invention have a broad unimodal molecular weight distribution and they are obtained using a continuous polymerization process. Polybutadienes exhibit an appropriate balance of solution viscosity, Mooney viscosity, and vinyl content for the fabrication of HIPS and ABS plastics. Coupled polybutadienes with chlorosilanes is claimed to increase gel content, equipment corrosion, and reactor fouling during the production of HIPS and ABS plastics. Coupled polybutadienes with silicon tetrachloride:. The most used chlorosilane is silicon tetrachloride.

[0011] EP 3,655,442 B1 discloses production of polybutadienes coupled with 3-glyCidoxyprdpyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, having viscosity in styrene at 5 wt.% between 30 to 60 cP. Advantages shown were Mooney to styrene Solution viscosity ratio of greater than 1.0 (to reduce cold flow), and low color, relative to polybutadienes coupled with other coupling agents such as n-propyltrimethoxysiiane, tetramethoxysilane, SiCl4, 1,1,1, 1-tetra(glycidyloxymethyl) methane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and (3-methacryloxypropyl)trimethoxysilane.

[0012] WO 2023 / 104783 A1 discloses a method for production of polydienes and copolymers of diene with vinyl aromatic monomers, which includes a coupling reaction employing a coupling agent comprising 2 to 20 unsaturated siloxane units, such as 1,3,5, 7-tetra vin l-1,3,5,7- tetramethylcyclotetrasiloxane and octavinyloctasilasesqui oxane, in combination with additional functionalizing agents. Likewise, WO 2023 / 104784 Al discloses a method for production Of polydienes and Copolymers of diene with vinyl aromatic monomers, which includes a coupling reaction employing a cyclic coupling agent comprising 2 to 20 unsaturated siloxane units, such as 1,3,5,7- tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, but excluding polycyclic coupling agents. Both documents only shown advantages of coupled and functionalized rubbers in the scope of vulcanizate silica filled composition properties for end-use in tires.Attorney Docket No.: DYN-10-PCT

[0013] US 2005 / 0107541 discloses the use of polyhedral oligosilsesquioxahes (POSS compounds) as coupling agents to produce radial polydienes, where the coupling of the living polymer chains is carried out through the substituents with vinyl groups. Some of the siloxanes used were isobutyl-, vinyl-, octavinyl- or octaglycidyl imethylsilyl-POSS.

[0014] It is identified the need for coupled BR, S-SBR, SBS, and SEBS rubbers substantially free of chloride residuals. It is also needed formulations and processes for coupled rubber industrial production that depletes the amount of alcohol byproduct relative to coupled rubbers using monomeric alkoxysilanes. It is also needed to improve rubber production throughput, particularly in the dewatering and drying steps. Moreover, it is needed to achieve rubbers exhibiting reduced levels of gel and faster dissolution capability, particularly in HIPS and ABS polymerization recipes.SUMMARY OF THE INVENTION

[0015] The present invention provides polymeric rubber compositions comprising partially coupled conjugated diene polymers, partially coupled styrene-butadiene tapered block copolymers, partially coupled styrenebutadiene block copolymers, or their hydrogenated versions, wherein polymeric branches or arms are covalently bonded to residues of coupling reactions between living anionic polymers and blends of functionalized siloxane oligomers. Compared with prior art polymers, the inventive polymeric rubber compositions are characterized by broader molecular weight distributions in their coupled fraction, lower gel content, and faster dissolution capability in end-use HIPS and ABS recipes;

[0016] The present invention also discloses processes to produce polymeric rubber compositions comprising partially coupled conjugated diene polymers, partially coupled styren -butadiene tapered block copolymers, partially coupled styrene-butadiene block copolymers, and their hydrogenated versions, wherein polymeric branches or arms are covalently bonded to residues of coupling reactions between living anionic polymers and blends of functionalized siloxane oligomers. Compared with using prior art monomeric alkpxysilanes as coupling agents, the use of blends of functionalized siloxaneAttorney Docket No.: DYN-10-PCToligomers as coupling agents produce smaller amounts of byproduct alcohol, thus reducing contamination and the need of purification of the reclairned and recycled hydrocarbon solvent and of the steam-stripping serum, also depleting volatile organic compounds (VOC) emissions, and ultimately lowering alkyllithium initiator consumption in the polymerization step. Embodiments to the present invention also comprise processes where smaller quantities of blends of functionalized siloxane oligomers are needed to achieve a specific coupling percentage compared with larger amounts required when using prior art monomeric alkoxysilanes as coupling agents. The invention also provides processes that increase industrial production throughput of such partially coupled polymeric rubber compositions, particularly in the finishing steps of rubber dewatering and drying.

[0017] The invention also covers novel HIPS and ABS plastics, with desired and unexpected performance properties and prepared by improved process, polymerized in the presence of the inventive rubbers such as partially coupled conjugated diene polymers, partially coupled styrene-butadiene tapered block copolymers, and / or partially coupled styrene-butadiene block copolymers, or their hydrogenated versions, wherein the polymeric branches or arms of such rubbers are covalently bonded to residues of coupling reactions between living anionic polymers and blends of functional ized siloxane oligomers.

[0018] Additional embodiments of the invention are end-use applications of inventive hydrogenated partially coupled styrene-butadiene block copolymers (SEBS) for toughening polyolefins and, wherein compounding of partially coupled SEBS provides a thermoplastic elastomer (TPE) composition that unexpectedly exhibits low haze and high transparency. Similarly, end-use applications of inventive partial ly coupled styrene-butadiene block copolymers (partially coupled SBS) for toughenihg polystyrene. Also, ome of the inventive polymers are Useful for plastic modification by mechanical mixing, asphalt modification, adhesives, sealants, vulcanized compounds, microcellular compounds, oil gel compositions and battery cell binders.Attorney Docket No.: DYN-10-PCTBRIEF DESCRIPTION OF THE DRAWINGS

[0019] A clearer understanding of the invention can be achieved by considering the detailed description of exemplary embodiments provided below:

[0020] Figure 1. Coupling efficiency as a function of the methoxy / NBL molar ratio for Dynasylan 6490 (vinyl-methoxy functionalization).

[0021] Figure 2. Molecular weight istribution of polybutadienes coupled with Dynasylan 6490.

[0022] Figure 3. Coupling efficiency as a function of the ethoxy / NBL molar ratio for Dynasylan 6498 (vinyl-ethoxy functionalization).

[0023] Figure 4. Molecular weight di stri but io h of polybutadienes coupled with Dynasylan 6498.

[0024] Figure 5. Coupling efficiency as a function of the methoxy / NBL molar ratio for Dynasylan VPS 4721 (eppxy-methoxy).

[0025] Figure 6. Molecular weight distribution of polybutadienes coupled with Dynasylan VPS: 4721.

[0026] Figure 7, Coupling efficiency as a function of vinyl groups / NBL molar ratio for 1,3,5;7-tetramethyM,3,5,7-tetravinylcyclotetrasiloxane (vinyl-D4).

[0027] Figure 8. Molecular weight distribution of polybutadienes coupled With 1,3,5, 7- tetra methy l- 1,3, 5, 7-te trav iny I cyclot etra s iloxane (v iny I- D4), Dynasylan 6490 or Dynasylan 6498.DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

[0028] The polymeric rubber compositions to the present invention comprise polymers of generalized formulas (P)n- and P, wherein P is an uncoupled linear polymer, prepared by living anionic polymerization, comprising conjugated diene repeating units, or optionally comprising conjugated diene and vinyl aromatic repeating units, and wherein (P)n-X is a coupled polymer comprising n arms Of polymer P covalently coupled to residue X by electrophilic addition or substitution reaction of living polymer with a coupling agent, wherein n ranges from 2 up to 25, and wherein X is the residue of the coupling agent, and wherein the coupring agent is selected from the group of olefinically functionalized siloxane oligomer blends, epoxy functionalized siloxane oligomer blends, and their mixtures thereof, The molecular weight distribution (MWD) ofAttorney Docket No.: DYN-10-PCTthe polymeric rubber cornpositions of the invention comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value. The polymeric rubber compositions to the present invention comprise polymers wherein the poly dispersity i ndex of the coupled fraction (P)n-X, Mw_c / Mn_c, specifically the ratio of weight-average molecular weight of the coupled polymer fraction to the number-average molecular weight of the coupled polymer fraction, is greater than 1,10, wherein the MWD is measured by GPC calibrated with polystyrene standards. The olefinically functionalized siloxane oligomer blends, used as coupling agents in the production of coupled polymer (P)n-X, comprise unsaturated hydrocarbyi functional groups, alkoxy functional groups, and optionally saturated hydrocarbyi groups. The epoxy functionalized siloxane oligomer blends used as coupling agents in the production of coupled polymer (P)n-X comprise alkyl ether functional groups substituted by epoxide or alkyl functions I groups substituted by epoxide, alkoxy functional groups, and optionally saturated hydrocarbyi groups. The functionalized siloxane oligomer blends may optionally comprise other functional groups such as those formed by a combination of atoms selected from the group of carbon, hydrogen, nitrogen, oxygen, or sulfur atoms,

[0029] The production of a coupled polymer molecule (P)n-X implies multiple coupling reactions between living polymeric anions R and an olefinically functionalized siloxane oligomer molecule, or between P' arid an epoxy functionalized siloxane oligomer molecule. Without being bound to any theory, it is expected that these coupling reactions include at least one of the following: substitution reactions of alkoxy functional groups bound to silicon atoms on the siloxane oligomer molecule by polymeric anions to form n arms or branches of polymer P covalently bonded to silicon atoms on residue X; addition or substitution reactions of unsaturated hydrocarbyi functional groups bound to silicon atoms on the siloxane oligomer molecule to or by polymeric anions, which are later protonated, thus forming n arms or branches of polymer P covalently bonded to silicon atoms on residue X; ring opening addition reactions of epoxide ring of epoxy functional groups bound to silicon atoms on the siloxane oligomerAttorney Docket No.: DYN-10-PCTmolecule and polymeric anions, which are later protonated, thus forming n arms or branches of polymer P covalently bonded through -R-CH(OH)-CH2- groups to silicon atoms on residue. Also, without being bound to any theory, there could be siloxane Si-O-Si cleavage reactions by direct attack of polymeric anions or remaining organolithium initiator, The exact configuration of the residue X in each coupled polymer molecule (P)n-X will thus vary depending on the structure of each functionalized siloxane oligomer molecule, the stoichiometry of functional groups to polymeric anions, and the extent and dependencies of such coupling or cleavage reactions.

[0030] In a preferred embodiment, the polymeric rubber compositions to the present invention comprise polybutadienes, which are partially coupled with blends of functionalized siloxane oligomers selected from the group of blends of olefinically functionalized siloxane oligomers, blends of e oxy functionalized siloxane Oligomers, or their mixtures thereof. The molecular weight distribution (MWD) of the partially coupled polybutadienes of the invention comprises at least two peaks, which correspond to the ge neralized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value. The peak of lower molecular Weight accounts for the uncoupled polybutadiene fraction P, while the rest of the MWD accounts for the coupled polybutadiene fraction (R)n-X. The uncoupled polybutadiene and the coupled polybutadiene fractions are separated by a minimum in the MWD. Coupling efficiency (we) of the polybutadiene rubber of the invention, understood as the percent area of the coupled polybutadiene fraction relative to the whole area of the MWD,;is preferably greater than 10%, more prefe ably greater than 30%, and most preferably in the range from 30% to 95%. The polydispersity index of the coupled fraction, Mw_c / Mn_c, specifically the ratio of weight^average molecular weight of the coupled polybutadiene fraction to the number-average molecular weight of the coupled polybutadiene fraction, is greater than 1.10, wherein the MWD is measured by GPC calibrated with polystyrene standards. Preferably, the partially coupled polybutadienes of the invent ion have a polydispersity index (Mw / M n), understood as the ratio of the weight-average molecular weight of the whole MWD, Mw, to the humber-average molecular weight of the whole MWD, Mn, in the range from 1,3 to 2.0. moreAttorney Docket No.: DYN-10-PCTpreferably in the range from 1,3 to 1.8, and most preferably in the range from 1 4 to 1.7, wherein the MWD is measured by GPC calibrated: with polystyrene standards. The partially coupled polybutadienes of the invention have a coupling degree, DC, calculated according with equation (1), in the range from 2.0 to 6.0, preferably from 3,0 to 5.0 more preferably in the range from 3, 1 to 4,5, and most preferably from 3.3 to 4.0, wherein Mp_uc is the peak molecular weight of the uncoupled fraction, and wherein Mw, and Mp_uc are relative molecular weights measured by GPC calibrated with polystyrene standards. Moreover, the partially coupled polybutadienes of the invention have a coupling degree, DC, according with equation (1), in the range from 5.0 to 7.0 wherein MW, and Mp_uc are absolute molecular weights measured by G PC equipped with a light scattering detector.DC = [1 + (M / Mp_uc )WB] (1)

[0031] In another embodiment, the polymer compositions of the invention com prise polyb ta dienes, partially coupled with blends of olefinically functionalized siloxane oligomers, or partially coupled with blends of epoxy functionalized siloxane oligomers, that have a peak molecular weight of the uncoupled fraction, Mp_uc in the range from 100 to 300 kg / moi, measured by GPC calibrated with polystyrene standards.

[0032] In another embodiment, the polymer compositions of the invention are polybutadienes, partially coupled with blends of olefinically functionalized siloxane oligomers, or partially coupled with blends of epoxy functionalized siloxane oligomers, that have a vinyl content lower than 17 wt.%, more preferably lower than 15 wt.%, and most preferably lower than 13 wt.%, on a conjugated diene repeat unit basis.

[0033] In a particularly preferred embodiment, the polymer compositions of the invention are polybutadienes, partially coupled with blends of olefinically functionalized siloxane oligomers, or partially coupled with blends of epoxy fuhctidnalized siloxane Oligomers, that have a styrene solution viscosity, at 5 wt.% and 25 °C, from 30 to 290 cP, and a Mooney viscosity (ML1 +4 at 100 °C),Attorney Docket No.: DYN-10-PCTfrom about 30 to about 90, and a weight- average molecular weight (Mw), in the range from 260 to 790 kg / mol, relative to polystyrene standards,

[0034] In another particularly preferred embodiment, the polymer compositions of the invention are pplybutadienes, partially coupled with blends of olefin ically functionalized siloxane oligomers, or partially coupled with blends of epoxy functionalized siloxane oligomers, that have styrene solution viscosity, at 5 wt.% and 25 °C, from 40 to 270 cP, Mooney viscosity (ML1+4 at 100 °C) from 20 to about 100, and weight-average molecular weight (Mw) in the range from 300 to 760 kg / mol, relative to polystyrene standards.

[0035] In an embodiment, the polymer compositions of the invention are tapered block copolymers, or block copolymers, partially coupled with blends of olefinically functionalized siloxane oligomers, or partially coupled with blends of epoxy functionalized siloxane oligomers, comprising conjugated diene and vinyl aromatic repeating units, that have vinyl aromatic repeating unit degree of blockihess from about 30 mole %to 100 mole %, where vinyl aromatic repeating unit degree of blockiness is determined by proton NMR analysis as the mole percent of vinyl aromatic repeating units in the rubber that are not covalently bo nded to conjugated diene repeating units, on a tota l vinyl aromatic repeat in g uh it bas is.

[0036] In an embodiment, the polymeric rubber composition of the invention comprise tapered block copolymers, or block copolymers, partially coupled with blends of olefinically functionalized siloxane oligomers, or partially coupled with blends of epoxy functionalized siloxane oligomers, comprising conjugated diene and vinyl aromatic repeating units, that has at least bimodal molecular weight distribution, which exhibits Mw from about 100 kg / mol to 800 kg / mol, Mn from about 30 kg / mol to about 600 kg / mol, and polydispersity index, Mw / Mh, from about 1.3 to about 3.0, measured by GPG calibrated with polystyrene standards. The molecular weight distribution (MWD) of the inventive partially coupled tapered block copolymers, or the inventive partially coupled block copolymers^ comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may f rthe comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value. The polymeric rubber compositions of the presentAttorney Docket No.: DYN-10-PCTinvention comprise polymers wherein the pplydispersity index of the coupled fraction (P)n~X, Mw_c / Mn_c, specifically the ratio of weight-average molecular weight of the coupled polymer fraction to the number-average molecular weight of the coupled polymer fraction, is greater than 1.10, wherein the MWD is measured by GPC calibrated with polystyrene standards. The inventive poiyrheric rubber compositions optionally comprise tapered, counter tapered, random, controlled distribution blocks or segments of conjugated diene and viny l aromatic repeating units, as described in prior art compositions.

[0037] In an embodiment, the present invention provides hydrogenated versions of the pre iously escribed polymeric rubber compositions, where at least 95% of the conjugated diene repeating units are replaced by the respective saturated olefinic repeating units. Unsaturation of vinyl aromatic repeating units is left intact;

[0038] In another embodiment, the polymeric rubber compositions of the invention are produced by organolithiurn initiated anionic polymerization of conjugated diene monomer, or anionic copolymerization of conjugated diene and vinyl aromatic monomers, or anionic block copolymerization of conjugated diene and vinyl aromatic monomers in hydrocarbon solution, where the living polymer, copolymer, dr block copolymer living chains are reacted with blends of siloxane oligomers, thus obtaining inventive partially coupled homopolymers, partially coupled copolymers, or partially coupled block copolymers. Suitable siloxane oligomers to prepare the polymeric rubber compositions of the invention comprise either blends of olefinical ly functionalized siloxane oligomer molecules or blends of epoxy functionalized siloxane oligomer molecules, or mixtures thereof, with different number of silicon atoms per siloxane oligomer molecule and varying number and nature of functional groups or radicals (substituents) per Silicon atom. Thus, suitable blends of siloxane oligomers to prepare the polymeric rubber compositions of the invention exhibit a molecular weight distribution, spanning across defined molecular weight ranges. Suitable siloxane oligomers are blends of olefinically functionalized, or epoxy functionalized, siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, Cyclic, and / or crosslinked struct res. The siloxane oligomer molecules have not more than one olefinic radical (functional group) per silicon atom, and / orAttorney Docket No.: DYN-10-PCTnot more than one epoxy radical (functional group) per silicon atom, and their silicon atoms may further comprise alkoxy, saturated hydrocarbyl, and / or hydroxyl radicals (functional groups). Coupling of homopolymer anions, copolymer anions, or block copolymer anions by these blends of functionalized siloxane oligomers provides inventive polymeric rubber compositions comprising a coupled polymer fraction with a polydispersity index (ratio of weight average molecular weight to number average molecular weight) Mw_c / Mn_c greater than 1.10.

[0039] Suitable olefinically functionalized siloxane oligomer blends used in the present invention as coupling agents to prepare the inventive polyrneric rubber compositions are described in U. S. Patent No, 9,273,186, U. S. Patent No.9,296,766, and U. S. Patent No. 9,828,392, which are incorporated by reference. Suitable epoxy functionalized siloxane oligomer blends used in the present invention as Coupling agents to prepare the inventive polymeric rubber compositions are described in U. S. Patent No. 11,091,657, U. S. Patent No.8,394,972, and U. S. Patent No. 6,391,999, which are incorporated by reference.

[0040] In a preferred embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules With the general formula (I),[(R1O)z(R2)xSi(A)(O)(3-x-2y2]a [(R3O)ySi(O)f -v) / 2]c [(R3O)y(R4)wSi(B)(O:(3-^ ) / 2]b(l)wherein [(R'O^tR^SitAXO)^-^], [(R3Q)vSi(O)( -vy2]„ and [(R3O)y(R4)wSi(B)(C))(^x-z) / 2] are structural elements that appear a, c, and b times, respectively, in any order throughout each siloxane oligomer molecule in the blend, anwherein a is an integer greater-than or equal to 1, andwherein b and c are integers gr ater-than or equal to 0, andwherein a+b+c is greater-than or equal to 2, andwherein A corresponds to a linear, branched or cyclic alkenyl- or cycloalkenyl¬ alkylene- functional group, having in each case 2 to 16 0 atoms, R2independently at each occurrence is a linear, branched or cyclic alkyl radicalAttorney Docket No.: DYN-10-PCThaying 1 to 15 C atoms, R1independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 G atoms, or H, and x is 1 or 0, z is Q, 1, or 2, and x+z is less-than or equal to 2. andwherein Rs independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, or H, and v is 0, 1, 2, or 3, andwherein B corresponds to an unsubstituted hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 160 atoms, R4 independently at each occurrence is a linear branched or cyclic alkyl radical having 1 to 15 C atoms, and y is 0, 1, or 2, w is 0 or 1, and y+w is less-than or equal to 2, and herein each structural eleme t is covalently bonded to one, two, three, or four other structural element(s) of the siloxane oligomer molecule, with same of different radicals and functional groups, through its O1 / 2 moieties, i.e, shared oxygen moieties, thereby giving place to a distribution of siloxane oligomers with different molecular topologies, ranging from linear, branched, cyclic, up to crosslinked molecular topologies.

[0041] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules with the general formula (I), wherein A, independently at each occurrence, comprises non-hydrolyzable olefinic functional groups selected from vinyl, allyl butenyl, 3-butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-CI to C8-alkylene, cyclohexenyl- 2-ethylene, 3'-cyclohexenyl-2-efhylene, cyclo hex ad ienyl-01 to CB-alkylene, and cyclohex a die hy I- 2- eth l e ne.

[0042] In an embodiment, the Suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules with the general formula (I), wherein B comprises, independently at each occurrence, hoh-hydrolyzable uhsubstituted hydrocarbon radicals selected from methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2,2- dimethylbutyl, 2, 3-d i methyl butyl, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, n- octyl, isooctyl, neooctyl, nonyl, decyl, undecyl, dodecyl, C13H27, C14H29, C15H31, and hexa ecyl.Attorney Docket No.: DYN-10-PCT

[0043] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules with the general formula (l), wherein R2and R4, independently at each occurrence, comprise non- hydrolyzable alkyl radicals selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl,. n-butyl, tert-butyl, pentyl, mpentyl, isopentyl, neopentyl, hexyl, isbhexyl, neohexyl, 2,2-dimethylbutyl, 2,3- imethylbutyi, 2-methylpentyl, 3-methylpentyl, heptyl, octyl, n-octyl, neooctyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C13H27, C14H29, and C15H31.

[0044] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules with the general formula (I): wherein, a+b+c is greater-than or equal to 2, and less-than or equal to 25, and Wherein the blends of siloxane oligomers comprise distributions of multiple molecules spanning all the possible values of a+b+c with upper bounds from 5 to 25, for example with a+b+c equal to 2, 3, 4, and 5, or a+b+c equal to 2, 3, 4, 5, and 6, a+b+c equal to 2, 3, 4, 5, 6, and 7, a+b+c equal to 2, 3, 4, 5, 6, 7, and 8, a+b+c equal to 2, 3, 4, 5, 6, 7, 8, and 9, a+b+c equal to 2, 3, 4, 5, 6, 7, 8, 9, and 10, a+b+c equal to 2, 3. 4, 5, 6, 7, 8, 9, 10, and 11, a+b+c equal to 2, 3, 4, 5... 10, 11, and 12, a+b+c equal to 2, 3, 4, 5... 11, 12, and 13, a+b+c equal to. 3, 4, 5... 12, 13, and 4, a+b+c equal to 2, 3, 4, 5... 13, 14, and 15, a+b+c equal to 2, 3, 4, 5... 14, 15, and 16, a+b+c equal to 2, 3, 4, 5... 15, 16, and 17, a+b+c equal to 2, 3, 4, 5 16, 17, and 18, a+b+c equal to 2, 3. 4, 5... 17, 18, and 19, a+b+c equal to 2, 3, 4, 5... 18, 19, and 20, a+b+c equal to 2, 3, 4, 5... 19, 20, and 21, a+b+c equal to 2, 3, 4, 5... 20, 21, and 22, a+b+c equal to 2, 3, 4, 5... 21, 22, and 23, a+b+c equal to 2, 3, 4, 5... 22, 23. and 24, or a+b+c equal to 2, 3, 4, 5...23, 24, and 25, Wherein the rest of the characteristics of the general formula (I) remain defined as in previous paragraphs.

[0045] In an embodiment, the molecular weight distributions of the blends of olefinically functionalized siloxane oligomers with formula (I), employed to prepare the polymeric rubber co positiohs of the invention, comprise 100% of GPC area with molecular weights of less-thah or equal to 2500 g / moi, and less- than or equal to 5% of GPC area with molecular weights of less-than or equal toAttorney Docket No.: DYN-10-PCT250 g / mol, and at least 20% of GPC area with molecular weights of greater-than 250 g / mol and of less-than or equal to 500 g / mol, and at least 20% of GPC area with molecular weights of gre ter-than 500 g / mol and of less-than or equal to 750 g / ol, and at most 20% of GPC area with molecular weights of greater than 750 g / mol and of less-than or equal to 1000 g / mol, and at most 15% of GPC area with molecular weights of greater-th n 1000 g / mol.

[0046] In an embodiment, the suitable blends of olefinically functionalized siloxane oligomers with formula (I), employed to prepare the polymeric rubber composition to the invention, comprise from 5 to 80 mol% of M structural units relative to the total number of silicon atoms ih the blend of olefinically functionalized siloxane oligomers. M structural unit is known as a structure with one oxygen bonded and shared in a si loxa ne bond, i.e., M=[-OI / 2- S((R)3], as described in U. S. Patent No. 9,273,186, which is incorporated by reference. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 5 to 80 mol% of one or more structural units with formulas: [(R1G)2Si(A)(d)i / 2], [(R1O)(R2)Si(A)(O)i / 2], [(R3O)2Si(B)(O) / 2], [(R3O)(R4)Si(B)(G)i / 2], and ['R3O)3Si(0)iz2]. The suitable blends of functionalized siloxane oligomers with formula (I) also comprise from 15 to 75 mol% of D structural units relative to the total number of silicon atoms in the blend of olefinically functionalized siloxane oligomers. D structural unit is known as a structure with two oxygens bonded and shared in siloxane bonds, i e., D=[-O 2- Si(R)2-Oi / 2-] or [-O2 / 2'Si(R)2], as described in U. S. Patent No. 9,273,186, which is incorporated by reference. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 15 to 75 mol of one of more structural units with formulas: [(R ’0)Si(A)(O)272], [(R^S A ©)^], [(R3O) Si (B)(0) 2 / 2], [(R4)Si(B)(O)2 / 2], and [(R3O)2Si(O)2 / 2]. The suitable blends of olefinicall functionalized siloxane oligomers also comprise from 0 to 35 ol% of T structural units relative to the total number of silicon atoms in the blend of olefinically functionalized siloxane oligomers. T structural unit is known as a structure with three oxygens bonded and shared in siloxane bonds, i.e., T=[RSi(- Oi / 2-)3] or [RSi(-O3 / 2-)], as described in U. S. Patent No. 9,273,186, which is incorporated by reference. Specifically, the suitable blends of functionalizedAttorney Docket No.: DYN-10-PCTsiloxane oligomers with formula (I) comprise from 0 to 30 mo|% of on© of more structural units with formulas: [Si(A)(P)3^],: [S 1(B)(0) 3 / 2]^ and [(R3O)Si(O 2]1

[0047] In a particularly preferred embodiment, the suitable blends of olefinically functionalized siloxane oligomers with formula (I), employed to prepare the polymeric rubber composition to the invention, comprise from 30 to 80 mol% of M structural units, relative to the total number of silicon atoms in the blend of olefinically functionalized siloxane oligomers. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 30 to 80 mol% of one or more structural units with formulas: [(R1O 2Si(A)fO)i / 2l, [(R1O)(R2)Si(A):(O i / 2]i[(R3Q)2Si(B)(O)i / 2], [(R^Oj R4) Si(B (O)i and [(R3O)3Si(O) / 2]. The suitable blends of functionalized siloxane oligomers with formula (I) also comprise from 40 to 75 mol % of D structural units, relative to the total number of silicon atoms in the blend. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 40 to 75 mol% of one of more structural units With formulas: [(R1O)Si(A)(O)2 / 2], [(R^SifA) (0 2 / 2], [(3O)Si(B)(O)2 / 2], [(R^Si B (O)2 / 2], and [(R3O)2Si (0)2 / 2]. The suitable blends of plefinically functionalized siloxane oligomers also comprise from 0 to TO mol% of T structural units, relative to the total number of silicon atoms in the blend. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 0 to 10 mol% of one of more structural units with formulas:[Si(A)(O)3 / 2], [Si(B) (0)3 / ], and [(R3O)Si(O)3 / 2]. Wherein R1, R2, R3, R4, A, and B are defined as above.

[0048] In an alternative embodiment, the blends of olefinically functionalized siloxane oligomers With formula (I), employed to prepare the polymeric rubber composition to the invention, comprise from 5 to 50 mol% of M structural units, relative to the total number of silicon atoms in the blend of olefinicall functionalized Siloxane oligomers. Specifically, the suitable blends of functionalized siloxane oligomers with formula (I) comprise from 5 to 50 moi% of one or more structural units with formulas: [(R ’O)2Si(A)(O) 1 / 2], [(R1O)(R^)Si(A) (0)1 / 2], [(R3O 2Si(B (O)i / 2], [(R (R4)Si(B)(O)i / 2], and {(R3O)3Si(O)i72]. The suitable blends of functionalized siloxane oligomers with formula (I) also comprise from 50 to 70 mol% of D structural units, relative to the total number of silicon atoms in the blend. Specifically, the suitable blends ofAttorney Docket No.: DYN-10-PCTfunctionalized siloxane oligomers with formula (I) comprise from 50 to 70 rnol% of one of more structural units with formulas: [(R4O)Si(A)(O)2 / 2j, [(R2)Si( )(O)2 / 2], [(R3O)Si(B)(O) [(R4)Si(B)(O 2?2], and [(R3O)2Si(O)2 / 2]. The suitable blends of plefinically functionalized siloxane oligomers also comprise from 0 to 35 mol% of T structural units, relative to the total number of silicon atoms in the blend. Specifically, the suitable blends of functionalized siloxane oligo ers with formula (I) comprise from 10 to 35 ol% of one of more structural units with formulas:[Si(A)(O).v2], [Si(B)(O)3 / 2], and [(R3O)Si(O)3 / 21. Wherein R1, R2, R3, R4, A, and B are define as above.

[0049] In an embodiment, the suitable blends Of olefinically functionalized siloxane oligomers of formula I, used to prepare the polymeric rubber compositions of the present invention, comprise two or more siloxane oligomers selected from the group of: disiloxane, cyclotrisiloxane, linear trisiloxane, branched trisilbxane, cy clot etrasi lo ane, linear tetrasiloxane, branched tetrasiloxane, cyclo pehtasiloxane, linear pehtasiloxane, branched pentasiloxane, and / or cyclohexasiloxane, altogether in an amount greater-than or equal to 60% (% area GPC), preferably of greater-than or equal to 70%, and most preferably of greater-than or equal to 75%. Wherein all the siloxane oligomers in the blend have the functional groups and radicals stated in formula I.

[0050] In an alternative embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of epoxy functionalized siloxane oligomer molecules With the general formula (II),[(R1O)zSi(E)(0)(S- z / 2]a [(R^vSiCOh^h [(R3O)y(R3)wSi(O)r3y- ) / 2]b (II)Wherein [(R1O)zSi(E)(O)(3-z) / 2], [3O)vSi(O)(4-v) / 2], and [ R3O) (R3)wSi(O)(3-y-wy2] are structural elements that appear a, c,:and b times, respectively, throughout each siloxane oligomer molecule in the blend, in any order, andwherein a is an integer greater-than or equal to 1, and b is an integer greater- than or equal to 0, and c is an integer greater-than or equal to 0, and a+b+c is greater-than or equal to 2, andAttorney Docket No.: DYN-10-PCTwherein E corresponds, independently at each occurrence, to linear or branched alkyl ether functional groups of 3 to 11 C atoms, with each functional group substituted by an epoxide, Otto linear, or cyclic alkyl functional groups of 2 to 11 C atoms, with each functional group substituted by an epoxide, and wherein R1independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 4 G atoms, or H, and z is 0, 1, or 2, andwherein Rs independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 40 atoms, or H, and v is 0, 1, 2, or 3, ndwherein y is 0, 1, or 2, and w is 0 or 1, and y+w is less-than or equal to 2, and wherein each Structural element is bonded to One, two, three, or fo r other structural ele ent(s) of the siloxane oligomer molecule, with same or different radicals and functional groups, through its O1 / 2 moieties, i.e. shared oxygen moieties, thereby giving place to a distribution of siloxane oligomers with different molecular topologies, ranging from linear, branched, cyclic, up to crosslinked molecular topologies.

[0051] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of epoxy functionalized siloxane oligomer molecules with the general formula (11), wherein E comprises, independently at each occurrence, non-hydrolyzable, linear or branched, alkyl ether functional groups substituted with an epoxide, selected from glycidoxymethyl, 2-glycidoxyethyl, 1-glycidoxyethyl, 3-glycidoxypropyl, a- glycid oxy propyl, |3-glyc id oxypropyl, 4-glycidoxybutyl, a-glycid oxy butyl, y- glycidoxy butyl, 5-glycidoXypentyl, 6-glyciddxyhexyl, 3-glycidyloxyhexyl, 7- glycid oxy heptyl, or 8-g lye id oxy octyl, preferably 3-glycido ypropyl, or non- hydrolyzable, linear or cyclic, alkyl functional gro ps substituted with an epoxide, selected from oxiranyl, glycidyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 5,6- epoxyhexyl, or 2-(3,4-epoxycycloheXyl)ethyl.

[0052] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of olefinically functionalized siloxane oligomer molecules with the general formula (I) or a blend of epoxy functionalized siloxane oligomer molecules With the general formula (II) or mixtures thereof, wherein R1and R3, independently at each occurrence,Attorney Docket No.: DYN-10-PCTcornprise non -hydrolyzable alkyl radicals selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, mbutyl, or tert-butyl.

[0053] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber compositions of the invention comprises a blend of epoxy functionalized siloxane oligomer molecules with the general formula (II), wherein the molecular weight distribution of the blend of epoxy functionalized oligomer molecules has a number-average molecular weight (Mn) from 600 to 2000 g / mol, and a ratio of weight-average molecular weight to the number-average molecular weight (Mw / Mn) greater-than or equal to 1.5,

[0054] In an embodiment, the suitable siloxane oligomer to prepare the polymeric rubber Compositions of the invention comprises a blend of epoxy functionalized siloxane oligomer molecules with the general formula (II), wherein the dynamic viscosity of the blend at 25 °C is from 600 to 2000 cP,

[0055] Examples Of suitable functionalized siloxane oligomer blends include but are not limited to: Dynasylan® 6490, which is a blend of siloxane oligomer molecules functionalized with vinyl and methoxy groups, Dynasylan® 6498 which is a blend of siloxane oligomer molecules functionalized with vinyl and ethoxy groups, and Dynasylan® VPS 4721, which is a blend of siloxane oligomer molecules functionalized with glycidoxypropyl and methoxy groups, all of them commercialized by Evonik, The concentration of R-OH per kg of oligomer is typically reported as a control parameter in siloxanes functionalized with alkoxy groups. Knowledge of this parameter is key for the proper control of coupling efficiency.

[0056] In one embodiment, the invention provides a process to prepare the inventive polymeric rubber compositions comprising: reacting at least a conjugated diene monomer, optionally reacting at least a vinyl aromatic monomer, with organolithium initiator, and performing the anionic polymerization in a hydrocarbon solvent. Upon completion of the polymerization, a portion of the polymeric anions is coupled to a siloxane oligomer molecule in the blend, then the remaining active polymeric anions are deactivated by a suitable termination agent, thereby obtaining a solution of the partially coupled polymer composition according to the present invention in hydrocarbon solvent. Compared with prior art, the process of the invention achieves the polymeric rubber compositionsAttorney Docket No.: DYN-10-PCTwithout the long reaction time needed when using the continuous process described in prior art U. S. Patent No. 8,481,644 or without the low efficiency coupling of prior art monomeric alkoxysilanes.

[0057] In some embodiments, the process to prepare the polymeric rubber compositions of the invention further comprises a hydrogenation step. Selective hydrogenation of dienic unsaturations may be performed by any known prior art method, leaving the aromatic unsaturation in the rubber intact. This can be achieved by contacting the deactivated rubber solution in a hydrocarbon solvent with pressurized hydrogen and a titanocene compound, including but not limited to structures Cp2Ti(PhOCH3)2 or Cp2Ti(CH2PPh3)2, as described in U. S. Patent N o. 5,321,175, U. S. Patent No. 5,985,995, U. S. Patent No. 9,211,532 B2, European patent EP 2,489,688 B1 and PCT patent application WO 2010 / 149812 A1, which are incorporated by reference.

[0058] In some of the embodiments of the process to prepare the polymeric rubber compositions of the invention, the rubber solution is formulated with an antioxidant package, and optionally formulated with other additives, including an oil-extended rubber formulation.

[0059] Finally, the polymeric rubber composition of the invention is separated and isolated from solvent by any known prior art process, such as steam stripping in boiling aqueous serum, followed by dewatering, extrusion drying, fluidized bed drying, precipitation, direct devolatilization, vacuum assisted devolatilization, drum drying, roll milling, and the like, or combinations thereof. A particularly preferred industrial isolation process comprises steam stripping in boiling aqueous serum, followed by dewatering in an expander type extruder, and then followed by drying in extrusion drying expander. It has been surprisingly discovered that the polymeric rubber compositions of the present invention increase throughput by this finishing treatment in about 25 to 30%, while reducing gel contents in about 20 to 50%, in comparison with the processing of rubbers of same Mooney and solution viscosities but coupled by means of silicon tetrachloride.

[0060] Surprisingly, it was found that the inventive polymeric rubber compositions, especially the polybutadienes partially coupled with blends of olefinically functionalized siloxane oligomers, exhibit faster dissolution in styreneAttorney Docket No.: DYN-10-PCTand in solutions of styrene / acrylonitrile / ethylbenzene, reducing their dissolution times 15 and 25%, respectively, than prior art polybutadienes of same Mooney and solution viscosities but coupled by means of silicon tetrachloride. This advantage can be employed to improve throughput in the production of styrenic plastics such as HIPS and ABS, where the initial step of dissolving the rubber in such monomers is typically the slowest operation in the HIPS or ABS manufacture process.

[0061] An additional embodiment of the invention is end-use applications of inventive hydrogenated partially coupled styrene-butadiene block copolymers for toughening polyolefins and, wherein compounding of partially coupled SEBS provides a thermoplastic elastomer (TPE) composition that unexpectedly exhibits low haze and high transparency. Similarly, end-use applications of inventive partially coupled styrene-butadiene block copolymers (partially coupled SBS) for toughening polystyrene.

[0062] In the thermoplastic elastomer (TPE) composition of the present invention, the components of the TPE composition may be blended by any known method as described in European patent EP 2015382385, which is incorporated by reference. The inventive partially-coupled SEBS can be first mixed with a thermoplastic resin, preferably polyolefins such as polypropylene, polyethylene, ethylene / alpha-olefin copolymer, ethylene / propylene copolymer, ethylene / propylene / diene terpolymer, propylene / 1 -butene copolymer, propyle ne / ethylene / alpha-olefin terpolymer, impact propylene / ethylene copolymer, or a mixture of the foregoing, and their recycled equivalents, including post-consumer and / or post-industrial recycling materials. Optionally, stabilizers, fillers, colorants, cross-linking agents (if any), processing aids, and other appropriate additives may also be added. The inventive partially coupled SBS can also be first mixed with a thermoplastic resin, preferably polystyrene, and its recycled equivalents, including post-consumer and / or post-industrial recycling materials. Optionally, stabilizers, fillers, colorants, cross-linking agents (if any), processing aids, and other appropriate additives may also be added.

[0063] The inventive partially coupled SEBS also finds application in a variety of high-end value fields, such as high flow SEBS copolymers as described in European patent EP1730201 and U. S. Patent No. 7,439,301, which areAttorney Docket No.: DYN-10-PCTincorporated by reference, Some partially coupled SEBS are valuable for making products that need to avoid plasticizers and low molecular weight additives, as these can migrate and affect usability, feel, or user health. The inventive partially coupled SEBS: exhibits high compatibility with polypropylene as disclosed in European patent EP1002813, which is incorporated by reference, making them very useful for the manufacture of elastic films, fibers and non-wovens compounds; are useful for soft elastomeric films as described in U. S. Patent Application Ser. No. 22 / 311,767, which is incorporated by reference; are useful in oil gel compositions for use in cable filling compounds as described in European patent EP0822227, which is incorporated by reference; are useful for sealant formulations as described in U. S, Patent No. 5,777,043, which is incorporated by reference; provide high clarity and improved mechanical properties when compounded with polyolefins as described in U. S, Patent Application No. 2010 / 0331465 Al, which is incorporated by reference; for the formulation of polypropylene compositions with oxygen absorbing capability as described in U. S, Patent Application No, 2012 / 0252922 A1, which is incorporated by reference; for use in radiation curable hot melt adhesive compositions as described in U. S. Patent No. 6,486,229, which is incorporated by reference; and for use in hot melt pressure sensitive adhesives as described in U. S. Patent Application No. 2015 / 0191637 A1, which is incorporated by reference.

[0064] The expert in the art would find the inventive polymeric rubber compositions suitable for other end-use applications, such as: toughened plastic compositions by mechanical mixing, modified asphalt compositions, solvent based adhesive compositions, hot melt adhesive compositions, sealant formulations, and others, as described in European patent EP2668214B1 and U. S. Patent No. 11,370,873 B2, and U. S. Patent Application No. 20220396654 Al, which are incorporated by reference. Other inventive polymers would be suitable for thermoplastic elastomer (TPE) compositions, vulcanized compounding, microcellular foamed compositions, oil gel compositions, battery cell binder compositions, and others, as described in European patents EP3325519B1 and EP3853274B1, and European patent application EP4183809A1 and U. S. Patent Application No. 20220396654 A1, which are incorporated by reference.Attorney Docket No.: DYN-10-PCT

[0065] In a preferred embodiment, the invention provides a process for preparing a partially coupled conjugated diene polymer composition, or a hydrogenated partially coupled conjugated diene polymer composition, comprising the steps of:(a) adding to a batch reactor, under inert atmosphere, the following ingredients, in any order desired: a hydrocarbon solvent, a conjugated diene monomer, optionally other conjugated diene monomers, optionally a polar modifier or a combination of polar modifiers, and an organolithium initiator;(b) essentially completely polymerizing the monomer or monomers originally added to the batch reactor, to form living anionic polymer chains, optionally polymerizing the monomer or monomers up to a pre-determined reaction time or conversion;(c) optionally:, charging simultaneously more and / or a different conjugated diene monomer and / or vinyl aromatic monomer to the batch reactor, at predetermined flow rates or times, and allowing for essentially complete polymerization of the charged mono mer or monomers;(d) adding an olefinically functionalized siloxane oligomer blend, or an epoxy functionalized siloxane oligomer blend, as coupling agent to couple part of the living anionic polymer chains, optionally charging the coupling agent at pre-determined flow rate or time, and completely polymerizing the remaining monomer or monomers;(e) optionally, charging simultaneously more and / or a different conjugated diene monomer and / or vinyl aromatic monomer to the batch reactor, at pre¬ determined flow rates or times, and allowing for essentially complete polymerization of the charged mono mer or monomers;(f) adding a suitable termination agent to deactivate all the remaining living polymer chains in the batch reactor, to form a diene polymer solution; (g) optionally, hydrogenating the diene polymer solution, in the same batch reactor or in a separate reactor, to form a hydrogenated diene polymer solution;(h) formulating the diene polymer solution, or the hydrogenated diene polymer solution, with an antioxidant package;Attorney Docket No.: DYN-10-PCT(i) optionally, formulating the diene polymer solution, or the hydrogenated diene polymer solution, with an extended oil, optionally formulating with other additives;(j) separating the diene polymer solution, or optionally separating the hydrogenated diene polymer solution, from the hydrocarbon solvent, to recover the partially coupled conjugated diene polymer composition, or optionally to recover the hydrogenated partially coupled conjugated diene polymer composition.

[0066] In a preferred embodiment of the invention, a process for producing a partially coupled tapered block copolymer composition comprises the steps of:(a) adding to a batch reactor, under inert atmosphere, the following ingredients, in any order desired: a hydrocarbon solvent, a conjugated diene monomer, optionally other conjugated diene monomers, a vinyl aromatic monomer, optionally other vinyl aromatic monomers, optionally a polar modifier or a combination of polar modifiers, and an organolithium initiator;(b) essentially completely polymerizing monomers originally added to the batch reactor, to form living anionic polymer chains, optionally polymerizing the monomers up to a pre-determined reaction time or conversion;(c) optionally, charging simultaneously more and / or different conjugated diene and / o r vinyl aromatic monomers to the batch reactor, at pre-determined flow rates or times, and allowing for essentially complete polymerization of the charged monomer or monomers;(d) adding an olefinically functionalized siloxane oligomer blend, or an epoxy functionalized siloxane oligomer blend, as coupling agent to couple part of the living anionic polymer chains, optionally charging the coupling agent at pre-determined flow rate or time, and completely polymerizing the remaining monomers;(e) optionally, charging simultaneously more and / or different conjugated diene and / or vinyl aromatic monomers to the batch reactor, at pre-determined flow rates or times, and allowing for essentially complete polymerization of the charged monomer or mono mers;Attorney Docket No.: DYN-10-PCT(f) adding a suitable termination agent to deactivate all the remaining living polymer chains in the batch reactor, to form a tapered block copolymer solution;(g) optionally, hydrogenating the tapered block copolymer solution, in the same batch reactor or in a separate reactor, to form a hydrogenated tapered block copolymer solution;(h) formulating the tapered block copolymer solution with an antioxidant package;(1) optionally, formulating the tapered block copolymer solution with an extended oil, optionally formulating with other additives;(j) separating the tapered block copolymer solution, or optionally separating the hydrogenated tapered block copolymer solution, from hydrocarbon solvent, to recover the partially coupled tapered block copolymer composition, or optionally to recover the hydrogenated partially coupled tapered block copolymer composition.

[0067] In an embodiment of the invention, a process for producing a partially coupled block copolymer composition comprises the steps of:(a) adding to a batch reactor, under inert atmosphere, the following ingredients, in any order desired- a conjugated diene monomer, optionally other conjugated diene and / or vinyl aromatic monomers, optionally a polar modifier or a combination of polar modifiers, and an organolithium initiator; (b) essentially completely polymerizing monomer or monomers originally added to the batch reactor, to form living anionic polymer chains, optionally polymerizing the monomer or monomers up to a pre-determined reaction time or conversion;(c) optionally, charging simultaneously more and / or a different conjugated diene monomer and / or vinyl aromatic monomer to the batch reactor, at pre¬ determined flow rates or times, and allowing for essentially complete polymerization of the charged mono mer or monomers;(d) adding an olefinically functionalized siloxane oligomer blend, or an epoxy functionalized siloxane oligomer blend, as coupling agent to couple part of the living anionic polymer chains, optionally charging the coupling agent atAttorney Docket No.: DYN-10-PCTpre-determined flow rate or time, and completely polymerizing the remaining monomer or monomers;(e) optionally, charging simultaneously more and / or a different conjugated diene monomer and / or vinyl aromatic monomer to the batch reactor, at pre¬ determined flow rates or times, and allowing for essentially complete polymerization of the charged monomer or monomers;(f) adding a suitable termination agent to deactivate all the remaining living polymer chains in the batch reactor, to form a block copolymer solution; (g) optionally, hydrogenating the block copolymer solution, in the same batch reactor or in a separate reactor, to form a hydrogenated block copolymer solution;(h) formulating the block copolymer solution with antioxidant package;(i) optionally, formulating the block copolymer solution with an extended oil,, optionally formulating with other additives;(j) separating the block copolymer solution, or optionally separating the hydrogenated block copolymer solution, from hydrocarbon solvent, to recover the partially coupled block copolymer composition, or optionally to recover the hydrogenated partially coupled block copolymer composition.

[0068] In an embodiment of the invention, a process for producing a partially coupled block copolymer composition comprises the steps of:(a) adding to a batch reactor, under inert atmosphere, the following ingredients, in any order desired: a vinyl aromatic monomer, optionally other vinyl aromatic and / or conjugated diene monomers, optionally a polar modifier or a combination of polar modifiers, and an organolithium initiator;(b) essentially co mpletely polyme rizing monomer or monomers origina lly added to the batch reactor, to form living anionic polymer chains, optionally polymerizing the monomer or monomers up to a pre-determined reaction time or conversion;(c): optionally, charging simultaneously more and / or a different vinyl aromatic monomer and / or conjugated diene monomer to the batch reactor, at pre-determined flow rates or times, and allowing for essentially complete polymerization of the charged monomer or monomers;Attorney Docket No.: DYN-10-PCT(d) adding an olefinically functionalized siloxane oligomer blend, or an epoxy functionalized siloxane oligomer blend, as coupling agent to couple part of the living anionic polymer chains, optionally charging the coupling agent at pre-determined flow rate or time, and completely polymerizing the remaining monomer or monomers;(e) Optionally, charging simultaneously more and / or a different vinyl aromatic monomer and / or conjugated diene monomer to the batch reactor, at pre¬ determined flow rates or times, and allowing for essentially complete polymerization of the charged monomer or monomers;(f) adding a suitable termination agent to deactivate all the remaining living polymer chains in the batch reactor, to form a block copolymer solution; (g) optionally, hydrogenating the block copolymer solution, in the same batch reactor or in a separate reactor, to form a hydrogenated block copolymer solution;(h) formulating the block copolymer solution with an antioxidant package; (i) optionally, formulating the block copolymer solution with an extended oil, optionally formulating with other additives;(j) separating the block copolymer solution, or optionally separating the hydrogenated block copolymer solution, from hydrocarbon solvent, to recover the partially coupled block copolymer composition, or optionally to recover the hydrogenated partially coupled block copolymer composition,

[0069] The polymerization process of the invention is typically carried out in inert hydrocarbon solvents under inert atmosphere with highly purified reagents to prevent the premature termination of the polymerization reaction. Suitable hydrocarbon solvents to practice this invention include, but are not limited to, aliphatic and cycloaliphatic solvents, such as pentane, isopentane, hexane, heptane, octane, isooctane, decane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and the like or mixtures thereof. Cyclohexane is a preferred solvent for the present invention.

[0070] In some embodiments of the processes provided in the present invention, a polar modifier or a combination of polar modifiers is added to a reactor, in any order desired relative to monomers and initiator, or charged at any step of the processes, at pre-determined reaction times or conversions,Attorney Docket No.: DYN-10-PCTcontinuously or intermittently to a reactor, at pre-determined flow rates or times, or in combination with co ntrol of temperature profile of polymerization. This could either be practiced for the purpose of increasing and / or controlling the 1,2-addition or 3,4-addition of conjugated dienes, to increase and / or modify the level of randomization of vinyl aromatic and conjugated diene monomers in copolymerization, including the inventive tapered block copolymer and block copolymer compositions, or as well as to accelerate polymerization, as described in European patents EP2668214B1, EP3325519B1, EP3853274B1 and U. S. patent No. 11,370,873 B2, European patent application EP4183809A1, and U. S. Patent Application No. 2022 / 0396654 Al, which are incorporated by reference. Polar modifiers that may be used to prepare polymeric rubber compositions of the present invention include Lewis bases such as ethers, tertiary amines, aminoethers and group IA alkali metal alkoxides, and combinations thereof Specific examples of these suitable ether polar modifiers include, but are not limited to, monofunctiohal, multifunctional and oligomeric alkyl and cyclic ethers, such as dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, di-n- propyl ether, methyl tert-butyl ether, tetra methylene oxide (tetra hydrofuran), 1,2-dimethoxyethane, bis-tetrahydrofuran, ditetrahydrofurylpropane (DTHFP), ethyl tetrahydrofurfuryl ether. Specific examples of suitable tertiary amine polar modifiers include, but are not limited to, monofunctional, multifunctional or oligomeric alkyl and cyclic tertiary amines such as dimethylethyl amine, trimethyl amine, triethylamine, N, N, N’, N '-tetra methyl ethylene diamine (TIVIEDA), N, N, N,, N”, N”-penta ethyldiethylenetriamine, 1,3,5-tri ethylhexahydro-1,3,5-triazine, combinations thereof, and the like. Specific examples of these suitable aminoether polar modifiers include, but are not limited to, tetra hydrofurfuryl-N, N -dimethylamine, bis(2- dimethyl amino)ethyl) ether, 2, 2 -di morpholino ethyl ether, arid the like, and mixtures thereof. Specific examples of these suitable Group IA alkali metal alkoxides (lithium, sodium, potassium, rubidium and cesium salts) include, but are not limited to, monofunctional, multifunctional and oligomeric alkyl and cyclic metal alkoxides such as sodium tert-butoxide, sodium tert- amylate, sodium mentholate, potassium tert-butoxide, potassium tert-amylate, potassium mentholate, potassium 3,7-dimethyl-3-octanolate and the like, and mixtures thereof. Polar modifiers can be loaded directly to the reactor or can beAttorney Docket No.: DYN-10-PCTpreviously dissolved in the solvent for use in the process. Polar modifier concentration in the reaction system of the invention is at least 2 parts per million weight parts of solvent, preferably from 5 to 5000 parts per million weight parts of solvent, more preferably from 10 to 1000 parts per million weight parts of solvent, most preferably from 20 to 100 parts per million weight parts of solvent. Polar modifier combinations can be added or charged in any specific molar or mass ratio, either relative to each other, or relative to initiator in the reactor.

[0071] In the embodiments of the processes provided in the present invention, the ratio of the mass of hydrocarbon solvent to the mass of total monomer(s) charged to the reactor is from 2.0 to 15.0, preferably is from 3.0 to 11.0, most preferably from about 4.5 to about 9.0.

[0072] Suitable conjugated diene monomers for use in making the polymer compositions of the present invention include, but are not limited to, 1,3-butadiene, isoprene, phenyl-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-3- ethyl-1,3-butadiene, 2,4-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3- heptadiene, 3-methyl-1,3-heptadiene, i,3-octadiene, 3-butyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 2-phenyl-1,3-butadiene, b-myrcene, b-farnesene, and the like, or combinations thereof. 1,3-butadiene is a preferred conjugated diene monomer for the present invention.

[0073] Suitable vinyl aromatic monomers for use in making the polymer compositions of the present invention include, but are not limited to, styrene, 3-methylstyrene, α-methylstyrene, p-methylstyrene, a,4-dimethylstyrene, 3,5-diethylstyrene, 2-ethyl-4-benzylstyrene, t-butyl styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-butenyl naphthalene, 4- phenylstyrene, 4-t-butoxystyrene, 3-isopropenyl biphenyl, 4-vinyl pyridine, 2-vinylpyridine, isopropenyl naphthalene, 4-n-propylstyrene, and combinations thereof. Styrene is the preferred vinyl aromatic monomer in the present invention.

[0074] In some of the embodiments of the process described in the present invention, the preferred amount of vinyl aromatic monomer charged to the reactor ranges from 0 to approximately 55 wt.% of the total monomer basis.

[0075] Suitable organolithium initiators for practicing the process of the present invention include organolithium compounds capable of initiating anionicAttorney Docket No.: DYN-10-PCTpolymerization of conjugated diene or vinyl aromatic monomers. Monofunctional organolithium compounds, generically represented as R-Li, where R represents a hydrocarbyl radical, can be employed. Specific examples of such monofunctional organolithium initiators are methyllithium, ethyllithium, tert- butyllithium, sec-butyllithium, n-butyllithium, n-decyllithium, isopropyllithium, eicosyllithium, cycloalkyllithium cornpounds, such as cyclohexyllithium, and aryllithium compounds, such as phenyllithium, naphthyllithium, p-toluyllithium, 1,1-diphenylhexyllithium, and the like. Monofunctional organolithium compounds substituted with protected polar functionafgroups may also be used as initiators for anionic polymerization. Multifunctional organolithium initiators may also be used as initiators to prepare branched and radial copolymers with a desired functionality range of 2 to about 30 anionically polymerized polymers chains per initiator molecule. Multifunctional organolithium initiators are readily prepared by direct addition reaction of a stoichiometric amount of a monofunctional organolithium compound to a polyvinyl compound such as 1,3-diisopropenyl benzene, 1,3,5-triisopropenyl benzene, 1,3-bis(1 -phenylethenyl) benzene, 1,3,5-tris(1-phenylethenyl)benzene, 1,3-divlnylbenzene; 1,3,5-trivinylbenzene, and the like. Oligomeric polyvinyl compounds may be used to prepare multifunctional organolithium initiators with high functionality. Monofunctional organolithium compounds, such as butyllithium, are examples of commonly used initiators for the above addition reaction; Specific examples of these commonly used initiators include tert-butyllithium, sec-butyllithium, and n-butyllithium.[0076J In the embodiments related to the process for making the polymeric rubber compositions of the present invention, the amount of organolithium initiator varies depending upon the desired molecular weight of the polymer and the purity levels of the solvent and monomers Only a portion of the Organblithium initiator charged to the reactor becomes active in the polymerization process, as humidity and other protic polar impurities will consume part of the organplithium initiator before initiation of monomer polymerization. Preferably, the amount of organolithium initiator in the process of making the partially coupled polymers of the invention is from about 0.5 millimoles to about 30 millimoles per kilogram of total conjugated diene monomer plus vinyl aromatic monomer loaded to the reactor, more preferably from aboutAttorney Docket No.: DYN-10-PCT1.0 millimoles to about 15 millimoles per kilogram of total conjugated diene monomer plus vinyl aromatic monomer loaded to the reactor, most preferably from about 4 millimoles to about 10 millimoles per kilogram of total conjugated diene monomer plus vinyl aromatic monomer loaded to the reactor.

[0077] In an embodiment of the invention, coupling agents based on blends of olefinically functionalized siloxane oligomers or blends of epoxy functionalized siloxane oligomers or mixtures thereof are employed in the process to produce polymeric rubber compositions with partially coupled polymer structures, such as linear, radial, star, branched or multiarm configurations, and mixtures thereof. Preferably, to mitigate gel issues, the total molar amount of living polymer chain-ends should exceed the molar amount of alkoxy groups bound to silicon atoms in the siloxane oligomer molecules charged for coupling. In some embodiments of the invention, coupling agents may optionally be charged at pre-determined flow rates or times to control the formation and / or proportion of the partially coupled polymer structures, either by favoring the coupling reaction with the more reactive functional groups and residual less reactive functional groups in all siloxane oligomer molecules, or by favoring the reaction of most of the functional groups in all siloxane oligomer molecules.

[0078] At the completion Of the polymerization and coupling reactions, the total reaction mixture is treated with termination agent to deactivate remai ning polymeric a nions and recover the polymeric ru bber compositions of the present invention. Suitable termination agents are polar proton donor compounds, such as water, alcohol, phenol, organic acid, or inorganic acid. The amount of termination agent to be added needs to be at least equal to a stoichiometric amount relative to the moles of polymeric anions remaining in the reactor after coupling. In some embodiments of the process of the invention, the total reaction mixture is treated with a suitable termination agent to deactivate a portion of the polymeric anions, at any time or conversion but before the monomer is exhausted, and then after polymerization is completed, continue with the coupling reaction of the remaining polymeric anions with a suitable functionalized siloxane oligomer blend to obtain a partially coupled composition with broader molecular weight distribution (MWD) of the coupled polymer.Attorney Docket No.: DYN-10-PCT

[0079] In the embodiments of the process of the invention, anionic polymerization is normally carried out at temperatures in the range from -100 to 150 °C, preferably between 25 and 100 °C, most preferably between 40 to 130 °C. In some embodiments of the process of the invention, the temperature profile of the polymerization is either adiabatic, isothermal, or combinations thereof. The temperature profile of the polymerization may be controlled by any means, and / or with adjustments in the polymerization formula and / or conditions such as solvent to monomer ratio, polar modifier concentration, charging of monomer at pre¬ determined flow rates or times, and so forth.

[0080] Typical reactor residence times for anionic polymerization in the process of the invention vary depending on the initial reaction temperature, monomer concentration, number of sequential monomer additions and organolithium initiator concentration from 3 to 60 minutes, preferably from 6 to 45 minutes, and most preferably from 9 to 30 minutes. In some embodiments of the process of the present invention, the polymerization and / or co upling reactions are performed either in batch, semi-batch, semi-continuous, or continuous operation, or combinations thereof, by using at least one reactor configuration,

[0081] A further step in all the embodiments of the process of the present invention is to add an antioxidant package while the partially coupled polymer composition is still in hydrocarbon solution. The antioxidant package protects the polymeric rubber composition from undesirable degradation and crosslinking during later processing steps to separate and isolate it from solvent and to prolong the shelf life of the final product. A wide variety of antioxidant packages are well known in the art, and any system can be used without limiting the scope of the present invention. Preferred antioxidant package dosage is from 0.1 to 1.5 parts per hundred weight parts of polymeric rubber composition of the present invention,

[0082] In some embodiments extender oil is incorporated into the polymeric rubber composition. In this optional practice, oil is preferably added while the partially coupled polymer composition is still in hydrocarbon solvent solution after it has been discharged from the reactor, or afterwards at any stage of its finishing process. Suitable oils to perform oil extension include, but are not limited to mineral oils, paraffinic oils, naphthenic oils, relatively naphthenic oils,Attorney Docket No.: DYN-10-PCTrelatively aromatic oils, aromatic oils, highly aromatic oils, extremely high aromatic oils and the like, or mixtures of thereof Oil content varies from 2 to 50 parts per hundred weight parts Of the rubber. The preferred oil content is from 2 to 12 parts per hundred weight parts of the rubber, with a more specific range being from 4 to 10 parts per hundred weight parts of the rubber. Optionally, other processing aids or additives may be added to the inventive polymeric rubber compositions.EXAMPLES

[0083] The following examples have the purpose of showing the features of the present invention and are not intended to limit the scope thereof Comparative examples using previous art technologies are included as reference, The rubbers synthetized in the following invention and comparative examples are characterized by the following techniques:

[0084] Gel permeation chromatography (GPC), employing a Waters Alliance 2690 equipment, with a three-column set (Shodex KF-803, KF-804 and KF-805), and a differential refractive index detector; THF was used as solvent, at flowrate of 1 ml / min and temperature of 40 °C, with sample injection volume of 25 mL, and polymer sample concentration of 2 mg / mL. Molecular Weight distribution (MWD), weight-average molecular weight (Mw), number-average molecular weight (Mn), peak molecular weight of uncoupled fraction (Mp_uc), polydispersity index (Mw / Mn), and polydispersity of the coupled fraction (Mw_c / Mn_c) are relative to calibration Of GPC With polystyrene standards. Coupling efficiency (wB) was calculated as the percentage of the coupled area relative to the total area of the MWD and degree of coupling (DC) was calculated using the uncoupled peak molecular weight (Mp_uc^ the coupling efficiency (we), and the weight-average molecular weight (Mw) in the following formula: DC = [1 + (Mw / Mp_uc-1) / wB].

[0085] Proton nuclear magnetic resonance (¹H-NMR), using a 300 MHz Bruker was used to quantify vinyl content, as indicated by International Standard ISO 21561-2005. Vinyl content is reported on a butadiene repeating unit weight basis.Attorney Docket No.: DYN-10-PCT

[0086] Mooney viscosity (M L1 +4) was determined at 100 °C, using a Monsanto Mooney MV 2000 equipment, following to ASTM D1646, on isolated polymer.

[0087] Solution viscosity of polymer sample was measured at 5 wt.% in styrene, Measurements were performed with certified glass capillary Cannon- Fenske viscometers at 25 °C.EXAMPLES OF POLYBUTADIENE RUBBER SYNTHESIS

[0088] In the first series of examples, butadiene is polymerized anionically in a batch reactor process to produce inventive partially coupled polybutadienes with an olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490).

[0089] Invention Examples lnv-1-5:

[0090] A total of 2609 of cyclohexane and 357 g of butadiene were charged to a 4.0- L stirred batch reactor. Initial reactor temperature was set at 60 °C by circulating a heating fluid through an internal coil. Then, circulation of heating fluid through internal coil was interrupted. Immediately afterwards, a specific quantity of n-butyllithium was injected into the reactor. Polymerization was carried out under quasi-adiabatic conditions and a specific peak polymerization temperature, TP(114 °C) Was reached 15 minutes after adding the initiator. Subsequently, a specific quantity of an olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490) was added to the reactor as coupling agent. Then, after an exhausting time of 15. minutes, the living polymer chains were terminated by adding a high molecular weight alcohol with high boiling temperature. It was confirmed by measuring the solids content that complete conversion of butadiene was achieved. The molecular weight distribution consists of two populations: an uncoupled and a coupled fraction. Characteristic molecular weights, polydispersity index (Mw / Mn), coupling efficiency and degree of coupling, vinyl content, styrene solution viscosity, and Mooney viscosity (ML1 +4 at 100 °C) are listed in Table 1 for different quantities of n-butyllithium and Dynasylan 6490. Where Mp__uc is the peak molecular weight of the uncoupled fraction, and Mw_c / Mn_c is the polydispersity index of the coupled fraction. CouplingAttorney Docket No.: DYN-10-PCTefficiency as a function of the ethoxy / N BL molar ratio and the molecular weight distribution curves of polybutadienes coupled with Dynasylan 6490 are shown in Figures 1 and 2, respectively. I t was possible to obtain coupled polybutadienes in a controlled manner with Dynasylan 6490, achieving a coupling efficiency of up to 93% and apparent coupling degrees of up to 5.

[0091] An embodiment of the present invention is a process to produce a polymer composition comprising the steps of:(i) polymerizing conjugated diene monomer in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions;(ii) reacting part of the polymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490);(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition.wherein the coupling agent may comprise an epoxy functionalized siloxane oligomer blend.

[0092] Another embodiment of the present invention is a process to produce a polymer composition, wherein the coupling efficiency can be adjusted from 0 to 95% by controlling the molar ratio of alkoxysilane groups in siloxane oligomers to polymer anions, wherein the siloxane oligomer coupling agent is selected to achieve a precise degree of coupling (i.e., from 2 to 6) and optimal branching, such that the resulting polymeric material comprises a.controlled distribution of molecular topologies— including linear, branched, cyclic, and crosslinked structures— thereby enabling tailored physical properties and processability.

[0093] An additional embodiment of the present invention is a process to produce a polymer composition, wherein the molar ratio of alkoxide groups in the coupling agent of functionalized siloxane oligomer blend to the polymer anions is between 0.05 and 3.0.

[0094] A particular embodiment of the present Invention is a process to produce a polyme r composition, wherein the molar ratio of alkoxide groups in theAttorney Docket No.: DYN-10-PCTcoupling agent of functionalized siloxane oligomer blend to the polymer anions is between 0,07 and 0.5.

[0095] In a particular embodiment of the present invention, a polymer composition comprising polymers of formulas:(P)n-X and P,comprises a conjugated diene monomer, wherein the conjugated diene repeating units are made from 1,3- butadiene monomer, wherein peak molecular Weight of P is from 100 to 320 kg / mol as measured per GPC calibrated with polystyrene standards, wherein (P)n-X accounts for 30 to 95 wt.%, wherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, on a conjugated diene basis, and wherein styrene solution viscosity of the polymer composition at 5 wt % and 25 °C is from 30 to 270 cP, and wherein Mooney ML1 +4 viscosity of the polymer composition at 100 °C is from 30 to 110,

[0096] In an embodiment of the present invention, a polymer composition comprising polymers of formulas:(P)n-X and P,comprises a conjugated diene monomer, wherein the conjugated diene repeating units are made from 1,3- butadiene monomer, wherein peak molecular weight of P is from 240 to 260 kg / mol as measured per GPC calibrated With polystyrene standards, wherein (P)n-X accounts for 40 to 60 wt.%, and wherein the polydispersity of the coupled polymer (P)n-X, Mw_c / Mn_c, is greater than 1.10, when measured by GPC calibrated with polystyrene standards, and wherein 1,2- vinyl content of the polymer composition is from 6 to 17 wt.%, and wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 140 to 180 cP. and wherein Mooney viscosity ( 1+4) of the polymer composition at 100 °C is from 46 to 66.

[0097] In another embodiment of the present invention, a polymer composition comprising polymers of formulas:(P)n-X and P,comprises a conjugated diene monomer, wherein the conjugated diene repeating units are made from 1,3-butadiene monomer, and wherein peak molecular weight of P is from 175 to 205 kg / mol as measured per GPC calibrated with polystyrene standards, and wherein (P)n-X accounts for 40 to 60 wt.%, andAttorney Docket No.: DYN-10-PCTwherein the polydispersity of the coupled polymer (P)n-X, Mw_c / Mn_c, is greater than 1.10, when measured by GPC calibrated with polystyrene standards, and wherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, and wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 70 to 110 cP, and wherein Mooney viscosity (ML1+4) of the polymer composition at 100 °C is from 46 to 66.

[0098] In an additional embodiment of the present invention, a polymer composition comprising polymers of formulas;(P)n-X and P,comprises a conjugated diene monomer, wherein the conjugated diene repeating units are made from 1,3-butadiene monomer, wherein peak molecular weight of P is from 100 to 140 kg / mol as measured per GPC calibrated with polystyrene standards, wherein (P)n-X accounts for 85 to 95 wt.%, wherein the polydispersity of the coupled polymer (P)n-X, Mw_c / Mn_c, is greater than 1.10, when measured by GPC calibrated with polystyrene standards, and wherein 1,2-vinyl Content of the polymer composition is from 6 to 17 wt.%, wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 40 to 60 cP, and wherein Mooney viscosity (ML1+4) of the polymer composition at 100 °C is from 50 to 65.

[0099] In a particular embodiment of the present invention, a polymer composition comprising polymers of formulas:(P)n-X and P,comprises a conjugated diene monomer, wherein the conjugated diene repeating units are made from 1,3-butadiene monomer, Wherein the molecular weight distribution of the polymer composition comprises at least two peaks; the peak with lowest molecular weight encompasses P, and the rest of the molecular weight distribution comprehends (P)n-X, and wherein peak molecular weight of P is from 100 to 320 kg / mol as measured per GPC calibrated With polystyrene standards, wherein (P)n-X accounts for 30 to 95 wt.% wherein the degree of coupling is from 3 to 5, when molecular weight distribution of the polymer composition is measured by G PC calibrated with polystyrene standards, and wherein the poly dis ersity Mw_c / Mn_c of the coupled polymer (P)n-X is greater than 1,10, when measured by GPC calibrated with polystyrene standards, wherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, on aAttorney Docket No.: DYN-10-PCTconjugated diene basis, and wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 30 to 270 cP and wherein Mooney viscosity (ML1+4) of the polymer composition at 100 °C is from 30 to 110.

[0100] Invention Examples lnv-6-10:

[0101] The same procedure was used as described in Invention Examples 1-5 to produce inventive partially coupled polybutadienes, but an olefinically functionalized siloxane oligomer blend with vinyl and ethoxy functional groups (Dynasylan 6498) was used as coupling agent. The molecular weight distribution showed two populations: a linear fraction and a coupled fraction. Characteristic molecular weights, polydispersity index, coupling efficiency and degree of coupling, vinyl content,styrene solution viscosity and Mooney viscosity (ML1+4 at 100 °C) are listed in Table 2 for different quantities of n-butyllithium and Dynasylan 6498. Coupling efficiency as a function of the ethoxy / NBL molar ratio and the molecular weight distribution curves of polybutadienes coupled with Dynasylan 6498 are shown in Figures 3 and 4, respectively. It was possible to obtain coupled polybutadienes in a controlled manner with Dynasylan 6498, achieving a coupling efficiency of up to 96% and apparent coupling degrees of up to 4.

[0102] An embodiment Of the present invention is a process to produce a polymer composition comprising the steps of:(i) polymerizing conjugated diene monomer in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions(il) reacting part of the polymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and ethoxy functional groups (Dynasylan 6498);(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition.wherein the coupling agent may comprise an epoxy functionalized siloxane oligo mer blend.

[0103] Invention Examples lnv-11 -13:Attorney Docket No.: DYN-10-PCT

[0104] A total of 786 g of cyclohexane and 88 g of butadiene were charged to a 2.0-L stirred batch reactor. Initial reactor temperature was set at 60 °C by circulating a heating fluid through an internal coil. Then, circulation of heating fluid through internal coil was interrupted. Immediately afterwards, 3.437 millimoles of n -butyllithium were added to the reactor. A peak polymerization temperature, Tp, was reached in 14 minutes. Then, 15 minutes after Tp, different amounts of ah epoxy functionalized siloxane oligomer blend with glycidoxypropyl and methoxy functional groups (D nasylan VPS 4721) were added to the reactor as coupling agent. Then, after an exhausting time of 10 minutes the living polymer chains were terminated by adding a high molecular weight alcohol. It was confirmed by measuring the solids content that complete conversion of butadiene was achieved. The molecular weight distribution consists of two populations: a linear and a coupled. Characteristic molecular weights, poly dispersity index, coupling efficiency and degree of coupling are listed in Table 3.

[0105] The displayed results in the table suggest that Dynasylan VPS 4721 is a highly effective coupling agent in living anionic polymerization, enabling the production of inventive partially coupled polybutadienes with actual coupling degrees close to four. The results suggest that the living polymer chains primarily couple through the methoxy functional groups than In the glycidyloxypropyl functional groups. Coupling efficiency as a function of the methoxy / NBL molar ratio and the molecular weight distribution curves of polybutadienes coupled with Dynasylan VPS 4721 are shown in Figures 5 and 6, respectively. It was possible to obtain coupled polyb tadienes in a controlled manner with Dynasylan VPS 4721, achieving a coupling efficiency of up to 91% and apparent coupling degrees of up to 3.3.

[0106] An embodiment of the present invention is a process to produce a polymer composition comprising the steps of:(i) polymerizing conjugated diene monomer in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions;(ii) reacting part of the polymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the epoxy functionalizedAttorney Docket No.: DYN-10-PCTsiloxane oligomer blend with glyc id oxy propyl and methoxy functional groups (Dynasylan VPS 4721);(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition.wherein the coupling agent may comprise an olefinically functionalized siloxane oligo er blend.

[0107] Comparative Examples C-1-5:

[0108] The same procedure as described in Invention Example 1-5 was used to produce comparative polybutadienes, but silicon tetrachloride (SiCl4) was used as coupling agent. The molecular weight distribution showed two populations: a linear and a coupled. Characteristic molecular weights, polydispersity index, coupling efficiency and degree of coupling, vinyl content, styrene solution viscosity and Mooney viscosity (ML1+4 at 100 °C) are listed in Table 4 for different quantities of n-butyllithium and SiCk.

[0109] Comparative Example C-6:

[0110] A 2-gallon stirred reactor was charged with 2754 grams of cyclohexane and 602 grams of butadiene. The temperature of the initial charge was set to 55°C by controlling flow of steam through the reactor jacket. Then, the heating was stopped, and polymerization was initiated by charging n-butyllithium. Reaction reached a peak temperature (Tp) of 109 °C in 11 minutes. Coupling was performed with SiCl4, which was charged to the reactor 1 minute after record of Tp. Polybutadienyllithium was shortstopped after an exhaust time of 5 minutes with a high molecular weight alcohol with a high boiling temperature. The lot was formulated with 0.18 wt.% of Irganox 1520 and 0.09% of Irganox 1076 while in solution (percentages on a solvent-free basis), then comparative polybutadiene was isolated by boiling water stripping and oven drying of wet crumbs. Characteristic molecular weights, polydispersity index, coupling efficiency and degree of coupling, vinyl content, styrene solution viscosity and Mooney viscosity (ML1+4 at 100 °C) of the comparative polybutadiene recovered are listed in Table 4 along with n-butyllithium and SiCl4 dosages.

[0111] Comparative examples C-1 to C-6 exhibit the characteristics of prior art polybutadienes obtained through batch anionic polymerization using SiCl4 as a coupling agent.Attorney Docket No.: DYN-10-PCT

[0112] Through an analysis conducted on inventive partially coupled polybutadienes obtained using the olefinically functionalized siloxane oligomer blends Dynasylan 6490 or Dynasylan 6498 with a gel permeation chromatograph equipped with a light scattering detector, it was determined that the average degree of coupling of the coupled fraction was in the range from 5 to 6, Furthermore, since the coupled population is a mixture of species with different degrees of coupling, this is reflected in an increase in the polydispersity index of the molecular weight distribution of the coupled fraction.

[0113] In the following comparative examples, the implications of using monomeric alkoxy silanes as a coupling agent are illustrated. Comparative examples C-7 to C-10 are listed in Table 5 and exhibit the properties of prior art polybutadienes obtained through batch anionic polymerization using tetraethoxysilane as coupling agent. It was observed that the polybutadienes obtained in C-7 to C-10 have lower coupling efficiency and degree of branching compared with lnv-1 to lnv-13. Furthermore, it was observed that the degree of coupling decreases as the coupling percentage increases. On the other hand, the amount of tetraethoxysilane required to achieve a certain percentage of coupling is much higher than that required with the functionalized siloxane oligomer blends of the present invention. In an industrial process, the use of high amounts of tetraethoxysilane as coupling agent would result in a greater amount of alcohol present in the recycled solvent, contamination of the stripping aqueous serum and release of VOC to the environment. This would increase the purification requirements of the reclaimed solvent, produce an uncontrolled increase in initiator consumption, and complicate the control of the macrostructure of prior art polybutadienes.

[0114] In the following comparative examples, the implications of using a cyclic siloxane as a coupling agent are illustrated. Comparative examples C-11 to C-14 are listed in Table 6 and exhibit the properties of prior art polybutadienes obtained through batch anionic polymerization using 1,3, 5, 7- tetramethyM,3,5,7’tetravinylcyclotetrasiloxane (vinyl-D4) as the coupling agent. A total of 918 g of cyclohexane and 125 g of butadiene were charged to a 2.0-L stirred batch reactor. Initial reactor temperature was set at 75 °C by circulating heating fluid through an internal coil. Then, circulation of heating fluid throughAttorney Docket No.: DYN-10-PCTinternal coil was interrupted, Immediately afterwards, a specific quantity of n- butyllithium was injected into the reactor. Polymerization was carried out under non-isothermal conditions and a specific peak polymerization temperature, TP(T ≥ 110 °C) was reached 4 minutes after adding the initiator. Subsequently, a specific quantity of vinyl-D4 was added to the reactor as coupling agent. Then, after an exhausting time of 10 minutes, the living polymer chains were terminated by adding a high molecular weight alcohol, it was observed that the polybutadienes obtained in C-11 to C-14 have lower coupling efficiency compared with Inv-1 to Inv-13 In contrast, the amount of cyclic siloxane required to achieve a given coupling percentage is greater than that required when using the functionalized siloxane oligomer blends of the present invention, which contain ethoxy or methoxy groups, Coupling efficiency as a function of the vinyl groups / N BL molar ratio is shown in Figure 7. It was possible to obtain coupled polybutadienes in a controlled manner With vinyTD4, achieving a coupling efficiency of up to 83% and apparent coupling degrees of up to 3.4.

[0115] The polybutadienes obtained in comparative examples C-11 to C-14 exhibit lower coupling efficiency (Le., up to 83%) than those in inventive examples lnv-1 to lnv-13 (i.e., up to 96%). The use of large amounts of vinyl-D4 as a coupling agent would lead to elevated concentrations of residual compounds in the recycled solvent and increase the risk of contaminating the stripping aqueous phase, the recycled solvent, and / or the final product. To achieve the same coupling efficiency, the consumption of vinyl-D4 as a coupling agent can be 40% higher than the amount required when using a siloxane oligomer functionalized with methoxy or ethoxy groups. A similar behavior is expected for other cyclic siloxanes containing a higher concentration of vinyl groups in their structures. The localization of functional groups on a small molecule such as vinyl- D4 restricts coupling efficiency, resulting in lower coupling percentages and degrees of coupling compared to those achieved with functionalized siloxane oligomers functionalized with methoxy or ethoxy groups, where steric hindrance is reduced due to their molecular nature. The lower polydispersity index (i.e., Mw_c / Mn_c lower than 1.10) of the molecular weight distribution observed in the coupled polymer fraction with vinyl-D4 may negatively impact on the processability of the polybutadienes, compared to those obtained using theAttorney Docket No.: DYN-10-PCTblends of functionalized siloxane oligomers of the present invention (i.e,, Mw_c / Mn_c higher than 1.10). This effect is illustrated in Figure 8, which compares the MWDs of polybutadienes coupled with vinyl-D4 or olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490) or olefinically functionalized siloxane oligomer blend with vinyl and ethoxy functional groups (Dynasylan 6498).

[0116] An embodiment of the invention is a polymer composition comprising polymers of formulas:(P)n-x and P,herein P is an uncoupled polymer prepared by living anionic polymerization comprising conjugated diene repeating units, wherein (P)n-X is a polymer comprising n arms of polymer P coupled to X, wherein X is a residue of an olefinically functionalized siloxane oligomer coupling agent, and wherein the olefinically functionalized siloxane oligomer coupling agent comprises at least one non-hydrolyzable olefinic functional group per siloxane oligomer molecule, alkoxy groups, and optionally saturated hydrocarbyl functional groups, and wherein the olefinically functionalized siloxane oligomer coupling agent comprises no more than one non-hydrolyzable olefinic functional group per silicon atom, and Wherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and wherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple numbers of silicon atoms per molecule, ranging from 2 up to 25,[001171 Another embodiment of the invention is a polymer composition comprising polymers of formulas:(P)n-X and P,wherein X is a residue of an epoxy functionalized siloxane oligomer coupling agent, and wherein the epoxy functionalized siloxane oligomer coupling comprises at least one alkyl ether functional group substituted by an epoxide per siloxane oligomer molecule, or at least one alkyl functional group substituted by an epoxide per silicon atom, alkoxy groups, and optionally saturated hydrocarbyl functional groups, and wherein the epoxy functionalized siloxane oligomerAttorney Docket No.: DYN-10-PCTcoupling comprises no more than one alkyl ether functional group substituted by an epoxide per silicon atom, or no more than one alkyl functional group substituted by an epoxide per silicon atom, and wherein the epoxy functional ized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and wherein the epoxy functionalized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules exhibiting a molecular weight distribution wherein the weight-average molecular Weight ratio to the number-average molecular weight (Mw / Mn) is greater-than or equal to 1.5, and wherein the epoxy functionalized siloxane oligomer has a dynamic viscosity from 600 to 2000 cP at 25 °C.

[0118] In another embodiment of the invention, the polymer compositions comprising polymer of formulas:(P)n-X and P,are characterized by having broader molecular weight distribution (MWD) and / or higher coupling efficiency than prior art polymers, wherein the molecular weight distribution of the polymer composition comprises at least two peaks: the peak with lowest molecular weight encompasses P, and the rest of the molecular weight distribution comprehends (P)n-X, and wherein the degree of coupling ranges from 2 to 6, when molecular weight distribution of the polymer composition is measured by GPC calibrated with polystyrene standards, and wherein the polydispersity Mw_c / Mn_c of the coupled polymer (P)n-X is greater than 1.10, when measured by GPC calibrated with polystyrene standards. For this purpose, the functionalized siloxane oligomer coupling agent is selected to achieve a precise degree of coupling (i.e., from 2 to 6), coupling efficiency and optimal branching, such that the resulting polymeric material comprises a controlled distribution of molecular topologies — including linear, branched, cyclic, and crosslinked structures — thereby enabling tailored physical properties and processability.Attorney Docket No.: DYN-10-PCTTable 1. Synthesis parameters and characterization results of Invention Examples Inv-1 to Inv-5. invention lnv-1 lnv-2 lnv-3 lnv-4 lnv-5ExampleCyclohexane, 7.31 7.31 7.31 7.31 7.31kg / kg-monomerButadiene 0.357 0.357 0.357 0.357 0.357monomer, kgn-buty I lithiumactive,0.854 9.358 9.755 3.754 8.419mmol / kg-monomerDynasylan 6490 0.185 0.196 0.261 0.239 0.239charged, g / kg- monomerMethanol 10 11 14 13 13concentration insolvent*, ppmInitial 60.1 60.3 60.2 604 61.0polymerizationtemperature, °CTp, °C 113.1 114.3 115.4 114.8 114.1Polymerization 15 15 15 15 15time up to Tp.minutesMp"_uc, kg / mol 198,3 208.8 200.3 2232 232.1Coupling 43.5 51.4 61.6 73.3 69.3efficiency, %Degree of 3.3 3.4 3.7 3.4 3.6couplingMw_c / Mn_c** 1.155 1.182 1.197 1.234 1.217Mw, kg / mol 393.4 469.8 531.7 623.9 649.3Mw / Mn** 1.476 1.546 1.607 1.513 1.558Vinyl content, 10.0 10.6 10.4 10.9 10.3wt.%Styrene solution 73.7 101.5 129.5 165.1 225.2viscosity at 5wt.%, cPMooney 30.9 48,5 62,4 677 86.0viscosity, MLj+4at 100 °C*Methanol concentration in solvent assuming complete hydrolysis of siloxane oligomer.“Relative molecular 'weights to polystyrene standards.Attorney Docket No.: DYN-10-PCTTable 2: Synthesis parameters and characterization results of Invention Examples Inv-6 to Inv-10. Invention Inv-6 Inv-7 Inv-8 Inv-9 Inv-10 ExampleCyclohexane, 7.31 7.31 7.31 7.31 7.31 kg / kg-monomerButadiene 0.357 0.357 0.357 0.357 0.357 monomer, kgn-butyllithium 10.959 9.707 9.919 8.448 7.966 active, mmol / kg-monomerDynasylan 6498 0.31 0.199 0.487 0.398 0.163charged, g / kg-monomerEthanol 21 13 33 27 11 concentration insolvent*, ppmInitial 60.4 60.9 60.0 61.0 60.2polymerizationtemperature, °CTp, °C 114.7 114.3 114.5 116.0 115.6 Polymerization 15 15 15 15 15 time up to Tp,minutesMp*_uc, kg / mol 178.3 201.3 197.0 231.3 245.3 Coupling 53.7 51.0 75.5 59.5 61.9 efficiency %Degree of cou pl i ng 3.5 4.1 3.6 3.8 3.9 Mw“, kg / mol: 413:2 517.7 582.6 613.9 680,5 Mw_c / Mn_c** 1.251 1.331 1.173 1.221 1.211 Mw / Mn** 1.583 1.770 1.476 1.634 1.624 Vinyl content, wt% 10.2 10.4 10.1 10.8 10.5 Styrene solution 64.9 88.5 115.0 143.2 214.0 viscosity at 5 wt.%,cPMooney viscosity, 31.7 42.2 58.4 59.0 74.2ML1+4 at 100°C‘Ethanol concentration in solvent assuming complete hydrolysis of siloxane oligomer.“Relative molecular weights to polystyrene standards;.Attorney Docket No.: DYN-10-PCTTable 3. Synthesis parameters and characterization results of Invention Examples Inv-11 to Inv-13.Invention Inv-11 Inv-12 Inv-13ExampleCyclohexane, 8.93 8.93 8.93kg / kg-monomerButadiene 0.088 0.088 0.088monomer, kgn-butyllithium 30.918 33.007 26.549active, mmol / kg-monomerDynasylan VPS 1.580 2.107 3.5064721 charged,g / kg-monomerMethanol 44 59 98concentration insolvent*,: ppmInitial 60.1 603 60,2pOlymefiZatidntemperature, °CTp, °C 77.4 75.3 77.1Polymerization time 30 30 30up to Tp, minutesMp*’_uc,:kg / mol 63,2 592 73.6Coupling efficiency, 61.6 74.5 91.8%Degree of coupling 3.1 3.2 3.2Mw_c / Mn_c 1.101 1.106 1.107Mw**, kg / mol 141.1 154.2 216.3Mw / Mn 1.394 1.359 1.207Vinyl content, wt.% 10.4 10.2 10.9*Methanol concentration in solvent assuming complete hydrolysis of siloxane oligomer.**Relative molecular weights to polystyrene standards.Attorney Docket No.: DYN-10-PCTTable 4. Synthesis parameters and characterization results of Comparative Examples C-1 to C-6. Invention C-1 C-2 C-3 C-4 C-5 C-6 ExampleCyclohexane, 7.31 7.31 7.31 7.31 7.31 7.38 kg / kg-monomerButadiene 0.357 0.357 0.357 0.357 0.357 0.373 monomer, kgn-butyllithium 10.103 8.248 10.284 7.487 7.062 7.296 active, mmol / kg-monomerSiCl4 charged, 0.083 0.142 0.159 0.080 0.094 0.131 g / kg-monomerInitial 60.0 60.1 60.4 60.2 61.1 55.0 polymerizationtemperature, °CTp, °C 114.2 113.0 112.6 115.0 115.7 108.7 Polymerization 15 15 15 15 15 14 time up to Tp,minutesMp*_uc, kg / mol 191.6 236.9 190.0 261.7 276.7 267.8 Coupling 28.7 40.9 40.3 37.4 40.3 44.6 efficiency, %Degree of 3.1 3.1 3.1 3.0 3.0 3.0 coupling:Mw_c / Mn_c 1.031 1.053 1.048 1.050 1.060 1.053 Mw*, kg / mol 308.6 342.7 385.5 454.8 499.5 504.4 Mw / Mn 1.358 1.440 1.420 1.433 1.391 1.373 Vinyl content, 10.2 10.3 10.6 10.8 10.5 N.D. wt.%Styrene solution 45.2 57.1 72.6 101.6 187.5 154.4 viscosity at 5wt.%, cPMooney 16.2 21.0 33.0 51.0 55.0 49.5 viscosity, ML1+4at 100°C‘Relative: o lecu la T we i ghts: to po ly styterie sta nda rds,Attorney Docket No.: DYN-10-PCTTable 5. Synthesis parameters and characterization results of Comparative Examples C-7 to C-14 Invention Example C-7 C-8 C-9 C-10 Cyclohexane, 7.24 7.24 7.24 7.24kg / kg-monomerButadiene 0. 137 0.137 0.137 0.137 monomer, kgn-butyl lithium 8.632 8.431 9.291 11.186 active, mmol / kg- monomerTetraethoxysilane 0.235 0.349 0.524 0.641 charged, g / kg- monomerEthanol 129 193 290 354 concentration insolvent*, ppmInitial 70.5 70.0 705 70.4 polymerizationtemperature, °CTp °C 985 97.8 994 101.2 Polymerization: time 7 8 7 6uptoTp, minutesMp**_uc, kg / mol 233.7 231.8 210.3 174.7 Coupling efficiency, 37 62.6 76.2 77.2%Degree of coupling 3.1 2.9 27 2.8Mw", kg / mol 415.5 500.7 474.1 420.1 Mw_c / Mn_c 1.037 1.068 1.076 1.074Mw / Mn 1.393 1.349 1.424 1.313Vinyl content, v / t% 106 10.9 11.1 10.2Styrene solution 96. 1 138.0 140.7 97.5viscosity at 5 wt.%,cPMooney viscosity, 34.7 60.9 72.6 63.4ML1+4 at 100 °C* Ethanol concentration in solvent assuming complete hydrolysis of tetraethoxysilane.“Relative molecular weights to polystyrene standardsAttorney Docket No.: DYN-10-PCTTable 6. Synthesis parameters and characterization results of Comparative Examples C-11 to C-14.Invention Example C-11 C-12 C-13 C-14 Cyclohexane, 7.33 7.33 7.33 7.33kg / kg-monomerButadiene 0.125 0.125 0.125 0 125 monomer, kgn-butyl lithium 8.593 8.514 9.759 9.611 active, mmol / kg- monomerCyclic siloxane 0.378 0.481 1.442 1.992 charged, g / kg- monomerinitial 74.3 75.0 76.5 75.6 polymerizationtemperature, ’CTp, °C 109.2 108.7 110.9 110.0 Polymerization time 4.5 4.5 3.5 4.1upto Tp. minutesMp**_uc, kg / mol 207.8 209.7 183.0 185.3 Coupling efficiency, 55.8 70.6 78.0 82.5%Degree of coupling 3.3 3.2 3.2 3.2 Mw_c / Mn_c 1.061 1.059 1.069 1.089Mw‘, kg / moi 476.8 533.1 493.6 529.0 Mw / Mn 1.480 1.415 1.391 1.354Vinyl content, wt% 10.3 11.6 9.6 11.0Styrene solution 117.5 152.0 169.0 194.6 viscosity at 5 wt.%,cPMooney viscosity, 47.6 62.2 69.4 80.2ML1+4 at 100 ’C‘Relative molecular weights to polystyrene standards.Attorney Docket No.: DYN-10-PCTEXAM PLES OF R U BBER PROCESSABILITY IN INDUSTRIAL DRYING PROCESS

[0119] The following examples show the unexpected advantage of higher throughput of partially coupled polybutadiene rubber compositions of the present invention through an industrial drying setup, compared against drying of prior art polybutadiene coupled with SiCl4.

[0120] Invention Example Inv-14 industrial drying of polybutadiene of the invention, partially coupled by using a functionalized siloxane oligomer blend.

[0121] A solution of polybutadiene in cyclohexane was produced by batch polymerization in industrial reactors; using a functionalized siloxane oligomer blend as coupling agent, to render poly mer with a degree of coupling = 3.59, Mw_c / Mn_c = 1.152, and styrene solution Viscosity = 149.5 cP. Antioxidants 2-methyl-4,6-bis[(octylthio)methyl]phenol and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl ester, pre- di s solved i n cyclo hexa ne, we re homogenized into the rubber solution to get levels of 0.18 and 0.09 wt.% on a polybutadiene basis, respectively. Cyclohexane was removed from the polymer by steam stripping in boiling water, rendering a stream of porous rubber crumbs in water. Part of the water was removed by sieving, reducing volatile matter to about 40-50 wt.%. The inventive partially coupled polybutadiene was further dried by processing the polybutadiene through an Anderson Expeller®, an Anderson Expander®, a hot box, vibrating conveying trays and a spiral conveyor blown with hot air, in series. The rubber was cooled with air in the upper section of the spiral conveyor and subsequently baled using a press. Surprisingly, it was feasible to produce inventive partially coupled polybutadiene at a rate of 3.1 metric tons per hour on a drying line, rendering rubber with a volatile matter ranging from 0.16 to 0.40 wt.%, and without exceeding a gel content of 0.038 wt%.

[0122] Comparative Example C-15 industrial drying of polybutadiene of prior art, coupled by SiCk.

[0123] Production of prior art polybutadiene was performed using the same procedure and equipment as in Inventive Example Inv-14 but obtaining a SiCl4-coupled polymer with exact characteristics as in Comparative Example C- 6. The operating conditions of the drying process were optimized to get a maximum polybutadiene throughput of 2.4 metric tons per hour on a drying line,Attorney Docket No.: DYN-10-PCTrendering rubber with average volatile content of 0.55%, specif ically ra nging from 0.33 to 0.75 Wt.%, and with gel content ranging from 0.048 to 0.056 wt.%.

[0124] Polybutadienes industrially dried in invention Example 14 and Comparative Example C-15 share the features of being synthetized by batch polymerization using a partial coupling step, and having roughly the same styrene solution viscosity, 149.5 and 154.4 cP, respectively, but differ in the kind of coupling agent used in their synthesis. It is noteworthy that in Invention Example 14, the ind ustrial drying of the inventive polybutadiene, synthesized with a functionalized siloxane oligomer blend as coupling agent, was capable to be processed at significantly higher throughput, 29% higher than the case illustrated in Comparative Example C-15, where prior art polybutadiene synthetized by partial coupling with silicon tetrachloride was dried. Advantageously and surprisingly, the higher throughput obtained in Invention Example 14 was obtained rendering a drier product, i.e. with lower volatile matter content, and with lower gel content than in Comparative Example C-15, A drier polybutadiene is advantageous because it is purer than a polybutadiene with higher moisture content, thus, at equal weight loading in a formulation more polybutadiene weight fraction is obtained if the polybutadiene used is drier. Moreover, moisture is known to lower the rate of bulk copolymerization of styrene and acrylonitrile, therefore an advantage of slightly higher rate in the polymerization of ABS is to be expected when drier polybutadiene is used in its formulation. A polybutadiene with lower gel content is advantageous because gel is a very deleterious impurity in polybutadiene to be used in production of ABS and HIPS plastics by mass polymerization: some gels from the polybutadiene may pass through the filtration step of polybutadiene solution in the ABS or HIPS production process and appear as surface protuberances in the final plastic product, impairing its aesthetics. Moreover, a polybutadiene with lower gel content reduces the frequency of filter plugging in the ABS and HIPS production processes.EXAMPLES OF DISSOLUTION TIME OF RUBBER IN H IPS AND ABS RECIPES

[0125] The following examples show the unexpected advantage of shorter dissolution time of the inventive partially coupled polybutadiene rubber ofAttorney Docket No.: DYN-10-PCTthe invention in monomers used to polymerize HIPS and ABS. Dissolution time is compared against that of prior art polybutadiene coupled with SiCl4

[0126] Invention Example Inv-15. Dissolution time in styrene of a polybutadiene of the invention, partially coupled by a functionalized siloxane oligomer blend.

[0127] Dissolution time of polybutadiene prepared in Invention Example Inv-14 was evaluated using the following procedure: 8 grams of inventive partially coupled polybutadiene were placed in between non-stick coated steel plates, and then placed into a molding press with platens at 60 °C, clamping force was gradually increased within 3 minutes to 20 tons and was kept co nsta nt for 20 additional minutes, then platens were cooled down to 25 °C by circulating cold water thru the platens internal coil. A polybutadiene film of about 1.5 mm thickness obtained, which was further dried in a vacuum oven at 100 °C and -29.8 in Hg for 1 hour. The polybutadiene film was cut into circular sections with a hole punch, and 3 grams of those sections were piled up into a mold cavity with 1.6 cm diameter and 1 cm height, The mold was compression molded employing the same conditions as for the film. A void-free polybutadiene cube, with a mass of 0.565 g, was sectioned from the molded button. The void-free polybutadiene cube and 10.74 g of styrene were placed within a 20 mL glass vial and shaken with a Burrell Wrist Action Shaker, model 75, operating at 385 oscillations per minute, with a shaking angle of 10 degrees and clamps tilted 20 degrees relative to the horizontal. Surprisingly, complete dissolving of the void-free polybutadiene cube required 6 hours and 7 minutes.

[0128] Invention Example Inv-16. Dissolution time in styrene / acrylonitrile / ethylbenzene mixture of a polybutadiene of the invention, partially coupled by a functionalized siloxane oligomer blend.

[0129] The procedure of Inventive Example Inv-15 was performed, but it employed 10 ml of a solution composed of 69.4 wt.% of styrene, 15.3 wt.% of acrylonitrile, and 15,3 wt.% of ethylbenzene, instead of 10.74 g of styrene. Surprisingly, complete dissolving of the void-free polybutadiene cube required 6 hours and 53 minutes.

[0130] Comparative Example C-16. Dissolution time in styrene of prior art pplybutadiene, coupled with SiCl4Attorney Docket No.: DYN-10-PCT

[0131] The procedure of Inventive Example Inv-15 was performed but using prior art polybutadiene prepared in Comparative Example C-6 instead of partially coupled poiybutadiene prepared in Inventive Example Inv-14. Complete dissolving of the void-free polybutadiene cube required 8 hours and 15 minutes.

[0132] Comparative Example C-17. Dissolution time in styrene / acrylonitrile / ethylbenzene of prior art polybutadiene, coupled with SiCl4

[0133] The procedure of Inventive Example lnv-16 was performed but using prior art poiybutadiene prepared in Comparative Example C-6 instead of partially coupled poiybutadiene prepared in Inventive Example Inv-14. Complete dissolving of the void-free poiybutadiene cube required 8 hours and 5 minutes.

[0134] Comparison of Invention Example 15 with Comparative Example C-16 illustrate that an inventive polybutadiene, obtained by batch polymerization involving partial coupling by using a functionalized siloxane oligomer blend, dissolves 2 hours and 8 minutes faster in a monomer formulation for HIPS polymerization than a prior art polybutadiene, partially coupled with silicon tetrachloride, of roughly same solution viscosity. Analogously, comparison of Inventive Example 16 with Comparative Example C-17 shows that the inventive poiybutadiene dissolves 1 hour and 13 minutes faster than the prior art polybutadiene in a monomer / solvent formulation for ABS polymerization. Fast dissolution of polybutadiene in ABS and HIPS monomer formulation is highly desirable because dissolution is a lengthy step in the process to produce such plastics. Thus, reducing the time to complete such process step may debottleneck the process, enabling higher ABS and HIPS process throughput. Additionally, a faster dissolution reduces the risk of not fully dissolving the polybutadiene in the monomer prior to ABS or HIPS polymerization. If any minute amount of polybutadiene does not get fully dissolved, but just reaches a swollen state, it may pass through the filtering process and appear as surface protuberances in the final plastic product, impairing its appearance. Swollen polybutadiene may also contribute to higher frequency of filter plugging in the ABS or HIPS process.EXAMPLES OF IMPACT MODIFICATION OF STYRENIC PLASTICSAttorney Docket No.: DYN-10-PCT

[0135] The following examples compare properties of styrenic plastics, HIPS and ABS, produced with partially coupled polybutadienes according to the present invention. Performance is compared against usage of commercial benchmark prior art polybutadiene produced by continuous process. In these examples rubber toughened plastic performance properties were measured as follows:(a): Izod impact strength as per ASTM D-256, using injection molded probes of 1 / 8-inch thickness, notched. Probes conditioned at 23 °C and 50% relative humidity.(b) Tensile modulus and tensile yield strength, as per ISO 527-2 / 1A / 5, using injection molded probes. Probes conditioned at 23 °C and 50% relative humidity.(c) Flexural modulus and flexural yield strength as per ASTM D790, using injection molded probes. Probes conditioned at 23 °C and 50% relative humidity.(d) Melt flow index as per ASTM D1238, at 200 °C and 5 kg load for H IPS, or at 220 °C and 10 kg load for ABS.

[0136] Invention Example Inv-17. Unexpected properties of HIPS polymerized with inventive polybutadiene partially coupled with a functionalized siloxane oligomer blend.

[0137] A 1 -gallon stirred reactor was charged with 117 grams of the inventive polybutadiene of Invention Example Inv-14, 1141 grams of styrene, 19.4 grams of mineral oil, and 0.65 grams of Irganox 1076. The air within the reactor was purged with nitrogen. Then the reactor stirred at 60 rpm and room temperature overnight Then, the stirring speed was increased to 80 rpm, and heating oil began to circulate through the reactor's jacket. By the moment the reactor contents reached a temperature of 92 °C, 0.39 grams of Sulfole 120, a chain transfer agent, were injected into the reactor, plus 5 grams of styrene to rinse the syringe employed. When reactor contents reached a temperature of 96 °C, 0.65 grams of Luperox 331 M80 radical initiator were injected, plus 5 grams of styrene to rinse the syringe employed, which started polymerization. Rate of polymerization was followed by frequent reactor sampling and measurement of solids content. The last sampling took place when the solids content was 32.8%,Attorney Docket No.: DYN-10-PCTby that moment the temperature of reaction was 105 °C. Simultaneously to the last sampling, stirring speed was reduced to 50 rpm and cooling began through the reactor jacket. After 20 minutes of cooling, when the reacting mass had reached 99 °C, 0.26 grams of Sulfole 120 were injected into the reactor, plus 5 grams of styrene to rinse the syringe employed. Then, 10 minutes afterwards, when temperature of reactor contents had dropped to 91 °C, 0.65 grams of Luperox 331 M80 were injected into the reactor, plus 5 grams of styrene to rinse the syringe employed. Then, 20 minutes afterwards, when the temperature of reactor contents reached 73 °C, stirring was stopped. Reactor cooling continued until the prepolymer temperature dropped to 25 °C. Then 1004.06 grams of prepolymer were transferred to a 13-inch diameter aluminum pan and placed within a hermetically closed mold with cavity height of 1.625 in. The mold was placed within a press. After purging the air within the mold with nitrogen through a manifold, the system was closed back and temperature of the press plates was controlled with the following profile: 30 minutes at 100 °C, 30 minutes at 115 °C, 90 minutes at 130 °C, and 210 minutes at 160 °C. Then, the devolatilization of the polymer was performed by opening a vacuum line connected to the mold’s manifold, operating at -29.8 in Hg. Volatiles pulled out from the polymer were condensed in cold traps. During devolatilization, temperature of the press plates was controlled with the following profile: 10 minutes at 160 °C, 5 minutes at 180 °C, 5 minutes at 200 °C, 5 minutes at 220 °C, 5 minutes at 240 °C, and 20 minutes at 260 °C. Then, the press plates were cooled down to 36°C 'within 36 minutes. Then, the vacuum line was closed, and air was let enter the mold. By this process 864.5 grams of HIPS were obtained. Final inventive polybutadiene content in the HIPS, by material balance, was 10.5%, Surprisingly, properties of the HIPS were the following: Izod impact strength = 93.0 J / m, tensile modulus = 764 MPa, tensile yield strength = 17.2 MPa, flexural modulus = 1392 MPa, flexural yield strength = 37.1 MPa, and melt flow index = 4.7 g / 10 min.

[0138] Comparative Example C-18. Properties of HIPS polymerized with polybutadiene of prior art.

[0139] The procedure of Inventive Example Inv-17 was carried out replacing partially coupled polybutadiene of the invention by commercial prior art polybutadiene Buna® CB 55 G PT from Arlanxeo, with a monomodal and broadAttorney Docket No.: DYN-10-PCTmolecular weight distribution, with / Mn“1,76, characteristic of being produced by a continuous polymerization: process; a styrene solution viscosity of 160.6 cP, and Mooney viscosity of 53.6; Very subtle differences were encountered during the process in comparison to Inventive Example lnv’17: solids content and reaction temperature at last sampling from stirred reactor were 31, 1 % and 104 °C, respectively, mass of prepolymer transferred to aluminum pan within the mold was 1006.3 grams, mass of final HIPS recovered was 907.6 grams, and final prior art polybutadiene content in HIPS, by material balance was 10.0%. Properties of the HIPS were the following: Izod impact strength = 76.1 J / m, tensile modulus 759 MPa, tensile yield strength = 17.1 MPa, flexural modulus = 1408 MPa, flexural yield strength = 37.8 MPa, and melt flow index = 5.2 g / 10 min.

[0140] Invention Example Inv-18, Unexpected properties of ABS polymerized with inventive polybutadiene partially coupled with a functionalized siloxane oligomer blend.

[0141] A 1 -gallon stirred reactor was charged with 137.7 g of polybutadiene, partially coupled with a functionalized siloxane oligomer blend. The degree of coupling was 3.65, Mw_c / Mn_c was 1.163, Mw / Mn was 1.569, arid the styrene solution viscosity was 90.7 cP. Additionally, 886.3 g of styrene, 258.8 g of acrylonitrile, and 116.7 g of ethylbenzene were loaded to the reactor. The air within the reactor was purged with nitrogen. Then, the reactor was stirred at 60 rpm and room temperature overnight. Then, the stirring speed was increased to 90 rpm, and heating oil began to circulate through the reactor’s jacket. By the moment the reactor contents reached a temperature of 95 °C, 1.232 g of Sulfole 120 chain transfer agent, 0.21 g of Luperox 331 M80 radical initiator, and 5 g of styrene to rinse styrene, were injected into the reactor. Rate of polymerization was followed by frequent reactor sampling and measurement Of solids content. The last sampling took place when the solids content was 31.2%, by that moment the temperature of reaction was 105 °C. Simultaneously to the last sampling, stirring speed was reduced to 50 rpm and cooling began through the reactor jacket. Then, 30 minutes afterwards, when the temperature of reactor contents reached 95 °C, stirring was stopped. Reactor cooling continued until the prepolymer temperature dropped to 25 °C. Then 1088.34Attorney Docket No.: DYN-10-PCTgrams of prepolymer were transferred to a 13-inch diameter aluminum pan and placed within a hermetically closed mold with cavity height of 1.625 in. The mold was placed within a press. After purging the air within the mold with nitrogen through a manifold, the system was closed back and temperature of the press platens was controlled with the following profile: 90 minutes at 100 °C, 20 minutes at 110 °C, 20 minutes at 12045 minutes at 130 °C, and 210 minutes at 140 °C. Then, the devolatilization of the polymer was performed by opening a vacuum line connected to the mold’s manifold, operating at -29.8 in Hg. Volatiles pulled out from the polymer were condensed in cold traps. During devolatilization, temperature of the press platens was controlled with the following profile: 30 minutes at 140 °C, 10 minutes at 150 °C, 10 minutes at 160 °C, 10 minutes at 170 °C, 5 minutes at 180 °C, 5 minutes at 200 °C, 5 minutes at 220 °C, 5 minutes at 240 °C, and 20 minutes at 260 °C; Next, the press plates were cooled to 43 °C in 30 minutes. Then, the vacuum line was closed, and air was let enter the mold. By this process 860.2 grams of ABS were obtained. Final inventive polybutadiene content in the ABS, by material balance, was 12.4%. Surprisingly, properties of the ABS were the following: Izod impact strength = 391 J / m, tensile modulus = 1143 MPa, tensile yield strength = 41.2 MPa, flexural modulus = 2231 MPa, flexural yield strength = 72.2 MPa, and melt flow index = 3.2 g / 10 min.

[0142] Comparative Example C-19. Properties of ABS polymerized with polybutadiene of prior art

[0143] The procedure of Inventive Example lnv-18 was carried out replacing partially coupled polybutadiene of the invention by prior art polybutadiene grade Diene™ 40AG15 from Lion Elastomers, which has a monomodal and broad molecular weight distribution, with Mw / Mn=2.30, characteristic of being produced by a continuous polymerization process, a styrene solution viscosity of 99,3 cP, and Mooney viscosity of 42.2. Very subtle differences were encountered during the process in comparison to Inventive Example Inv-18: injection of Sulfole 120 chain transfer agent and Luperox 331 M80 to the stirred reactor was performed when the lot reached a temperature of 96 °C, solids content and reaction temperature at the moment of last sampling from stirred reactor were 31.9% and 107 °C, respectively, mass of prepolymer transferred to aluminum pan within the mold was 1091.8 g, mass of final ABSAttorney Docket No.: DYN-10-PCTrecovered was 868,1 g, and final polybutadiene content in ABS, by material balance was 12.3%. Properties of the ABS were the following: Izod impact strength = 393 J / m, tensile modulus = 1125 MPa, tensile yield strength = 39.4 MPa, flexural modulus = 2129 MPa, flexural yield strength = 69.1 MPa, and melt flow index = 23 g / 10 min,

[0144] Comparison of Invention Example 17 and Comparative Example C-18 shows that usage of the inventive polybutadiene, obtained by batch polymerization with partial coupling using a functionalized siloxane oligomer blend, renders a HIPS plastic with improved impact strength, 22% higher than using a prior art polybutadiene, obtained by continuous polymerization process and with wider polybutadiene molecular weight distribution. Impact strength is the main mechanical property sought in HIPS plastic. It is usually found that when a polybutadiene with lower solution viscosity is employed in the production of HIPS plastic its impact strength is compromised. Nevertheless, in Invention Example 17 a polybutadiene with slightly lower solution viscosity 'was: employed than the one used in Comparative Example C-18, being 149.5 and 160.6 cP, respectively, which makes the impact strength improvement in Inventive Example 17 surprising and unexpected. The slightly higher tensile and flexural moduli obtained in Invention Example 17 are also surprising and unexpected, because it is usually seen in this kind of plastic that when impact strength is increased tensile and flexural moduli are compromised, but the opposite was found in Invention Example 17 relative to the moduli obtained in Comparative Example C^ 18.

[0145] Comparison of Invention Example 18 and Comparative Example C-19 shows that usage of the inventive polybutadiene, obtained by batch polymerization with partial coupling using a functionalized siloxane oligomer blend, renders a ABS plastic with practically the same impact strength than using a prior art polybutadiene, obtained by continuous polymerization process and with wider polybutadiene molecular weight distribution, Impact strength is the main mechanical property sought in ABS plastic. It is usually found that when a polybutadiene With lower solution viscosity is employed in the production of ABS plastic its impact strength is compromised. Nevertheless, in Invention Example 18 a polybutadiene with slightly lower solution viscosity was employed than theAttorney Docket No.: DYN-10-PCTone used in Comparative Example C-19, being 90,7 and 99;3 cP, respectively, which makes the impact strength match in Inventive Example 18 surprising and unexpected, Slightly higher flexural modulus and tensile modulus in the ABS produced in Invention Example 18 are also somewhat unexpected given the match of impact strength with Comparative Example C-19.

[0146] An embodiment of the present invention is a rubber toughened plastic composition comprising:i. a continuous vitreous polymer matrix phase comprising styrene repeating units; and optionally comprising randomized acrylonitrile repeating units, andii. the polymer composition of any one of claims 1 to 22 in the rubber toughened plastic composition from 3.5 to 17 wt.%, andiii. dispersed rubbery particles, with size in the range from about 0.1 microns to about 10 microns, comprising the polymer composition of any one of claims 1 to 22 which has been crosslinked, grafted, and physically occluded with the same kind of polymer as the matrix phase.Attorney Docket No.: DYN-10-PCTEXAM PLES OF RADIAL STYRENIC BLOCK COPOLYMERS

[0147] In the next series of examples, radial partially coupled styrene-butadiene block copolymers are synthetized anionically in a batch reactor process using different coupling agents as follows: SiCI4 for Comparative Example C -20, tetraethoxysilane for Comparative Example C-21, and Dynasylan 6490 for Invention Example lnv-19.

[0148] Cyclohexane solvent (2500 g) was added to a 4.0-liter stainless steel reactor under an inert nitrogen atmosphere. Tetrahydrofuran (THF) was then added to achieve a THF concentration in the solvent between 100 and 150 ppm. Styrene (104 g) was fed to the reactor at a rate adequate to complete its charge in 0.5 minutes. The reactor initial temperature stabilized at 65 °C. Immediately afterwards, 6.28 millimoles of active n-butyllithium were added to the reactor. Reactor circulation fluid of the controller temperature was stopped along styrene block polymerization. Reactor temperature reached a peak, temperature of 73 °C (Tp-Sty) in 5 minutes, and a wait time of 10 minutes was practiced, therefore first, block homopolymerization time was 15 minutes, immediately after butadiene (243 g) was fed in a period of about 2 minutes. The temperature right at the start of butadiene feed was 69 °C (Ti-Bd). Butadiene polymerization reached a peak temperature of 102 °C (Tp-Bd), 8 minutes after beginning butadiene loading. In every case butadiene polymerization occurred without circulation of water through the jacket. There was a wait time of 5 minutes before the respective coupling agent (SiCI4, tetraethoxysilane or Dynasylan 6490) was added to reactor. Past 5 minutes an alcohol was added to deactivate the remaining polymer anions. Characteristic molecular weights, polydispersity index, coupling efficiency, degree of coupling, vinyl content and total styrene content of the radial partially coupled styrene-butadiene block copolymers are listed in Table 7 for each coupling agent as follows: SiCI4 for Comparative Example -20, tetraethoxysilane for Comparative Example C-21, and Dynasylan 6490 for Invention Example lnv-19, The characteristics of the inventive partially coupled block copolymers are shown in Table 7. Surprisingly, the use of coupling agents based on functionalized siloxane oligomer blends allows an unexpected efficient production of radial partially coupled styrene-butadiene block copolymers, such as invention exa mple lnv-19, with higher polydispersity Mw / MnAttorney Docket No.: DYN-10-PCTthan prior art comparative examples C-20 and C-21, as well as their corresponding hydrogenated partially coupled styrene-ethylene / butylene block copolymers. Block copolymers obtained with the functionalized siloxane oligomer blends are free of hygroscopic chloride salts generated by using SiCl4 and the quantities of alcohol generated are lower than those produced if monomeric alkoxysilanes were used.

[0149] An embodiment of the present invention is a process to produce a polymer composition comprising the steps of:(i) copolymerizing conjugated diene and vinyl aromatic monomers in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions;(ii) reacting part of the polymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490);(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition.wherein the process may comprise a second charge of vinyl aromatic monomer after copolymerization of an initial charge of conjugated diene monomer and vinyl aromatic monomer, wherein the coupling agent may comprise an epoxy functionalized siloxane oligomer blend.

[0150] Another embodiment of the present invention is a process to produce a polymer composition comprisi ng the steps of:(i) polymerizing conjugated diene monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;(ii) block polymerizing vinyl aromatic monomer with the foregoing polymer anions;(iii) reacting part of the block copolymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490);Attorney Docket No.: DYN-10-PCT(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,(V) recovering the polymer composition.wherein vinyl aromatic monomer may be fed to the reactor after polymerization of more than 90% of the conjugated diene monomer, wherein the coupling agent may comprise an epoxy functionalized siloxane oligomer blend.

[0151] A particular embodiment of the present invention is a process to produce a polymer composition comprising the steps of:(i) polymerizing vinyl aromatic monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;(ii) block polymerizing conjugated diene monomer with the foregoing polymer anions;(iii) reacting part of the block copolymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dynasylan 6490);(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,(v) recovering the polymer composition.wherein the coupling agent may comprise an epoxy functionalized siloxane oligomer blend.

[0152] An additional embodiment of the present invention is a process to produce a polymer composition comprising the steps of:(i) polymerizing vinyl aromatic monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;(ii) block polymerizing conjugated diene monomer with the foregoing polymer anions;(iii) reacting part of the block copolymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend, such as the olefinically functionalized siloxane oligomer blend with vinyl and methoxy functional groups (Dy nasylan 6490);Attorney Docket No.: DYN-10-PCT(iv) deactivating the remaining block copolymer anions with a polar proton donor;(v) hydrogenating the conjugated diene unsaturations; and,(vi) recovering the polymer composition.wherein the coupling agent may comprise an epoxy functionalized siloxane oligomer blend.

[0153] An embodiment of the present invention is a polymer composition, wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein optionally P is a tapered block copolymer, and wherein the vinyl aromatic blocks in (P)n-X are bonded to X.

[0154] Another embodiment of the present invention is a polymer composition, wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein P is a di-block copolymer, and wwherein the vinyl aromatic blocks in (P)n-X are bonded to X.

[0155] A particular embodiment of the present invention is a polymer composition, wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein P is a di-block copolymer, and wherein the conjugated diene blocks in (P) n-X are bonded to X.

[0156] An additional embodiment of the present invention is a polymer composition, wherein conjugated diene repeating units are saturated by hydrogenation, and wherein vinyl aromatic repeating units are left intact.Attorney Docket No.: DYN-10-PCTTable 7 Synthesis parameters and: characterization: of Comparative Examples C-20 and C-21, and Invention Example Inv-19.Invention Example C-20 C-21 lnv-19 Cyclohexane, kg / kg- 7.33 7,33 7,33monomerStyrene monomer, kg 0 104 0.104 0.104Butadiene monomer, kg 0243 0.243 0:243n-buty I lithium active, 34.264 33.804 23.865mmol / kg-monomersSiCl4, charged, g / kg- 0.620 n / a n / amonomersTetraethoxysilane n / a 1,311 h / acharged, g / kg-monomersDynasylan 6490 charged, n / a n / a 0.765g / kg-monomersAlcohol concentration in n / a 159 30solvent*, ppmInitial polymerization 64.5 65.2 65,0temperature, °CTp styrene, °C 72.8 72.1 73.2Tp butadiene, °C 101.9 98.5 101.7Mp**_uc, kg / mol 114.4 112.1 109.7Coupling efficiency, % 94.5 87.2 90.9Degree of coupling 2.7 2.2 3.2Uw**, kg / mol 297.2 229.4 326.9Mvv / Mn 1.097 1.157 1.633vinyl content, wt.% 11.1 10.5 11.6Btd basisTotal Styrene, wt.% 30.8 29.2 30.3Block styrene, % 99.1 98.9 99.2Sty basis* Ethanol concentration in solvent for tetraethoxysilane and methanol for Dynasylan 6490 **Relative molecular weights to polystyrene standardsAttorney Docket No.: DYN-10-PCTEMBODIMENTS OF THE INVENTION

[0157] Embodiment 1. A polymer composition comprising polymers of formulas:(P)n-Xand P,wherein P is an uncoupled polymer prepared by living anionic polymerization comprising conjugated diene repeating units,wherein (P)n- is a polymer comprising n arms of polymer P coupled to X, wherein X is a coupling agent residue of an olefinically functionalized siloxane oligomer blend, andherein the molecular weight distribution (MWD) of the polymer composition comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value, andwherein the olefinically functionalized siloxane oligomer coupling agent comprises at least one non-hydrolyzable olefinic functional group per siloxane oligomer molecule, alkoxy groups, and optionally saturated hydrocarbyl functional groups, andWherein the olefinically fUhctionalized siloxane oligomer coupling agent comprises no more than one non-hydrolyzable olefinic functional group per silicon atom, andwherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and wherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple numbers of silicon atoms per molecule, ranging from 2 up to 25.

[0158] Embodiment 2. A polymer composition comprising polymers of formulas:(P)n-X and P,wherein P is an uncoupled polymer prepared by living anionic polymerization comprising conjugated diene repeating units,Attorney Docket No.: DYN-10-PCTwherein (P)n-X is a polymer comprising n arms of polymer P coupled to X, wherein X is a coupling agent residue of an epoxy functionalized siloxane oligomer blend, andwherein the molecular weight distribution (MWD) of the polymeric composition comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value, andwherein the epoxy functionalized siloxane oligomer coupling comprises at least one alkyl ether functional group substituted by an epoxide per siloxane oligomer molecule, or at least one alkyl functional group substituted by an epoxide per silicon atom, alkoxy groups, and optionally saturated hydrocarbyl functional groups, andwherein the epoxy functionalized siloxane oligomer coupling comprises no more than one alkyl ether functional group substituted by an epoxide per silicon atom, or no more than one alkyl functional group substituted by an epoxide per silicon atom, andwherein the epoxy functionalized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and wherein the epoxy functionalized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules exhibiting a molecular weight distribution wherein the weight-average molecular weight ratio to the number-average molecular weight (Mw / Mn) greater-than or equal to 1.5, and wherein the epoxy functionalized siloxane oligomer has a dynamic viscosity from 600 to 2000 cP at 25 °C.

[0159] Embodiment 3. A polymer composition comprising:(P)n-X and,wherein Pis an uncoupled polymer prepared by living anionic polymerization and comprises conjugated diene repeating units,wherein n spans from 2 up to 11,wherein (P)n-X accounts for 30 to 95 wt.% of the polymer composition,Attorney Docket No.: DYN-10-PCTwherein P accounts for 5 to 70 wt.% of the polymer composition,wherein (P)n-X with n = 2 to 4 accounts for up to 50 wt.% of the polymer composition,Wherein (P)n-X with n = 5 to 7 accounts for up to 70 Wt.% of the polymer composition,wherein (P)n-X with n - 8 to 11 accounts for up to 20 wt.% of the polymer Composition,wherein X is a coupling agent residue of a functionalized siloxane oligomer blend, wherein the molecular weight distribution (MWD) of the polymeric composition comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value, andwherein the absolute weight average molecular weight of (P)n-X is 5 to 7 times greater than the absolute peak molecular weight of P, both absolute molecular weights being measured by GPC coupled to differential refractive index and light scattering detectors,wherein the polydispersity Mw_c / Mn_c of coupled fraction (P)n-X, being measured by GPC calibrated with polystyrene standards, is greater than 1.10, wherein the functionalized siloxane oligomer coupling agent is a blend that comprises linear, catenary, branched, cyclic, and crosslinked, alkoxy-substituted siloxane oligomers having at least one non-hydrolyzable olefinic or epoxy functional group per siloxane oligomer molecule and no more than one non- hydrolyzable olefinic or epoxy functional group per silicon atom.

[0160] Embodiment 4. A polymer composition comprising:(P)n-X and P,wherein P is an uncoupled polymer prepared by living anionic polymerization and comprises conjugated diene repeating units,wherein n spans from 2 up to 11,wherein (P)n-X accounts for 30 to 95 wt.% of the polymer composition, wherein P accounts for 5 to 70 wt.% of the polymer composition,Attorney Docket No.: DYN-10-PCTwherein (P)n-X with n - 2 to 4 accounts for up to 50 wt.% of the polymer composition,wherein (P)n-X with n - 5 to 7 accounts for up to 70 wt.% of the polymer composition,wherein (P)n-X with n = 8 to 11 accounts for up to 20 wt,% of the polymer composition,wherein X is a cou ling agent residue of a functionalized siloxane oligomer blend, wherein the molecular weight distribution (MWD) of the polymeric composition comprises at least two peaks, which correspond to the generalized formulas P and (P)n-X for a peak n value, wherein the MWD may further comprise at least one distinctive coupled polymer (P)n-X for n values other than the peak n value, andwherein the coupling agent of functionalized siloxane oligomer blend comprises:(i) vinyl and methoxy functional groups, or(ii) vinyl and ethoxy functional groups, or(iii) epoxy and methoxy functional groups, or(iy) epoxy and ethoxy functional groups, and wherein at least 50% mol of the silicon atoms in the siloxane molecules have 1 to 1 ratio of vinyl to alkoxy functional groups or 1 to 1 ratio of epoxy to alkoxy functional groups, andwherein the molar ratio of alkoxy functional grou s to polymeric anions or living polymer chains is between 0.05 and 3.0, andwherein the coupling agent residue X optionally comprises unreacted vinyl, alkoxy, or epoxy functional moieties, andwherein more than 50% mol of the silicon atoms in the siloxane molecules have not more than one coupled P polymer per silicon atom.

[0161] Embodiment 5. A polymer composition comprising polymers of formulas:(P)n-X and P,Wherein P is an uncoupled polymer prepared by living anionic polymerization comprising conjugated diene repeating units,wherein (P)n-X is a polymer comprising n arms of polymer P coupled to X,Attorney Docket No.: DYN-10-PCTwherein X is a residue of an olefinically functionalized siloxane oligomer co upli ng ag e nt, an dwherein the olefinically functionalized siloxane oligomer coupling agent comprises at least one nbn-hydrolyzable olefinic functional group per siloxane oligomer molecule, alkoxy groups, and optionally saturated hydrocarbyl functional groups, andwherein the olefinically functionalized siloxane oligomer coupling agent comprises no more than one non-hydrolyzable olefinic functional group per silicon atom, andwherein the Olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with at least two molecular topologies, selected from linear, branched, cyclic, and / or crosslinked structures, andwherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple numbers Of silicon atoms per molecule, ranging from 2 up to 25

[0162] Having described the invention above, various modifications of the techniques, procedures, materials, and equipment will be apparent to those skilled in the art. It is intended that all such variations within the sco e and spirit of the invention be included within the scope of the appended claims.

Claims

1. Attorney Docket No.: DYN-10-PCT2.CLAIMS3.What is claimed is:

1. A polymer composition comprising polymers of formulas:5.(P)n-X and P,6.wherein P is an uncoupled polymer prepared by living anionic polymerization comprising conjugate diene repeating units,7.wherein (P)n-X is a polymer comprising n arms of polymer P coupled to X,8.wherein X is a residue of an olefinically functionalized siloxane oligomer coupling agent, and9.wherein the olefinically functionalized siloxane oligomer coupling agent comprises at least one non-hydrolyzable olefinic functional group per siloxane oligomer molecule, alkoxy groups, and optionally saturated hydrocarbyl functional groups, and10.Wherein the olefinically functionalized siloxane oligomer coupling agent comprises no more than one non-hy rolyzable olefinic functional group per silicon atom, and11.wherein the olefinically functionalized siloxane oligomer is a blend of olefinically functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and12.Wherein the olefinically functionalized siloxane oligomer is a blend of olefinically f unctionalized siloxane oligomer molecules with multiple numbers of silicon atoms per molecule, ranging from 2 up to 25.

2. The polymer co position of claim 1,14.wherein X is a residue of an epoxy functionalized siloxane oligomer coupling agent, and15.Wherein the epoxy functionalized siloxane oligomer coupling comprises at least one alkyl Other functional group substituted by an epoxide per siloxane oligomer molecule, or at least one alkyl functional group substituted by an Attorney Docket No.: DYN-10-PCT16.epoxide per silicon atom, alkoxy groups, and optionally saturated hydrocarbyl functional groups, and17.wherein the epoxy functionalized siloxane oligomer coupling comprises no more than one alkyl ether functional group substituted by an epoxide per silicon atom, or no more than one alkyl functional group substituted by an e pox id e pe r s i I i co n ato, an d18.wherein the epoxy functionalized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules with multiple molecular topologies, ranging from linear, branched, cyclic, and / or crosslinked structures, and wherein the epoxy functionalized siloxane oligomer is a blend of epoxy functionalized siloxane oligomer molecules exhibiting a molecular weight distribution wherein the weight-average molecular weight ratio to the number¬ average molecular weight (Mw / Mn) is greater-than or equal to 1 „5, and wherein the epoxy functionalized siloxane oligomer has a dynamic viscosity from 600 to 2000 cP at 25 °C.

3. The polymer composition of claim 1,20.wherein the molecular weight distribution of the polymer composition comprises at least two peaks: the peak with lowest molecular weight encompasses P, and the rest of the molecular-weight distribution comprehends (P)n-X, and21.wherein the degree of coupling ranges from 2 to22.

23. when molecular weight distribution of the polymer composition is measured by G C calibrated With polystyrene standards, and24.wherein the polydispersity Mw__c / Mn_c of the coupled polymer (P)n-X is greater than 1.10, when measured by GPC calibrated with polystyrene standards.

4. The polymer composition according to claim 3, wherein the siloxane oligomer coupling agent is selected to achieve a precise degree of coupling (2-6) and Optimal branching, such that the resulting polymeric material comprises a controlled distribution of molecular topologiesr—including linear, branched, cyclic, and crosslinked Structures — thereby enabling tailored physical properties and processability.Attorney Docket No.: DYN-10-PCT5. The polymer composition of claim 3,27.wherein the conjugated diene repeating units are made from 1,3- buta diene mono r,28.wherein peak molecular weight of P is from 100 to 320 kg / mol as measured per GPC calibrated with polystyrene standards,29.wherein (P)n-X accounts for 30 to 95 wt.%,30.wherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, on a conjugated diene basis, and31.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 30 to 270 cP, and32.wherein Mooney ML1+4 viscosity of the polymer composition at 100 °G is from 30 to 110.

6. The p o ly mer co rn po sit I on of cl aim 1,34.wherein the olefinically functionalized siloxane oligomer coupling agent is a blend of molecules comprised by the general formula (I),35.l(R WR2)^iXA)iO)(^-z) / 2]a[(R3O)y(R4)wSi(B)(O)(3.y-v / y2]b (I)36.

37. wherein KR10)z(R2)xSi(A)(0)(3^-zy2], [(R^vSKOfe-^L and [(R3O)y(4wSi(B Oj<3-x-?)72] are structural elements that appear a, c, and b times, respectively, in any order throughout each siloxane oligomer molecule in the blend, and38.wherein a is an integer greater-than or equal to 1, and39.wherein b and c are integers greater-than or equal to 0, and Wherein a+b+c is greater-than or equal to 2, and40.wherein A corresponds to a linear, branched, or cyclic alkenyl- or cycloalkenyl-alkylene- functional group, having in each case 2 to 16 C atoms, and41.wherein R2independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 15 G atoms and42.wherein1independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 4 C atoms, or H, and43.wherein x is 1 or 0, z is 0, 1, or 2, and x+z is less-than or equal to 2, a d Attorney Docket No.: DYN-10-PCT44.wherein R3independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, or H, and45.wherein v is 0, 1, 2, or 3, and46.wherein B corresponds to an unsubstituted hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 160 atoms, and wherein R4independently at each occurrence is a linear branched or cyclic alkyl radical having 1 to 15 C atoms, and y is 6, 1, or 2, w is 0 or 1, and y+w is less-than or equ l to 2, and47.wherein each structural element is covalently bonded to one, two, three, or four other structural element(s) of the siloxane oligomer molecule, with same or different radicals and functional groups, through its O1 / 2 moieties, i.e. shared oxygen moieties, thereby giving place to a distribution of siloxane oligomers with different molecular topologies, ranging from linear, branched, cyclic, up to crosslinked molecular topologies.

7. The polymer composition of claim 6,49.wherein the olefimcally functionalized siloxane oligomer coupling agent comprises two or more siloxane oligomers selected from the group of: disiloxane, cyclotrisiloxane, linear trisiloxane, branched trisiloxane, cyclotetrasildxane, linear tetrasiloxane, branched tetrasiloxane, Gyclopentasiioxane, linear pentasiloxane, branched pentasiloxane, and / or cyclohexasiloxane, altogether in an amount greater-than or equal to 60%, on a % G PC area basis, and50.wherein all the siloxanes and cyclosildxanes selected have the functional groups arid radicals stated in formula I.

8. The polymer composition of claim 6Swherein the olefinically functionalized siloxane oligomer coupling agent comprises from 5 to 80 mol% of one or more structural uhits with formulas [(R1O)2Si(A)(Q)i / 2], [(R^fR^SifAJ i / sJ, [(R3O)2Si(B)(O)i KR3O)(R4I(B)(Q)i / 2j5and / or [(F?3O)3fei(O)i72j, and from 15 to 75 mpl% of one or more structural units with formulas [(R'OJSifAKO)^], [(R^S1(A)(O)a2], [(R3O)Si(B) (0)2 / 2], [(R4)Si(B)(O) and / or [(R3O)2Si(O, and from 0 to 35 mol% of one or more structural units with formulas [Si(A) (0)3 / 2], [Si (B) (0)32], and / or [(R3O)Si(O)3 / 2].Attorney Docket No.: DYN-10-PCT9. The polymer composition of claim 6,53.wherein the conjugated diene repeating units are made from 1,3- butadiene monomer,54.wherein peak molecular weight of P is from 240 to 260 kg / mol as measured per GPC calibrated with polystyrene standards,55.wherein (P)n-X accounts for 40 to 60 wt.%, and56.wherein the polydispersity of the coupled polymer (P -X, w_c / n_c, is greater than 1. O, when measured by GPC calibrated with polystyrene standards, andwherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, and57.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from T40 to 180 cP, and58.wherein Mooney viscosity ( L1+4) of the polymer composition at 00 °C is fro 46 to 66.59.10'. The polymer composition of claim 6,60.wherein the conjugated diene repeating units are made from 1,3- buta iens monomer, and61.wherein peak molecular weight of P is from 175 to 205 kg / mol as measured per GPC calibrated with polystyrene standards, and62.Wherein (P)B-X accounts for 40 to 60 wt. %, and63.wherein the polydispersity of the coupled polymer (P)n’X, Mw_c / Mn_c, is greater than 1.10, when measured by GPC calibrated with polystyrene standards, and64.wherein 1,2-vinyl content of the po lymer composition is from 6 to 7 wt.%, and65.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 70 to 1 TO cP, and66.Wherein Mooney viscosity (M L1 +4) of the polymer composition at 1Q0 °C is from 46 to 66.

11. The polymer composition of claim 6,68.wherein the conjugated diene repeating units are made from 1,3- buta iehe mono er, Attorney Docket No.: DYN-10-PCT69.wherein peak molecular weight of is from 100 to 160 kg / mol as measured per GPC calibrated with polystyrene standards,70.wherein (P)n-X accounts for 85 to 95 wt %,71.wherein the polydispersity of the coupled polymer (P)n-X, Mw__c / n__c, is greater than 1,10, when measured by GPC calibrated with polystyrene Standards, and72.wherein 1,2-vinyl content of the polymer composition is from 6 to 17 t.%,73.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 40 to 60 cP, and74.wherein Mooney Viscosity (ML1+4) of the polymer composition at 100 °C is from 50 to 65.

1. The polymer composition of claim 1, wherein (P)n-X and P further comprise up to 50 t.% of Vinyl aromatic repeating units, wherein Optionally P is a tapered block copolymer, and wwherein the vinyl aromatic blocks in (P)r X are bonded to X.

13. The polymer composition of claim 1, wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein P is a di-biock copolymer, and wwherein the vinyl aromatic blocks in (Pjn-X are bonded to X.

14. The polymer composition of claim 1, wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein P is a di-block copolymer, and wherein the conjugated diene blocks in (P)n-Xare bonded to X.

15. The polymer co position of claim 14, wherein conjugated diene repeating units are saturated by hydrogenation, and wherein vinyl aromatic repeating units are left intact.

16. The polymer composition of claim 2,80.wherein the conjugated diene repeating units are made from 1,3- butadiene monomer,81.wherein the molecular weight distribution of the polymer composition comprises at least two peaks: the peak with lowest molecular weight encompasses P, and the rest of the molecular weight distribution comprehends (P)n-, and Attorney Docket No.: DYN-10-PCT82.wherein peak molecular weight of P is from 100 to 320 kg / mol as measured per GPC calibrated with polystyrene standards,83.wherein (P)n-X accounts for 30 to 95 wt. %,84.wherein the degree of coupling is from 3 to 5, when molecular weight distribution of the polymer composition is measured by GPC calibrated with po lySty re ne Standards, and85.wherein the polydispersity Mw_c / Mn_c of the coupled polymer (P)n-X is greater than 1.10, when measured by GPC calibrated with polystyrene standards,86.wherein 1,2-vinyl content of the polymer composition is from 6 to 17 wt.%, on a conjugated diene basis, and87.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 30 to 270 cP, and88.wherein Mooney viscosity (ML1 +4) of the polymer composition at 100 °C is from 30 to 110.

17. The polymer composition of claim 2,90.wherein epoxy functionalized siloxane oligomer is a blend of molecules comprised by the general formula (II),91.[(R1O)zSi(E)(O (3t- z) / 2]a [(R^vSitOJ^lc [(R3O)y(R3)wSi(O)^y-wy2]b (II) wherein [(R1O)zSi(E)(O)(3-z / 2], [(R3O)vSi(O)(4-v) / 2], and [(R30)y(3)wSi(O)(3-y-wV2] are struct ral elements that appear a, c, and b times, respectively, throughout each siloxane oligomer molecule in the blend, in any order, and92.wherein a is an integer greater-then or equal to 1, and b is an integer greateHhan or equal to 0, and c is an integer greater-than or equal to 0, and a+b+c is greater-than or equal to 2, and93.Wherein E corresponds, independently at each occurrence, to linear or branched alkyl ether functional groups of 3 to 11 C atoms, with each functional group substituted by an epoxide, or to linear, or cyclic alkyl functional groups of 2 to 11 C atoms, with each functional group substituted by an epoxide, and wherein R1independently at each occurrence is a linear, branched, or cyclic alkyrradical having 1 to 4 C atoms, or H, and z is 0, 1, or 2, and Attorney Docket No.: DYN-10-PCT94.wherein R3independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 4 C atoms, or H, and v is 0, 1, 2, or 3, and wherein y is 0, 1, or 2, and w is 0 Or 1, and y+w is less-than or equal to 2, and95.wherein each structural element is bonded to one, two, three, or four other structural eiement(s) of the siloxane oligomer molecule, with same or different radicals and functional groups, through its Oi® moieties, i.e. shared oxygen moieties, thereby giving place to a distribution of siloxane oligomers with different molecular topologies, ranging from linear, branched, cyclic, up to crosslinked molecular topologies.

18. The polymer composition of claim 17,97.wherein the conjugated diene repeating units are made from 1,3- butadiene monomer,98.wherein the molecular weight distribution of the polymer composition comprises at least two peaks: the peak with lowest molecular weight encompasses P, and the rest of the molecular weight distribution comprehe nds (P)n-X, and99.wherein peak molecular weight of P is from 100 to 320 kg / mol as measured per G PC ca librate d with polysty re ne sta nda rds,100.Wherein (P)fl- accounts for 30 to 95 wt.%,101.wherein the degree of coupling is from 3 to 5, when molecular weight distribution of the polymer composition is measured by GPC calibrated with polystyrene standards, and102.wherein the polydispersity Mw__c / Mn_c of the coupled polymer (P)n-X is greater than 1.10, when measured by GPC calibrated with polystyrene standards.103.wherein 1,2-vinyl content Of the polymer composition is from 6 to 17 wt.%, on a conjugated diene basis, and104.wherein styrene solution viscosity of the polymer composition at 5 wt.% and 25 °C is from 30 to 270 cP, and105.wherein Mooney viscosity (ML1+4) of the polymer composition at 100 °C is from 30 to 110. Attorney Docket No.: DYN-10-PCT19. The polymer composition of claim 2,107.wherein (P)n-X and P further comprise Up to 50 wt.% of vinyl aromatic repeating units:, wherein optionally P is a tapered block copolymer, and Wwherein the vinyl aromatic blocks in (P)n-X are bonded to X.

20. T he p o |y me r co m po s iti on of c la i m 2,109.wherein (P)n-X and P further comprise up to 50 wt.% of vinyl aromatic repeating units, wherein P is a dublock copolymer, and wwherein the vinyl aromatic blocks in (P)n-X are bonded to X.

21. The polymer composition of claim 2,111.wherein (P)rrX and P further comprise Up to 50 wt.% of vinyl aromatic repeating units, wherein P is a deblock copolymer, and wherein the conjugated diene blocks in (P)n-X are bonded to X,22. The polymer composition of claim 21, wherein conjugated diene repeating units are saturated by hydrogenation, and where in vinyl aro rnatic repeating units are left intact.

23. A process to produce a polymer composition comprising the steps of:114.(i) polymerizing conjugated diene monomer in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions;115.(ii) reacting part of the polymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend;116.(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition of claim 524. A process to produce a polymer composition comprising the steps of:118.(i) copolymerizing conjugated diene and vinyl aromatic monomers in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anions;119.(ii) reacting part of the polymer anions with a coupling agent of an olefinicaHy functionalized siloxane oligomer blend;120.(iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition of claim 12. Attorney Docket No.: DYN-10-PCT25. The process of clai m 24 comprising a second charge of vinyl aromatic monomer after co olymerization of an initial charge of conjugated diene monomer and vinyl aromatic monomer.

26. A process to produce a polymer composition comprising the ste s of;123.(i) polymerizing conjugated diene monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;124.(ii) block polymerizing vinyl aromatic monomer with the foregoing polymer anions;125.(iij) reacting part of the block copolymer anidris with a coupling agent of an olefinically functionalized siloxane oligomer blend;126.(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,127.(v) recovering the polymer composition of claim 13.

27. The process of claim 26, Wherein vinyl aromatic monomer is fed to the reactor after polymerization of more than 90% of the conjugated diene monomer.

28. A process to produce a polymer composition comprising the steps of:129.(i) polymerizing vinyl aromatic monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;130.(ii) block polymerizing conjugated diene monomer with the foregoing polymer anions;131.(iii) reacting part Of the block copolymer anions with a coupling agent of an olefi ically functionalized siloxane oligomer blend;132.(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,133.( ) recovering the polymer composition of claim 14.

29. A process to produce a polymer composition comprising the ste s Of:135.(i) polymerizing vinyl aromatic monomer in the presence of organolithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions; Attorney Docket No.: DYN-10-PCT136.(ii) block polymerizing conjugated diene monomer with the foregoing polymer anions;137.(iii) reacting part of the block copolymer anions with a coupling agent of an olefinically functionalized siloxane oligomer blend;138.(iv) deactivating the remaining block copolymer anions with a polar proton donor;139.(v): hydrogenating the conjugated diene unsaturations; and,140.(vi) recovering the polymer composition of claim 15.

30. The process of a ny one of the claims 23 to 29,142.wherein the olefinically functionalized siloxane oligo rner coupling agent is a blend of molecules with the general formula (I), [(R1O)z(R2)xSi(A)(O)^x-zv2]a[(R?0) Si(0)(4-v, / 2]c [(R3O)y(R Si(B)(Ox^y^) / 2]b (I) wherein KR1O)z(R2)xSi(A)(O)<3-x-zy2], [(R^vSii'Ojt+vya], and [(R3O)y(R4)wSi(BJ(Px3-y-wy2] are structural elements that appear a, c, and b times, respectively, in any order throughout each siloxane oligomer molecule in the blend, and143.wherein a is an integer greater-than or equal to 1, and144.wherein b and c are integers greater-than or equal to 0, and wherein a+b+c is greater-thari or equal to 2, and145.wherein A corresponds to a linear, branched, or cyclic alkenyl- or cycloalkenyl-alkylene- functional group, having in each case 2 to 16 C atoms, and146.wherein R2independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 15 C atoms, and147.wherein R1independently at each occurrence is a linear, branched, or cyclic alkyl radical having 1 to 4 C atoms, or H, and148.wherein x is 1 of 0, z is 0, 1, or 2, arid x+z is less-thah or eq u a l to 2, and wherein R3independently at each occurrence is a linear, branched or cyclic alkyl radical having 1 to 4 G atoms, or H, and149.wherein v is 0, 1, 2, or 3, and150.wherein B corresponds to an unsubstituted hydrocarbon radical arid is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms, and Attorney Docket No.: DYN-10-PCT151.wherein R4independently at each occurrence is a linear branched or cyclic alkyl radical having 1 to 15 C atoms, and152.wherein y is 0, 1, or 2, w is 0 or 1, a nd y+w is less-tha n or equal to 2, and153.wherein each structural element is covalently bonded to one, two, three, or four other structural elemerit(s) of the siloxane oligomer molecule, with sa me or different radicals and functional groups, through its O1 / 2 moieties, i.e. shared oxygen moieties, thereby giving place to a distribution of siloxane oligomers with different molecular topologies, ranging from linear, branched, cyclic, up to crosslinked molecular topologies.

31. A process to produce a polymer composition comprising the steps of:155.(!) polymerizing conjugated diene monomer in the presence of organolithium initiator and hydrocarbon solvent, and optionally polar modifier, to produce polymer anibhs;156.(ii) reacting part of the polymer anions with a coupling agent of an epoxy functionalized siloxane oligomer blend;157.(iii) deactivating the remaining polymer anions with a polar proton dbnor; and, (iv) recovering the polymer composition of claim 16.

32. A process to produce a polymer composition comprising the ste s of:159.(I) copolymerizing conjugated diene and vinyl aromatic monomers in the prese nee of organolithium initiator and hydrocarbon solvent, and 0 ptionally polar modifier, to produce polymer anions;160.(ii) reacting part of the polymer anions with a coupling agent of ah epoxy functionalized siloxane oligomer blend;161.(Iii) deactivating the remaining polymer anions with a polar proton donor; and, (iv) recovering the polymer composition of claim 19.

33. The process of clai m 32 comprising a second charge of viny l aromatic monomer after copolymerization of an initial charge of conjugated diene monomer and vinyl aromatic monomer,34. A process to produce a polymer composition comprising the ste s of:Attorney Docket No.: DYN-10-PCT164.(i) polymerizing conjugated diene monomer i the presence of organoiithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;165.(ii) block polymerizing vinyl aromatic monomer with the foregoing polymer anions;166.(iii) reacting part of the block copolymer anions with a coupling agent of an epoxy functionalized siloxane oligomer blend;167.(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,168.(v) recovering the polymer composition of claim 20.

35. The process of claim 34, wherein vinyl aromatic monomer is fed to the reactor after polymerization of more than 90% of the conjugated diene monomer. 36: A process to produce a polymer composition comprising the steps of:170.(i) polymerizing vinyl aromatic monomer in the presence of organoiithium initiator, polar modifier, arid hydrocarbon solvent to produce polymer anions;171.(ii) block polymerizing co njugated d ie ne mo nomer with the foregoi ng polyme r anions;172.(iii) reacting part of the block copolymer anions with a coupling agent of ah epoxy functionalized siloxane oligomer blend;173.(iv) deactivating the remaining block copolymer anions with a polar proton donor; and,174.V) recovering the polymer composition of claim 21.

37. A process to produce a polymer composition comprising the steps of:176.(i) polymerizing vinyl aromatic monomer in the presence of organoiithium initiator, polar modifier, and hydrocarbon solvent to produce polymer anions;177.(ii) block polymerizing conjugated diene monomer with the foregoing polymer anions;178.(iii) reacting part of the block copolymer anions with a coupling agent of an epoxy functionalized siloxane oligomer blend; Attorney Docket No.: DYN-10-PCT179.(iv) deactivating the remaining block copolymer anions with a polar proton donor;180.(v) hydrogenating the conjugated diene unsaturations; and181.(vi) recovering the polymer composition of claim 22.

38. The process of any one of the claims 23 to 37, wherein the molar ratio of alkoxide groups in the coupli ng agent of functionalized siloxane oligomer ble nd to the polymer anions is between 0,05 and 3039. The process of any one of claims 23 to 37, wherein the molar ratio of alkoxide groups in the coupling agent of functionalized siloxane oligomer blend to the polymer anions is between 0.07 and 0.5.

40. A rubber toughened plastic composition comprising:185.(i) a continuous vitreous polymer matrix phase comprising styrene repeating units, and optionally comprising randomized acrylonitrile repeating units, and186.(ii) the polymer composition of any one of claims 1 to 22 in the rubber toughened plastic composition from 3.5 to 17 wt.%, and187.(iii) dispersed rubbery particles, with size in the range from about 0.1 microns to about 10 microns, comprising the polymer composition of any one of claims 1 to 22 which has been crosslinked, grafted, and physically occluded with the same kind of polymer as the matrix phase.

41. A modified plastic composition comprising the polymer composition of any one of claims 1 to 22 and a plastic.189.>42. A modified asphalt composition comprising the polyrher co position of any one of claims 1 to 22 and an asphalt,43. An adhesive composition comprising the polymer composition of any one of claims 1 to 22.

44. A hot melt adhesive co position comprising the polymer composition of any one of claims i to 2 and a tackif ing resin.

45. Asealant composition comprising the polymer composition of any one of claims 1 to 22.

46. Elastic films, fibers or hon-woven materials comprising the polymer composition of any one of clai s i to 22.Attorney Docket No.: DYN-10-PCT47. A compounded material comprising the polymer composition of any one of claims 1 to 22 and a polyolefin.

48. A crosslinked rubber composition comprising the polymer composition of any one of claims 1 to 22.

49. A microcelliilar foamed composition comprising the polymer composition of any one of claims 1 to 22.

50. An oil gel composition comprising the poly mer composition of any one of cia ims 1 to 22.

51. A battery cell binder composition comprising the polymer composition of any one of clai s 1 to 22.

52. A thermoplastic elastomer composition comprising the polymer composition of any one of claims 1 to 22 and a thermoplastic resin.

53. The thermoplastic elastomer composition of claim 52, wherein the thermoplastic resin is selected from a group consisting of polyolefins, polystyrene, and their recycled equivalents, including post-consumer and. / or post-industrial recycling materials.

54. The thermoplastic elastomer composition of claim 53- wherein the polyolefin is selected from a group consisting of polypropylene, polyethylene, ethylene / alpha-olefih copolymer, ethylene / propylene copolymer, ethylene / propylene / diene terpolymer, propylene / 1 -butene copolymer, propylene / ethylene / alpha -olefin terpoly er, impact propylene / ethyle ne copolymer, or a mixture of the foregoing, and their recycled equivalents, including post-consumer and / or post-industrial recycling materials.

55. A thermoplastic elastomer composition comprising the polymer co position of any one of claims 1 to 22 and a polyolefin.

56. The thermoplastic elastomer composition of claim 55, wherein the polyolefin is a polypro ylene.

57. The thermoplastic elastomer composition of Claim 55, wherein the polyolefin is a blend of a polypropylene and a polyethylene, or their recycled equivalents, including post-consumer and / or post-industrial recycling materials.Attorney Docket No.: DYN-10-PCT58. A filrn comprising the thermo plastic elastomer composition of any one of clai ms 52 to 57.

59. A fiber comprising the thermoplastic e lastomer co mposition of any one of cla ims 52 to 57,208.6Q. A non-woven compound comprising the thermoplastic elastomer composition of any one of claims 52 and 57.

61. A polypropylene composition with oxygen-absorbing capability comprising the thermoplastic elastomer composition of any one of claims 52 and 57.

62. A thermoplastic elastomer composition comprising the polymer composition of any one Of claims 1 to 22 and a polystyrene.

63. The thermoplastic elastomer composition of claim 52, wherein the thermoplastic resin is a blend of a polystyrene and a r ecyc led polystyrene.

64. An article of manufacture comprising the composition of any one of claims 48 to 6365. A radiation curable hot melt adhesive composition comprising the polymer composition of any one of claims 1 to 22 and a tackifying resin.

66. A hot melt pressure sensitive adhesive composition comprising the polymer composition of any one of claims 1 to 2 and a tackifying resin.

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