Hydrogenated polybutadiene polymers and rubber compositions incorporating same - Patents.com

Abstract

Embodiments of the present disclosure are directed to polymers, including hydrogenated 1,4-polybutadiene having a cis content of about 50% to about 96%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%. The hydrogenated 1,4-polybutadiene has a degree of hydrogenation of about 3% to about 50%.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to hydrogenated polybutadiene polymers and, in particular, to partially hydrogenated high cis 1,4-polybutadiene rubber compositions that provide good tire performance at both low and high temperatures as well as being equally suitable for non-tire applications. [Background technology]

[0002] High cis polybutadienes (e.g., polymers with cis-1,4 bond content of 94% or more) are commonly used in tire manufacturing due to their excellent mechanical and viscoelastic properties. However, at low temperatures below 0°C, these compositions are prone to crystallization. Crystallization can make tires stiffer at these lower temperatures, reducing traction during snowy and icy conditions. These compositions can have crystallites with peak melting temperatures of 100°C or higher. Summary of the Invention [Problem to be solved by the invention]

[0003] Thus, there is a continuing need for improved 1,4-polybutadiene rubber compositions that resist the formation of crystals of cis-1,4 butadiene units at low crystallization temperatures and produce high melt crystallites.

[0004] SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure are directed to partially hydrogenated high cis 1,4-polybutadiene compositions that provide good tire performance at both low and high temperatures as well as non-tire applications.

[0005] According to one embodiment, a polymer is provided. The polymer comprises a partially hydrogenated 1,4-polybutadiene having a cis content of about 50% to about 96%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%. The partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of about 3% to about 50%.

[0006] According to another embodiment, a method is provided that includes polymerizing a solution containing 1,3-butadiene to obtain 1,4-polybutadiene having a cis content of about 50% to about 99.5%, a vinyl content of about 0.1% to about 1%, and a trans content of about 1% to about 10%, where the polymerization is catalyzed with a lanthanide metal complex or a nickel metal complex, and hydrogenating the 1,4-polybutadiene to form a hydrogenated 1,4-polybutadiene having a degree of hydrogenation of about 3% to about 50%, where the hydrogenation is catalyzed with a metal catalyst.

[0007] Additional features and advantages of the embodiments described herein are set forth in the Detailed Description below, and, in part, will be readily apparent to those of ordinary skill in the art from the specification or will be recognized by the practice of the embodiments described herein, including the Detailed Description and Claims below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Embodiments of the present disclosure are directed to polymers. The polymer may include partially hydrogenated 1,4-polybutadiene having a cis content of about 50% to about 96%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%. The partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 3% to about 50%. In other embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 5% to about 50%.

[0009] This disclosure should not be construed as being limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the subject matter to those skilled in the art.

[0010] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in the present disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0011] Ranges may be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0012] Unless expressly stated otherwise, it is never intended that any method described herein be interpreted as requiring that its steps be performed in a particular order, or as requiring a particular orientation of any physical entity. Thus, where a method claim does not actually recite an order that its steps should be followed, or where a claim relating to any physical entity does not actually recite an order or orientation for individual components, or where it is specifically stated otherwise in the claim or specification that the steps are to be limited to a particular order, or where no particular order or orientation for the components of the physical entity is recited, no order or orientation is ever intended to be inferred in any respect. This applies to any possible implicit criteria for interpretation, including questions of logic regarding the arrangement of steps, operational flow, order of components, or orientation of components; plain meaning derived from grammatical constructions or punctuation; and the number or type of embodiments described herein.

[0013] As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly dictates otherwise. Thus, for example, reference to "a" element includes aspects having two or more such elements unless the context clearly dictates otherwise.

[0014] As used herein, the term "1,4-polybutadiene" refers to the polymer before it is blended with other rubber additives to produce rubber compositions used in tire and non-tire applications.

[0015] As used herein, the term "1,4-polybutadiene rubber composition" or "rubber composition" refers to a polymer (e.g., 1,4-polybutadiene) and additional fillers and additives blended with the polymer for use in tire and non-tire applications.

[0016] As used herein, the term "cis content" refers to the percentage of cis-1,4 bonds in 1,4-polybutadiene.

[0017] As used herein, the term "high cis" refers to a cis content of 50% or greater in 1,4-polybutadiene.

[0018] As used herein, the term "vinyl content" refers to the percentage of vinyl-1,2 bonds in 1,4-polybutadiene.

[0019] The term "trans content" refers to the percentage of trans-1,4 bonds in 1,4-polybutadiene.

[0020] As described herein, the "number average molecular weight Mn" and the "weight average molecular weight Mw" are determined by gel permeation chromatography.

[0021] As used herein, the "cis content", "vinyl content", "trans content" and "degree of hydrogenation" are determined in tetrachloroethane-d2 at 80° C. 1 Determined by H-nuclear magnetic resonance spectroscopy.

[0022] As described herein, "degree of hydrogenation" refers to the percentage of double bonds of a polymer that are broken by hydrogen added to the chain.

[0023] As used herein, the melting temperature T m " refers to the peak maximum of the melting endotherm.

[0024] As used herein, the melting temperature T m ", "Enthalpy of fusion ΔH m " and "glass transition temperature T g " is measured by differential scanning calorimetry, as described in more detail in the Examples section.

[0025] As used herein, the term "phr" refers to parts by weight of a specified component per 100 parts of rubber.

[0026] As used herein, the term "natural rubber" refers to naturally occurring rubber, such as that which can be harvested from sources such as Hevea rubber trees, and from non-Hevea sources (e.g., guayule and dandelion, such as TKS). In other words, the term "natural rubber" should be interpreted to exclude synthetic polyisoprene.

[0027] As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, the term is used to indicate a polymer made from isoprene monomers and should not be construed to include naturally occurring rubber (e.g., Hevea natural rubber, natural rubber of guayule origin, or natural rubber of dandelion origin). However, the term polyisoprene should be construed to include polyisoprene made from natural sources of isoprene monomers.

[0028] As discussed herein above, high cis 1,4-polybutadiene compositions may provide desirable mechanical properties, but may not be equally suitable for both low and high temperature tire and non-tire applications. In particular, at low temperatures below 0°C, these compositions are prone to crystallization. Crystallization may stiffen tires at these lower temperatures, reducing traction during snow and ice conditions. These compositions may have crystallites with peak melting temperatures of 100°C or higher.

[0029] Disclosed herein is a rubber composition that alleviates the aforementioned problems. Specifically, the rubber composition disclosed herein comprises a partially hydrogenated high cis 1,4-polybutadiene. As described above, crystallization of cis-1,4 butadiene units at low temperatures (e.g., 0°C or lower) is undesirable because it can harden the tire. Therefore, reduced formation of crystallites formed from cis-1,4 butadiene units is desirable. High-temperature melt crystallites (e.g., Tm2 of 100°C or higher and 140°C or lower) are desirable because they provide improved tear and cut resistance. With the partially hydrogenated high cis 1,4-polybutadiene disclosed herein, reduced crystallization of cis-1,4 butadiene units at low temperatures and increased high-temperature melt crystallites are achieved.

[0030] The partially hydrogenated 1,4-polybutadiene disclosed herein has a cis content of from about 50% to about 96%, a vinyl content of from about 0% to about 1%, and a trans content of from about 1% to about 10%.

[0031] In embodiments, the partially hydrogenated 1,4-polybutadiene can be a partially hydrogenated high cis 1,4-polybutadiene. In embodiments, the partially hydrogenated 1,4-polybutadiene can have a cis content of about 50% or more, about 55% or more, about 60% or more, or even about 65% or more. In embodiments, the partially hydrogenated 1,4-polybutadiene can have a cis content of about 96% or less, about 95% or less, 90% or less, 85% or less, or even 80% or less. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a cis content of 50% to 96%, 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%, 55% to 96%, 55% to 95%, 55% to 90%, 55% to 85%, 55% to 80%, 60% to 96%, 60% to 95%, 60% to 90%, 60% to 85%, 60% to 80%, 65% to 96%, 65% to 95%, 65% to 90%, 65% to 85%, or even 65% to 80%, or any subrange formed from any of these endpoints.

[0032] In embodiments, the partially hydrogenated 1,4-polybutadiene may have a vinyl content of about 0% or more, about 0.1% or more, or even about 0.25% or more. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a vinyl content of about 1% or less, about 0.75% or less, or even about 0.25% or less. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a vinyl content of about 0% to about 1%, about 0% to about 0.75%, about 0% to about 0.5%, about 0.1% to about 1%, about 0.1% to about 0.75%, about 0.1% to about 0.5%, about 0.25% to about 1%, about 0.25% to about 0.75%, or even about 0.25% to about 0.5%, or any subrange formed from any of these endpoints.

[0033] In embodiments, the partially hydrogenated 1,4-polybutadiene may have a trans content of about 1% or more, about 2% or more, about 3% or more, or even about 4% or more. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a trans content of about 10% or less, about 9% or less, or even about 8% or less. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a trans content of about 1% to about 10%, about 1% to about 9%, about 1% to about 8%, about 2% to about 10%, about 2% to about 9%, about 2% to about 8%, about 3% to about 10%, about 3% to about 9%, about 3% to about 8%, about 4% to about 10%, about 4% to about 9%, or even about 4% to about 8%, or any subrange formed from any of these endpoints.

[0034] Without being bound by theory, it is believed that hydrogenation, even at a relatively low degree of hydrogenation (e.g., 10% or less), reduces crystallization of cis-1,4 butadiene units at lower temperatures, such as below 0° C. As a result, the partially hydrogenated 1,4-polybutadiene rubber composition of the present invention provides improved low temperature performance, which in turn enhances performance on snow and ice when incorporated into winter tire tread compounds.

[0035] Without being bound by theory, it is believed that as the degree of hydrogenation increases (e.g., greater than 10%), the high temperature melt crystallites (e.g., T above 100° C. and below 140° C.) become more readily disintegrated. m As a result, the partially hydrogenated 1,4-polybutadiene rubber composition of the present invention provides improved high temperature performance, which in turn provides improved tear and cut resistance when incorporated into tire components such as sidewalls and treads.

[0036] The partially hydrogenated 1,4-polybutadiene disclosed herein may have a degree of hydrogenation of about 5% to about 50%. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 5% or more, about 10% or more, about 15% or more, about 20% or more, about 25% or more, or even about 30% or more. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 50% or less, about 45% or less, or even about 40% or less. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 5% to about 50%, about 5% to about 45%, about 5% to about 40%, about 10% to about 50%, about 10% to about 45%, about 10% to about 40%, about 15% to about 50%, about 15% to about 45%, about 15% to about 40%, about 20% to about 50%, about 20% to about 45%, about 20% to about 40%, about 25% to about 50%, about 25% to about 45%, about 25% to about 40%, or even about 30% to about 50%, about 30% to about 45%, or even about 30% to about 40%, or any subrange formed from any of these endpoints.

[0037] The partially hydrogenated 1,4-polybutadiene disclosed herein may have a degree of hydrogenation of about 3% to about 50%. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 3% or more, or even about 5% or more. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 50% or less, about 40% or less, 30% or less, 20% or less, or even about 10% or less. In embodiments, the partially hydrogenated 1,4-polybutadiene may have a degree of hydrogenation of about 3% to about 50%, about 3% to about 40%, about 3% to about 30%, about 3% to about 20%, about 3% to about 10%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, or even about 5% to about 10%, or any subrange formed from any of these endpoints. In embodiments, relatively low hydrogenation (e.g., from about 3% to about 20%, or alternatively from about 3% to about 15%, or alternatively from about 3% to about 10%) results in improved complex shear modulus (G * ) and torque Lamborn abradibility.

[0038] Hydrogenation of 1,4-polybutadiene reduces the relatively low glass transition temperature T g (e.g., about -105°C) may not affect the relatively low glass transition temperature T g In an embodiment, the partially hydrogenated 1,4-polybutadiene has a glass transition temperature T of about -115°C to about -95°C. g In embodiments, the partially hydrogenated 1,4-polybutadiene may have a glass transition temperature T of about -115°C or greater, about -113°C or greater, about -110°C or greater, or even about -107°C or greater. g In embodiments, the partially hydrogenated 1,4-polybutadiene may have a glass transition temperature T of about -95°C or less, about -97°C or less, about -100°C or less, or even about -103°C or less. g In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a molecular weight of about -115°C to about -95°C, about -115°C to about -97°C, about -115°C to about -100°C, about -115°C to about -103°C, about -113°C to about -95°C, about -113°C to about -97°C, about -113°C to about -100°C, about -113°C to about -103°C, about -110°C to about -9 5°C, about -110°C to about -97°C, about -110°C to about -100°C, about -110°C to about -103°C, about -107°C to about -95°C, about -107°C to about -97°C, about -107°C to about -100°C, or further about -107°C to about -103°C, or any subrange formed from any of these end points g may have:

[0039] In an embodiment, the partially hydrogenated 1,4-polybutadiene has a first melting temperature T m1 and the second melting temperature T m2 The first melting temperature T m1 corresponds to the melting temperature of the crystallites derived from the cis-1,4 segments of the partially hydrogenated 1,4-polybutadiene. The second melting temperature T m2 corresponds to the melting temperature of the crystallites derived from the hydrogenated segments of the partially hydrogenated 1,4-polybutadiene.

[0040] In an embodiment, the partially hydrogenated 1,4-polybutadiene has a first melting temperature T m1 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a first melting temperature T of about -30°C or more, about -25°C or more, or even about -20°C or more. m1 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a first melting temperature T m1 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a first melting temperature T of about -30°C to about 0°C, about -30°C to about -5°C, about -30°C to about -10°C, about -25°C to about 0°C, about -25°C to about -5°C, about -25°C to about -10°C, about -20°C to about 0°C, about -20°C to about -5°C, or even about -20°C to about -10°C, or any subrange formed from any of these endpoints. m1 may have:

[0041] In an embodiment, the partially hydrogenated 1,4-polybutadiene has a second melting temperature T m2 In embodiments, the partially hydrogenated 1,4-polybutadiene may have a second melting temperature T of about 100° C. or more, about 105° C. or more, or even about 110° C. or more. m2 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a second melting temperature T m2 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a second melting temperature T of about 100° C. to about 140° C., about 100° C. to about 135° C., about 100° C. to about 130° C., about 105° C. to about 140° C., about 105° C. to about 135° C., about 105° C. to about 130° C., about 110° C. to about 140° C., about 110° C. to about 135° C., or even about 110° C. to about 130° C., or any subrange formed from any of these endpoints. m2 may have:

[0042] As described hereinabove, partial hydrogenation of the high cis 1,4-polybutadiene in the rubber composition provides resistance to the formation of low melting crystallites. Without being bound by theory, the first melting temperature Tm1 The lower melting enthalpy (e.g., 50 J / g or less) of the partially hydrogenated 1,4-polybutadiene polymer at (i.e., the melting temperature of crystallites derived from cis-1,4 segments) is a property that correlates to reduced cis-1,4 segment crystallization in tire applications. In an embodiment, the hydrogenated 1,4-polybutadiene has a first melting enthalpy ΔH of about 3 J / g to about 50 J / g when measured at a temperature of about -30°C to about 0°C. m1 In further embodiments, the hydrogenated 1,4-polybutadiene may have a first enthalpy of fusion ΔH of about 3 J / g or more, about 5 J / g or more, about 10 J / g or more, about 15 J / g or more, or even about 20 J / g or more, when measured at a temperature of about −30° C. to about 0° C. m1 In embodiments, the hydrogenated 1,4-polybutadiene may have a first enthalpy of fusion ΔH of about 50 J / g or less, about 45 J / g or less, or even about 40 J / g or less, when measured at a temperature of about −30° C. to about 0° C. m1 In an embodiment, the hydrogenated 1,4-polybutadiene may have a viscosity of from about 3 J / g to about 50 J / g, from about 3 J / g to about 45 J / g, from about 5 J / g to about 40 J / g, from about 5 J / g to about 50 J / g, from about 5 J / g to about 45 J / g, from about 5 J / g to about 40 J / g, from about 10 J / g to about 50 J / g, from about 10 J / g to about 45 J / g, a first enthalpy of fusion ΔH of about 10 J / g to about 40 J / g, about 15 J / g to about 50 J / g, about 15 J / g to about 45 J / g, about 15 J / g to about 40 J / g, about 20 J / g to about 50 J / g, about 20 J / g to about 45 J / g, or even about 20 J / g to about 40 J / g, or any subrange formed from any of these endpoints; m1 may have:

[0043] In another embodiment, the hydrogenated 1,4-polybutadiene has a first enthalpy of fusion ΔH of about 0 J / g to about 45 J / g when measured at a temperature of about −30° C. to about 0° C. m1 In further embodiments, the hydrogenated 1,4-polybutadiene may have a first enthalpy of fusion ΔH of about 0 J / g or more, about 3 J / g or more, about 5 J / g or more, or even about 10 J / g or more, when measured at a temperature of about −30° C. to about 0° C. m1In embodiments, the hydrogenated 1,4-polybutadiene may have a first enthalpy of fusion ΔH of about 45 J / g or less, about 35 J / g or less, about 25 J / g or less, or even 15 J / g or less, when measured at a temperature of about −30° C. to about 0° C. m1 In an embodiment, the hydrogenated 1,4-polybutadiene may have a molecular weight of from about 0 J / g to about 45 J / g, from about 0 J / g to about 35 J / g, from about 0 J / g to about 25 J / g, from about 0 J / g to about 15 J / g, from about 3 J / g to about 45 J / g, from about 3 J / g to about 35 J / g, from about 3 J / g to about 25 J / g, from about 3 J / g to about 15 J / g, from about 5 J / g to about 2 ... a first enthalpy of fusion ΔH of about 45 J / g, about 5 J / g to about 35 J / g, about 5 J / g to about 25 J / g, about 5 J / g to about 15 J / g, about 10 J / g to about 45 J / g, about 10 J / g to about 35 J / g, about 10 J / g to about 25 J / g, or even about 10 J / g to about 15 J / g, or any subrange formed from any of these endpoints; m1 may have:

[0044] As described herein above, the inclusion of hydrogenated 1,4-polybutadiene in the rubber composition provides for the formation of crystallites that melt at high temperatures. As the degree of hydrogenation of the 1,4-polybutadiene increases, the 1,4-butadiene segments are reduced and new saturated chain segments are generated. Without being bound by theory, the second melting temperature T m2 The higher melting enthalpy (e.g., 0.5 J / g or more) of the partially hydrogenated 1,4-polybutadiene polymer at (i.e., the melting temperature associated with the hydrogenated segments) is a property that correlates with the increased crystallinity associated with the hydrogenated segments. In embodiments, the partially hydrogenated 1,4-polybutadiene has a second melting enthalpy ΔH of about 0.5 J / g to about 20 J / g when measured at a temperature up to about 140° C. m2 In embodiments, the partially hydrogenated 1,4-polybutadiene may have a second enthalpy of fusion ΔH of about 0.5 J / g or more, about 1 J / g or more, about 5 J / g or more, or even 10 J / g or more, when measured at a temperature up to about 140° C. m2In embodiments, the partially hydrogenated 1,4-polybutadiene may have a second enthalpy of fusion ΔH of about 20 J / g or less, about 18 J / g or less, about 16 J / g or less, or even about 14 J / g or less, when measured at a temperature up to about 140° C. m2 In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a molecular weight of from about 0.5 J / g to about 20 J / g, from about 0.5 J / g to about 18 J / g, from about 0.5 J / g to about 16 J / g, from about 0.5 J / g to about 14 J / g, from about 1 J / g to about 20 J / g, from about 1 J / g to about 18 J / g, from about 1 J / g to about 16 J / g, from about 1 J / g to about 14 J / g, from about 5 ...6 J / g, from about 1 J / g to about 14 J / g, from about 5 J / g to about 20 J / g, from about 1 J / g to about 16 J / g, from about 1 J / g to about 14 J / g, from about 1 J / g to about 20 J / g, from about 1 J / g to about 16 J / g, from about 1 J / g to about 14 J / g, from about 1 J / g to about 20 J / g a second enthalpy of fusion ΔH of about 20 J / g to about 20 J / g, about 5 J / g to about 18 J / g, about 5 J / g to about 16 J / g, about 5 J / g to about 14 J / g, about 10 J / g to about 20 J / g, about 10 J / g to about 18 J / g, about 10 J / g to about 16 J / g, or even about 10 J / g to about 14 J / g, or any subrange formed from any of these endpoints. m2 may have:

[0045] In another embodiment, the partially hydrogenated 1,4-polybutadiene has a second enthalpy of fusion ΔH of about 0 J / g to about 20 J / g when measured at a temperature up to about 140° C. m2 In embodiments, the partially hydrogenated 1,4-polybutadiene may have a second enthalpy of fusion ΔH of about 0 J / g or more, about 0.1 J / g or more, about 0.5 J / g or more, about 1 J / g or more, about 5 J / g or more, or even 10 J / g or more, when measured at a temperature of up to about 140° C. m2 In embodiments, the partially hydrogenated 1,4-polybutadiene may have a second enthalpy of fusion ΔH of about 20 J / g or less, about 18 J / g or less, about 16 J / g or less, or even about 14 J / g or less, when measured at a temperature up to about 140° C. m2In an embodiment, the partially hydrogenated 1,4-polybutadiene may have a molecular weight of from about 0 J / g to about 20 J / g, from about 0 J / g to about 18 J / g, from about 0 J / g to about 16 J / g, from about 0 J / g to about 14 J / g, from about 0.1 J / g to about 20 J / g, from about 0.1 J / g to about 18 J / g, from about 0.1 J / g to about 16 J / g, from about 0.1 J / g to about 14 J / g, from about 0.5 J / g to about 20 J / g, from about 0.5 J / g to about 18 J / g, from about 0.5 J / g to about 16 J / g, from about 0.5 J / g to about 14 J / g, when measured at a temperature of up to about 140° C. g, about 1 J / g to about 20 J / g, about 1 J / g to about 18 J / g, about 1 J / g to about 16 J / g, about 1 J / g to about 14 J / g, about 5 J / g to about 20 J / g, about 5 J / g to about 18 J / g, about 5 J / g to about 16 J / g, about 5 J / g to about 14 J / g, about 10 J / g to about 20 J / g, about 10 J / g to about 18 J / g, about 10 J / g to about 16 J / g, or even about 10 J / g to about 14 J / g, or any subrange formed from any of these endpoints. m2 may have:

[0046] In an embodiment, the partially hydrogenated 1,4-polybutadiene has a weight average molecular weight M of about 100,000 g / mol to about 500,000 g / mol. w In embodiments, the partially hydrogenated 1,4-polybutadiene may have a weight average molecular weight M of about 100,000 g / mol or more, about 110,000 g / mol or more, or even about 120,000 g / mol or more. w In embodiments, the partially hydrogenated 1,4-polybutadiene may have a weight average molecular weight M of about 500,000 g / mol or less, about 400,000 g / mol or less, about 300,000 g / mol or less, about 200,000 g / mol or less, or about 160,000 g / mol or less. wIn an embodiment, the hydrogenated 1,4-polybutadiene may have a molecular weight of from about 100,000 g / mol to about 500,000 g / mol, from about 100,000 g / mol to about 400,000 g / mol, from about 100,000 g / mol to about 300,000 g / mol, from about 100,000 g / mol to about 200,000 g / mol, from about 100,000 g / mol to about 160,000 g / mol, from about 110,000 g / mol to about 500,000 g / mol, from about 110,000 g / mol to about 400,000 g / mol, from about 110,000 g / mol to about 300,000 g / mol. weight average molecular weight M of about 110,000 g / mol to about 200,000 g / mol, about 110,000 g / mol to about 160,000 g / mol, about 120,000 g / mol to about 500,000 g / mol, about 120,000 g / mol to about 400,000 g / mol, about 120,000 g / mol to about 300,000 g / mol, about 120,000 g / mol to about 200,000 g / mol, or even about 120,000 g / mol to about 160,000 g / mol, or any subrange formed from any of these endpoints. w may have:

[0047] In embodiments, the hydrogenated 1,4-polybutadiene has a number average molecular weight M of about 20,000 g / mol or more, about 40,000 g / mol or more, or even about 60,000 g / mol or more. n In embodiments, the hydrogenated 1,4-polybutadiene may have a number average molecular weight M of about 250,000 g / mol or less, about 150,000 g / mol or less, about 100,000 g / mol or less, or even about 80,000 g / mol or less. nIn an embodiment, the hydrogenated 1,4-polybutadiene may have a molecular weight of about 20,000 g / mol to about 250,000 g / mol, about 20,000 g / mol to about 150,000 g / mol, about 20,000 g / mol to about 100,000 g / mol, about 20,000 g / mol to about 80,000 g / mol, about 40,000 g / mol to about 250,000 g / mol, about 40,000 g / mol to about 150,000 g / mol, about 40,000 g / mol and a number average molecular weight M of about 100,000 g / mol, about 40,000 g / mol to about 80,000 g / mol, about 60,000 g / mol to about 250,000 g / mol, about 60,000 g / mol to about 150,000 g / mol, about 60,000 g / mol to about 100,000 g / mol, or even about 60,000 g / mol to about 80,000 g / mol, or any subrange formed from any of these endpoints. n may have:

[0048] Certain embodiments for producing a polymer include reacting living terminal polymer chains with a functionalizing compound having formula (I). According to an embodiment, the modified high cis polybutadiene polymer comprises polymer chains resulting from the polymerization of 1,3-butadiene that are bonded to a residue of a functionalizing compound having formula (I), each polymer chain being bonded to the residue of the functionalizing compound through an X group.

[0049] According to an embodiment, formula (I) is as follows:

[0050] [ka] wherein X is a group reactive with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and anhydride; and each R1 is a C1-C 20 (For example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16, C 17 , C 18 , C 19 , or C 20 ), preferably C1 to C 10 (For example, C1, C2, C3, C4, C5, C6, C7, C8, C9, or C 10 ), more preferably C1-C3 (e.g., C1, C2, or C3) hydrocarbylene, each of the foregoing optionally containing one unsaturated carbon-carbon bond; R' is selected from C1-C 20 (For example, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , or C 20 ) alkoxy or carboxy, preferably C1-C 10 (For example, C1, C2, C3, C4, C5, C6, C7, C8, C9, or C 10 R″ is selected from C1 to C6 (e.g., C1, C2, C3, C4, C5, or C6) alkoxy or carboxy, more preferably C1 to C6 (e.g., C1, C2, C3, C4, C5, or C6) alkoxy, most preferably C1 or C2 alkoxy or carboxy; 20 alkyl, alkoxy, or carboxy, or C6 to C2 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , or C 20 ) aryl, preferably C1-C 10 (For example, C1, C2, C3, C4, C5, C6, C7, C8, C9, or C 10 ) alkyl, alkoxy, or carboxy, or C6-C 14 (For example, C6, C7, C8, C9, C10 , C 11 , C 12 , C 13 , or C 14 ) aryl, more preferably C1-C6 alkyl, alkoxy, or carboxy, or C6 aryl. Formula (I) may also be represented by the following: XR 1 -Si(R')2(R''). In certain embodiments, the functionalized compound of formula (I) can be represented as R 1 In another embodiment, the functionalized compound of formula (I) has a structure in which R 1 R, R', and R'' all have structures selected from the groups described as preferred. Because the functionalized compounds of formula (I) have two alkoxy groups on the Si, the compounds can be referred to as dialkoxysilanes (more specifically, alkyldialkoxysilanes or aryldialkoxysilanes due to the presence of the R'' groups). 1 By stating that R is a hydrocarbylene group, it is meant that it is bonded to two other components (i.e., the X group and Si). In certain preferred embodiments of the first to third embodiments, R 1 is aliphatically unsaturated. In other embodiments, R 1 is aliphatic and may contain one unsaturated carbon-carbon bond. Generally, according to embodiments, R 1 The carbons in the group may be arranged in a linear chain or may be branched.

[0051] In some embodiments, X is a cyano group or an epoxy group, more preferably an epoxy group. According to embodiments, when X is a cyano group, its specific structure can vary as discussed in more detail below. According to embodiments, when X is an epoxy group, it preferably has 2 to 4 carbon atoms (e.g., 2, 3, or 4 carbon atoms) in the epoxy ring.

[0052] As mentioned above, according to embodiments, X of the functionalized compound of formula (I) (or a residue derived therefrom) is preferably selected from an epoxy group, more preferably the epoxy group is a glycidoxy group. Suitable compounds for use as functionalizing compounds of formula (I) where X is an epoxy group include, but are not limited to, (2-glycidoxyethyl)methyldimethoxysilane, (2-glycidoxyethyl)methyldiethoxysilane, (2-glycidoxyethyl)ethyldimethoxysilane, (2-glycidoxyethyl)ethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)ethyldimethoxysilane, (3-glycidoxypropyl)ethyldiethoxysilane, 2-(3,4-epoxyhexyl)ethyl(methyldimethoxy)silane, 2-(3,4-epoxyhexyl)ethyl(methyldiethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyl(ethyldimethoxy)silane, and 2-(3,4-epoxycyclohexyl)ethyl(ethyldiethoxy)silane. Of the above, (3-glycidoxypropyl)methyldimethoxysilane and (3-glycidoxypropyl)methyldiethoxysilane are particularly preferred.

[0053] In other embodiments, suitable compounds for use as functionalizing compounds of formula (I) where X is an epoxy group include, but are not limited to, (2-glycidoxyethyl)trimethoxysilane, (2-glycidoxyethyl)triethoxysilane, (2-glycidoxyethyl)trimethoxysilane, (2-glycidoxyethyl)triethoxysilane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(trimethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyl(triethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyl(trimethoxy)silane, and 2-(3,4-epoxycyclohexyl)ethyl(triethoxy)silane.

[0054] As mentioned above, according to the embodiment, X of the functionalized compound of formula (I) (or the residue derived therefrom) is preferably selected from a cyano group. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments include compounds in which the cyano group and Si are separated by a hydrocarbylene group having 1-10 carbons, preferably 3-8 carbons. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments include 2-cyanoethylmethyldiethoxysilane and 3-cyanopropylmethyldiethoxysilane. In these embodiments in which X of the functionalized compound of formula (I) (or the residue derived therefrom) is selected from a ketone group, various compounds may be suitable as the functionalized compound.

[0055] In these embodiments where X of the functionalized compound of formula (I) (or a residue derived therefrom) is selected from a ketone group, a variety of compounds may be suitable as the functionalized compound. A non-limiting example of such a compound is p-(methyldiethoxysilyl)acetophenone.

[0056] In those embodiments in which X of the functionalized compound of formula (I) (or a residue derived therefrom) is selected from an aldehyde group, various compounds may be suitable as the functionalized compound. A non-limiting example of such a compound is (methyldiethoxysilyl)undecanal.

[0057] In these embodiments where X of the functionalized compound of formula (I) (or the residue derived therefrom) is selected from an ester group, various compounds may be suitable as the functionalized compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic acid hydrocarbyl ester residue. Specific examples of such compounds include, but are not limited to, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylethyldiethoxysilane, and 3-methacryloyloxypropylmethyldiisopropoxysilane. Of the foregoing, 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldiethoxysilane are preferred.

[0058] In these embodiments where X of the functionalized compound of formula (I) (or the residue thereof) is selected from an acid anhydride group, various compounds may be suitable as the functionalized compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic acid anhydride residue. Specific examples of such compounds include, but are not limited to, 3-(methyldiethoxysilyl)propicuccinic anhydride and 3-(methyldimethoxysilyl)propylsuccinic anhydride. Among them, 3-(methyldiethoxysilyl)propylsuccinic anhydride is preferred.

[0059] According to the embodiment, the polymer chain (resulting from the polymerization of 1,3-butadiene using one of the defined catalytic systems) is attached to the functionalized compound via the X group. The structure of the functionalized compound changes to some extent when the polymer chain is attached to the X group, so the moiety to which the polymer chain is attached is described as the residue of the functionalized compound. Generally, one polymer chain is attached to the residue of the functionalized compound via the X group of each molecule of the functionalized compound. However, depending on the structure of the X group, it is possible for more than one polymer chain to be attached to the residue of the functionalized compound. The position on the functionalized compound to which the polymer chain is attached (i.e., using one of the defined catalytic systems) by the process of the first embodiment can be contrasted with the position on the functionalized compound to which the polymer chain is attached if an anionic initiator (e.g., n-butyl lithium) is used to polymerize 1,3-butadiene. More specifically, when an anionic initiator is used, the polymer chain may be attached to the functionalized compound via an alkoxy group on Si (substituting the OR of the OR alkoxy group and attaching directly to Si) or via the X group. When 1,3-butadiene is polymerized to produce living terminal polymer chains using one of the defined catalytic systems, the polymer chain is (only) bonded to the functionalizing compound via the X group. As a non-limiting example, if X of the functionalizing compound is an epoxy group, the polymer chain is bonded to one of the carbons alpha to the oxygen of the epoxy ring. More specifically, according to such a bonding reaction, one polymer chain is bonded to one of the carbon atoms alpha to the oxygen of the epoxy ring, and the bond causes a ring opening with conversion of the oxygen atom to OH.

[0060] According to embodiments, the amount of functionalizing compound of formula (I) used in the reaction of the living end polymer chains (i.e., according to the process of the first embodiment) or present as a residue in the modified high cis polybutadiene polymer (i.e., according to the process of the second and third embodiments) can vary. In certain embodiments, the functionalizing compound is present in a ratio of 100:1 to 0.5:1 (e.g., 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 8:1, 6:1, 4:1, 2:1, 1:1, 0.5:1), preferably 50:1 to 1:1 (e.g., 50:1, 40:1, 30:1, 20:1, 10:1, 8:1, 6:1, 4:1, 2:1, or 1:1), more preferably from 30:1 to 2:1 (e.g., 30:1, 25:1, 20:1, 15:1, 10:1, 8:1, 6:1, 4:1, or 2:1), the molar ratio being based on the moles of functionalizing compound to the moles of primary metal in the catalyst system (i.e., moles of lanthanide in a lanthanide-based catalyst system, moles of nickel in a nickel-based catalyst system, or moles of cobalt in a cobalt-based catalyst system).

[0061] Other embodiments for producing polymers include reacting a living terminal polymer chain with a functionalizing compound, including a heterocyclic nitrile compound such as pyrazinecarbonitrile, as described in U.S. Pat. No. 8,314,189, which is incorporated herein by reference.

[0062] In one or more embodiments, suitable other functionalizing compounds include those compounds that contain groups that can react with the reactive polymers produced according to the present invention. Exemplary functionalizing compounds include ketones, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothioketones, and acid anhydrides. Examples of these compounds are described in U.S. Patent Nos. 4,906,706, 4,990,573, 5,064,910, 5,567,784, 5,844,050, 6,838,526, 6,977,281, and 6,992,147, U.S. Patent Application Publication Nos. 2006 / 0004131(A1), 2006 / 0004132(A2), and 2006 / 0004133(A3). Nos. 025539(A1), 2006 / 0030677(A1), and 2004 / 0147694(A1), Japanese Patent Application Nos. 05-051406(A), 05-059103(A), 10-306113(A), and 11-035633(A), which are incorporated herein by reference. Other examples of functionalized compounds include azine compounds described in U.S. Patent No. 11 / 640,711, hydrobenzamide compounds described in U.S. Patent No. 11 / 710,713, nitro compounds described in U.S. Patent No. 11 / 710,845, and protected oxime compounds described in U.S. Patent No. 60 / 875,484, which are all incorporated herein by reference.

[0063] In certain embodiments, the functionalizing compounds used may be metal halides, metalloid halides, alkoxysilanes, metal carboxylates, hydrocarbyl metal carboxylates, hydrocarbyl metal ester-carboxylates, and metal alkoxides.

[0064] Exemplary metal halide compounds include tin tetrachloride, tin tetrabromide, tin tetraiodide, n-butyltin trichloride, phenyltin trichloride, di-n-butyltin dichloride, diphenyltin dichloride, tri-n-butyltin chloride, triphenyltin chloride, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, n-butylgermanium trichloride, di-n-butylgermanium dichloride, and tri-n-butylgermanium chloride.

[0065] Exemplary metalloid halide compounds include silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, boron trichloride, boron tribromide, boron triiodide, phosphorus trichloride, phosphorus tribromide, and phosphorus triiodide.

[0066] Exemplary metal carboxylate compounds include tin tetraacetate, tin bis(2-ethylhexanoate), and tin bis(neodecanoate).

[0067] Exemplary hydrocarbyl metal carboxylate compounds include triphenyltin 2-ethylhexanoate, tri-n-butyltin 2-ethylhexanoate, tri-n-butyltin neodecanoate, triisobutyltin 2-ethylhexanoate, diphenyltin bis(2-ethylhexanoate), di-n-butyltin bis(2-ethylhexanoate), di-n-butyltin bis(neodecanoate), phenyltin tris(2-ethylhexanoate), and n-butyltin tris(2-ethylhexanoate).

[0068] Exemplary hydrocarbyl metal ester-carboxylate compounds include di-n-butyltin bis(n-octylmaleate), di-n-octyltin bis(n-octylmaleate), diphenyltin bis(n-octylmaleate), di-n-butyltin bis(2-ethylhexylmaleate), di-n-octyltin bis(2-ethylhexylmaleate), and diphenyltin bis(2-ethylhexylmaleate).

[0069] Exemplary metal alkoxide compounds include dimethoxytin, diethoxytin, tetraethoxytin, tetra-n-propoxytin, tetraisopropoxytin, tetra-n-butoxytin, tetraisobutoxytin, tetra-t-butoxytin, and tetraphenoxytin.

[0070] As described above, the rubber composition may include 1,4-polybutadiene polymer, as well as various other ingredients and fillers discussed herein, such as reinforcing fillers and curatives. Fillers that may be used may include fillers conventionally used in tire manufacturing. Useful fillers include inorganic and organic fillers. In embodiments, organic fillers may include carbon black and starch. In embodiments, inorganic fillers may include silica, aluminum hydroxide, magnesium hydroxide, clay (hydrated aluminum silicate), and combinations thereof. In embodiments, reinforcing fillers may include carbon black, silica, or combinations thereof. In embodiments, curatives may include sulfur or sulfur donors.

[0071] In embodiments, the carbon black may include high speed extrusion furnace black, semi-reinforcement furnace black, high abrasive furnace black, medium super abrasive furnace black, super abrasive furnace black, and the like. In embodiments, the amount of carbon black in the rubber composition may be from about 1 phr to about 60 phr. In embodiments, the amount of carbon black in the rubber composition may be about 1 phr or more, about 5 phr or more, about 10 phr or more, or even about 20 phr or more. In embodiments, the amount of carbon black in the rubber composition may be about 60 phr or less, about 50 phr or less, about 40 phr or less, or even about 30 phr or less. In embodiments, the amount of carbon black in the rubber composition can be from about 1 phr to about 60 phr, from about 1 phr to about 60 phr, from about 1 phr to about 50 phr, from about 1 phr to about 40 phr, from about 1 phr to about 30 phr, from about 5 phr to about 60 phr, from about 5 phr to about 50 phr, from about 5 phr to about 40 phr, from about 5 phr to about 30 phr, from about 10 phr to about 60 phr, from about 10 phr to about 50 phr, from about 10 phr to about 40 phr, from about 10 phr to about 30 phr, from about 20 phr to about 60 phr, from about 20 phr to about 50 phr, from about 20 phr to about 40 phr, or even from about 20 phr to about 30 phr, or any subrange formed from any of these endpoints.

[0072] In embodiments, the silica may include silicon compounds such as wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or combinations thereof. In embodiments, the amount of silica in the rubber composition may be from about 25 phr to about 150 phr. In embodiments, the amount of silica in the rubber composition may be about 25 phr or more, about 50 phr or more, or even about 75 phr or more. In embodiments, the amount of silica in the rubber composition can be about 150 phr or less, about 125 phr or less, or even about 100 phr or less. In embodiments, the amount of silica in the rubber composition can be about 25 phr to about 150 phr, about 25 phr to about 150 phr, about 25 phr to about 125 phr, about 25 phr to about 100 phr, about 50 phr to about 150 phr, about 50 phr to about 125 phr, about 50 phr to about 100 phr, about 75 phr to about 150 phr, about 75 phr to about 125 phr, or even about 75 phr to about 100 phr, or any subrange formed from any of these endpoints.

[0073] In embodiments, the amount of silane in the rubber composition may be from about 1 phr to about 20 phr. In embodiments, the amount of silane in the rubber composition may be about 1 phr or more, about 3 phr or more, about 5 phr or more, about 7 phr or more, about 9 phr or more, or even about 11 phr or more. In embodiments, the amount of silane in the rubber composition may be about 20 phr or less, about 18 phr or less, about 16 phr or less, about 14 phr or less, about 12 phr or less, or even about 10 phr or less. In an embodiment, the amount of silane in the rubber composition is from about 1 phr to about 20 phr, from about 1 phr to about 18 phr, from about 1 phr to about 16 phr, from about 1 phr to about 14 phr, from about 1 phr to about 12 phr, from about 1 phr to about 10 phr, from about 1 phr to about 8 phr, from about 1 phr to about 6 phr, from about 1 phr to about 4 phr, from about 1 phr to about 2 phr, from about 3 phr to about 20 phr, from about 3 phr to about 18 phr, from about 3 phr to about 3 ... The range may be from about 3 phr to about 16 phr, from about 3 phr to about 14 phr, from about 3 phr to about 12 phr, from about 3 phr to about 10 phr, from about 3 phr to about 9 phr, from about 3 phr to about 7 phr, from about 3 phr to about 5 phr, from about 5 phr to about 15 phr, from about 5 phr to about 12 phr, from about 5 phr to about 9 phr, or even from about 5 phr to about 7 phr, or any subrange formed from any of these endpoints.

[0074] In embodiments, in addition to hydrogenated 1,4-polybutadiene, the rubber composition may include natural rubber or other rubbery elastomers, such as polybutadiene, polyisoprene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and synthetic rubbers, such as poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubbers, acrylic rubbers, urethane rubbers, silicone rubbers, epichlorohydrin rubbers, or combinations thereof.

[0075] Elastomers exclude hydrogenated 1,4-butadiene. Total rubber content includes hydrogenated 1,4-polybutadiene and elastomers (if present).

[0076] In embodiments, the amount of elastomeric material in the rubber composition may be from about 1 phr to about 90 phr. In embodiments, the amount of elastomeric material in the rubber composition may be about 0 phr or more, about 1 phr or more, about 15 phr or more, about 30 phr or more, about 45 phr or more, or even about 60 phr or more. In embodiments, the amount of elastomeric material in the rubber composition may be about 90 phr or less, about 75 phr or less, about 60 phr or less, about 45 phr or less, or even about 30 phr or less. In an embodiment, the amount of the rubbery elastomer in the rubber composition is from about 0 phr to about 90 phr, from about 0 phr to about 75 phr, from about 0 phr to about 60 phr, from about 0 phr to about 45 phr, from about 0 phr to about 30 phr, from about 0 phr to about 15 phr, from about 1 phr to about 90 phr, from about 1 phr to about 75 phr, from about 1 phr to about 60 phr, from about 1 phr to about 45 phr, from about 1 phr to about 30 phr, from about 1 phr to about 15 phr, from about 15 phr to about 90 phr, from about 15 phr to about 75 phr, It may be from 15 phr to about 60 phr, from about 15 phr to about 45 phr, from about 15 phr to about 30 phr, from about 30 phr to about 90 phr, from about 30 phr to about 75 phr, from about 30 phr to about 60 phr, from about 30 phr to about 45 phr, from about 45 phr to about 90 phr, from about 45 phr to about 75 phr, from about 45 phr to about 60 phr, from about 60 phr to about 90 phr, or even from about 60 phr to about 75 phr, or any subrange formed from any of these endpoints.

[0077] In embodiments, useful processing or extending oils may also be included. In embodiments, the oils may include those commercially available as paraffinic, aromatic, or naphthenic oils. In embodiments, the oil may be predominantly paraffinic. In embodiments, the extending oil may be oil-extending sulfur. The tire components may also include other additives such as antiozonants, waxes, scorch inhibitors, processing aids, zinc oxide, tackifiers, reinforcing resins, fatty acids such as stearic acid, peptizing agents, and one or more accelerators.

[0078] In an embodiment, the rubber composition may include a plasticizing component including about 0 to about 50 phr (e.g., about 0, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, or about 50 phr) of at least one plasticizing oil and about 0 to about 60 phr (e.g., about 0, about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, or about 60 phr) of at least one hydrocarbon resin having a Tg of at least 30° C. In an embodiment, at least one of the plasticizing oil or the hydrocarbon resin is present in the rubber composition. In an embodiment, the plasticizing component may include about 0 to about 30 phr of the plasticizing oil and about 5 to about 60 phr of the hydrocarbon resin. In some embodiments, the plasticizing component can include about 0 to about 15 phr of plasticizing oil and about 5 to about 50 phr of hydrocarbon resin. In certain embodiments, the plasticizing oil can be present in an amount of at least 1 phr (e.g., about 1 to 50 phr, about 1 to 30 phr, about 1 to 15 phr, about 1 to 10 phr, about 1 to 5 phr, etc.).

[0079] Various types of plasticizing oils may be utilized, including but not limited to aromatic, naphthenic, and low PCA oils. In an embodiment, the plasticizing oil is liquid (pourable) at 25°C. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 weight percent as measured by IP346 method. The procedure for IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd Edition, published by the Institute of Petroleum (UK). Suitable low PCA oils include mild extraction solvate (MES), treated distillate aromatic extract (TDAE), TRAE, and heavy naphthenic. Suitable MES oils are commercially available as CATENEX SNR (from SHELL), PROREX 15 and FLEXON 683 (from EXXONMOBIL), VIVATEC 200 (from BP), PLAXOLENE MS (from TOTAL FINA ELF), TUDALEN 4160 / 4225 (from DAHLEKE), MES-H (from REPSOL), MES (from Z8) and OLIO MES S201 (from AGIP). Suitable TDAE oils are available as TYREX 20 (from EXXONMOBIL), VIVATEC 500, VIVATEC 180 and ENERTHENE 1849 (from BP) and EXTENSOIL 1996 (from REPSOL). Suitable heavy naphthenic oils are available as SHELLFELX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400, and SAN JOAQUIN 2000 L. Suitable low PCA oils also include oils of various plant origins, such as those that may be obtained from vegetables, nuts, and seeds.Non-limiting examples include, but are not limited to, soybean oil, sunflower oil (including high oleic sunflower oil having an oleic acid content of at least 60%, at least 70%, or at least 80%), safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. In certain embodiments, the tire rubber composition includes only limited amounts of oil, such as less than about 10 phr (e.g., about 9, about 8, about 7, about 6, about 5, about 4, about 3, about 2, about 1, or about 0 phr), less than about 5 phr, between about 1 and about 5 phr, or even about 0 phr.

[0080] Various types of hydrocarbon resins may be utilized in the plasticizing component, including the plasticizing resin. As used herein, the term plasticizing resin refers to a compound that is solid at room temperature (23° C.) and is miscible in the rubber composition in the amount used, which is usually at least 5 phr. Generally, the plasticizing resin acts as a diluent, which can be contrasted with a tacky resin, which is generally immiscible, and can migrate and provide stickiness to the surface of the rubber composition. In certain embodiments of the third embodiment in which a plasticizing resin is utilized, the plasticizing resin comprises a hydrocarbon resin, which can be an aliphatic type, an aromatic type, or an aliphatic / aromatic type, depending on the monomers contained therein. Examples of suitable plasticizing resins for use in the rubber composition of the third embodiment include, but are not limited to, cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, and homopolymer or copolymer resins of C5 fraction. Such resins can be used, for example, individually or in combination. In a particular embodiment, a plastic resin is used that satisfies at least one of the following: Tg of 30° C. (preferably, above 40° C. and / or below 120° C. or below 100° C.), number average molecular weight (Mn) of 400-2000 grams / mole (preferably, 500-2000 grams / mole), and polydispersity index (PI) of less than 3 (preferably, less than 2) (PI=Mw / Mn, where Mw is the weight average molecular weight of the resin). The Tg of the resin can be measured by DSC (Differential Scanning Calorimetry) according to ASTM D3418 (1999).The Mw, Mn, and PI of the resins can be determined by size exclusion chromatography (SEC) using THF, 35° C., a concentration of 1 g / 1, a flow rate of 1 milliliter / minute, the solution filtered through a filter with a porosity of 0.45 pm prior to injection, Moore calibration with polystyrene standards, a series of three “Waters” columns ("Styragel" HR4E, HR1, and HR0.5), and detection with a differential refractometer ("Waters 2410") and its associated operating software ("Waters Empower").

[0081] Antiozonants may include N,N' disubstituted-p-phenylenediamines such as N-1,3-dimethylbutyl-N' phenyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N-phenyl-N-isopropyl-p-phenylenediamine (IPPD), and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine. Other examples of antiozonants include acetone diphenylamine condensation products, 2,4-trimethyl-1,2-dihydroquinoline, octylated diphenylamine, and 2,6-di-t-butyl-4-methylphenol.

[0082] The curing accelerator may include, but is not limited to, dithiocarbamate accelerators, including metal dialkyl dithiocarbamates, such as zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dimethyl dithiocarbamate, and iron dimethyl dithiocarbamate; thiazole accelerators, including benzothiazole disulfides, such as 2-mercaptobenzothiazole, mercaptobenzothiazole disulfide; benzothiazole sulfenamides, such as n-cyclohexyl-2-benzothiazole sulfenamide, and sulfenamide accelerators, such as t-butyl-2-benzothiadiyl sulfenamide.Furthermore, the curing accelerator may also include diphenylguanidine.

[0083] Various amounts of partially hydrogenated 1,4-polybutadiene are contemplated within the rubber composition. In embodiments, out of 100 total parts rubber, the partially hydrogenated 1,4-polybutadiene may comprise from about 10 to about 100 parts of the total, or from about 25 to about 75 parts of the total. In embodiments, the amount of partially hydrogenated 1,4-polybutadiene in the rubber composition may be about 10 phr or more, about 15 phr or more, about 20 phr or more, about 25 phr or more, about 30 phr or more, about 35 phr or more, or even about 40 phr or more. In embodiments, the amount of partially hydrogenated 1,4-polybutadiene in the rubber composition may be about 100 phr or less, about 90 phr or less, about 75 phr or less, or even 60 phr or less. In an embodiment, the amount of partially hydrogenated 1,4-polybutadiene in the rubber composition is from about 10 phr to about 100 phr, from about 10 phr to about 90 phr, from about 10 phr to about 75 phr, from about 10 phr to about 60 phr, from about 10 phr to about 50 phr, from about 15 phr to about 100 phr, from about 15 phr to about 90 phr, from about 15 phr to about 75 phr, from about 1 5phr~about 60phr, about 15phr~about 50phr, about 20phr~about 100phr, about 20phr~about 90phr, about 20phr~about 75phr, about 20phr ~60phr, 20phr~50phr, 25phr~100phr, 25phr~90phr, 25phr~75phr, 25phr~60p hr, about 25 phr to about 50 phr, about 30 phr to about 100 phr, about 30 phr to about 90 phr, about 30 phr to about 80 phr, about 30 phr to about 70 phr, about 30 phr to about 60 phr, about 30 phr to about 50 phr, about 35 phr to about 100 phr, about 35 phr to about 90 phr, about 35 phr to about 80 phr, about 35 phr to about 70 phr, about 35 phr to about 60 phr, about 35 phr to about 50 phr, about 40 phr to about 100 phr, about 40 phr to about 90 phr, about 40 phr to about 75 phr, about 40 phr to about 60 phr, or even about 40 phr to about 50 phr, or any subrange formed from any of these endpoints.

[0084] In embodiments, the 1,4-polybutadiene may have a cis content of from about 94% to about 99.5%, a vinyl content of from about 0.1% to about 1%, and a trans content of from about 0.1% to about 5%, prior to hydrogenation.

[0085] In embodiments, the 1,4-polybutadiene may have a cis content of about 94% or more, about 94.5% or more, about 95% or more, about 95.5% or more, or even about 96% or more prior to hydrogenation. In embodiments, the 1,4-polybutadiene may have a cis content of about 99.5% or less, about 99% or less, about 98.5% or less, or even about 95% or less prior to hydrogenation. In an embodiment, the 1,4-polybutadiene may have a molecular weight of about 94% to about 99.5%, about 94% to about 99%, about 94% to about 98.5%, about 94% to about 98%, about 94.5% to about 99.5%, about 94.5% to about 99%, about 94.5% to about 98.5%, about 94.5% to about 98%, about 95% to about 99.5%, about 95% to about 99%, or about 95% to about 98.5% prior to hydrogenation. , about 95% to about 98%, about 95.5% to about 99.5%, about 95.5% to about 99%, about 95.5% to about 98.5%, about 95.5% to about 98%, about 96% to about 99.5%, about 96% to about 99%, about 96% to about 98.5%, or even about 96% to about 98%, or any subrange formed from any of these endpoints.

[0086] In embodiments, the 1,4-polybutadiene may have a vinyl content of about 0.1% or more, or even about 0.25% or more, prior to hydrogenation. In embodiments, the 1,4-polybutadiene may have a vinyl content of about 1% or less, about 0.75% or less, or even about 0.25% or less, prior to hydrogenation. In embodiments, the 1,4-polybutadiene may have a vinyl content of about 0.1% to about 1%, about 0.1% to about 0.75%, about 0.1% to about 0.5%, about 0.25% to about 1%, about 0.25% to about 0.75%, or even about 0.25% to about 0.5%, or any subrange formed from any of these endpoints, prior to hydrogenation.

[0087] In embodiments, the 1,4-polybutadiene may have a trans content of about 0.1% or more, about 0.5% or more, about 1% or more, about 1.5% or more, about 2% or more, about 2.5% or more, or even about 3% or more prior to hydrogenation. In embodiments, the 1,4-polybutadiene may have a trans content of about 5% or less, about 4.5% or less, or even about 4% or less prior to hydrogenation. In embodiments, the 1,4-polybutadiene, prior to hydrogenation, may have a trans content of from about 0.1% to about 5%, from about 0.1% to about 4.5%, from about 0.1% to about 4%, from about 0.5% to about 5%, from about 0.5% to about 4.5%, from about 0.5% to about 4%, from about 1% to about 5%, from about 1% to about 4.5%, from about 1% to about 4%, from about 1.5% to about 5%, from about 1.5% to about 4.5%, from about 1.5% to about 4%, from about 2% to about 5%, from about 2% to about 4.5%, from about 2% to about 4%, from about 2.5% to about 5%, from about 2.5% to about 4.5%, from about 2.5% to about 4%, from about 3% to about 5%, from about 3% to about 4.5%, or even from about 3% to about 4%, or any subrange formed from any of these endpoints.

[0088] Various polymerization methods suitable for making the 1,4-polybutadiene of the present disclosure (i.e., prior to hydrogenation) are contemplated. In embodiments, the 1,4-polybutadiene compositions may be prepared by coordination polymerization, in which a monomer (e.g., a conjugated diene monomer) is polymerized by using a coordination catalyst system.

[0089] Conjugated diene monomer, as used herein, refers to a monomer composition having at least two double bonds separated by a single bond. The processes contemplated herein may use at least one conjugated diene monomer containing less than 20 carbon atoms (i.e., 4-19 carbons). Examples of conjugated diene monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Mixtures of two or more conjugated dienes may also be utilized in the copolymerization. While all monomers are believed to be suitable, the current discussion focuses on 1,3-butadiene monomer.

[0090] According to certain embodiments, the coordination catalyst system used for the polymerization of 1,4-polybutadiene (i.e., before hydrogenation) is selected from one of (a) lanthanide-based catalyst systems or (b) nickel or other transition metal-based catalyst systems. Preferably, a lanthanide-based catalyst system is used. Also preferably, the catalyst system used avoids the use of anionic initiators (e.g., organolithium compounds such as n-butyllithium).

[0091] Lanthanide-Based Catalysts As mentioned above, the process of one or more embodiments may utilize a lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, where (iii) may optionally be provided by (i), (ii), or both (i) and (ii). The lanthanide-based catalyst system is used to polymerize a quantity of conjugated diene monomer (discussed in more detail below) to produce polymer chains having living ends. Preferably, in certain embodiments, the lanthanide-based catalyst system is preformed before being added to any solution of conjugated diene monomer.

[0092] As mentioned above, in certain embodiments, the lanthanide-based catalyst system used in the polymerization process comprises a lanthanide compound. Lanthanide compounds useful in these processes are compounds that contain at least one atom of a lanthanide element. As used herein, "lanthanide element" refers to the elements found in the lanthanide series of the periodic table (i.e., element numbers 57-71), as well as didimium, which is a mixture of rare earth elements obtained from monazite sand. In particular, the lanthanide elements disclosed herein include lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and didimium. Preferably, the lanthanide compound comprises at least one atom of neodymium, gadolinium, samarium, or a combination thereof. Most preferably, the lanthanide compound comprises at least one neodymium atom.

[0093] The lanthanide atom in the lanthanide compound may be in various oxidation states, including, but not limited to, 0, +2, +3 and +4 oxidation states. According to certain preferred embodiments of the process of the first embodiment, a trivalent lanthanide compound is used in which the lanthanide atom is in the +3 oxidation state. In general, lanthanide compounds suitable for use in the process of the first embodiment include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organophosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide diketonates, lanthanide alkoxides or aryloxides, lanthanide halides, lanthanide pseudohalides, lanthanide oxyhalides, and organolanthanide compounds. Preferably, the lanthanide compound is a lanthanide carboxylate, more preferably a neodymium carboxylate, most preferably neodymium versatate.

[0094] According to certain embodiments of the process of the first embodiment, the lanthanide compound may be soluble in a hydrocarbon solvent, such as an aromatic, aliphatic, or cycloaliphatic hydrocarbon solvent disclosed herein, however, hydrocarbon-insoluble lanthanide compounds may also be useful in the process of the first embodiment because they can be suspended in the polymerization medium to form the catalytically active species.

[0095] For ease of illustration, the further discussion of useful lanthanide compounds for use in the polymerization processes of certain embodiments will focus on neodymium compounds, although one of ordinary skill in the art will be able to select similar compounds based on other lanthanide metals disclosed herein.

[0096] Examples of neodymium carboxylates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate (i.e., neodymium versatate or NdV3), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

[0097] Examples of neodymium organophosphates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl)phosphate, neodymium bis(2-ethylhexyl)phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium dioleyl phosphate, neodymium diphenyl phosphate, neodymium bis(p-nonylphenyl)phosphate, neodymium butyl(2-ethylhexyl)phosphate, neodymium(1-methylheptyl)(2-ethylhexyl)phosphate, and neodymium(2-ethylhexyl)(p-nonylphenyl)phosphate.

[0098] Examples of neodymium organic phosphonates suitable for use as the lanthanide compound in the process of the first embodiment include neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decyl phosphonate, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, neodymium (p-nonylphenyl) phosphonate, neodymium butyl butyl phosphonate, neodymium pentyl pentyl phosphonate, neodymium hexyl hexyl phosphonate, neodymium heptyl heptyl phosphonate, neodymium octyloctyl phosphonate, neodymium (1-methylheptyl) (1-ethylhexyl) phosphonate, neodymium butyl(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium 1-methylheptyl)(2-ethylhexyl)phosphonate, neodymium decyldecylphosphonate, neodymium dodecyldodecylphosphonate, neodymium octadecyloctadecylphosphonate, neodymium oleyloleylphosphonate, neodymium phenylphenylphosphonate, neodymium (p-nonylphenyl)(p-nonylphenyl)phosphonate, neodymium butyl(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)butylphosphonate, neodymium (1-methylheptyl)(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)(1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)(p-nonylphenyl)phosphonate, and neodymium (p-nonylphenyl)(2-ethylhexyl)phosphonate.

[0099] Examples of neodymium organophosphinates suitable for use as the lanthanide compound in the process of the first embodiment include neodymium butyl phosphinate, neodymium pentyl phosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphinate, neodymium (2-ethylhexyl) phosphinate, neodymium decyl phosphinate, neodymium dodecyl phosphinate, neodymium octadecyl phosphinate, neodymium oleyl phosphinate, neodymium phenyl phosphinate, neodymium (p-nonylphenyl) phosphinate, neodymium dibutyl phosphinate, neodymium dipentyl phosphinate, neodymium di neodymium hexyl phosphinate, neodymium diheptyl phosphinate, neodymium dioctyl phosphinate, neodymium bis(1-methylheptyl)phosphinate, neodymium bis(2-ethylhexyl)phosphinate, neodymium didecyl phosphinate, neodymium didodecyl phosphinate, neodymium dioctadecyl phosphinate, neodymium dioleyl phosphinate, neodymium diphenyl phosphinate, neodymium bis(p-nonylphenyl)phosphinate, neodymium butyl(2-ethylhexyl)phosphinate, neodymium (1-methylheptyl)(2-ethylhexyl)phosphinate, and neodymium (2-ethylhexyl)(p-nonylphenyl)phosphinate.

[0100] Examples of neodymium carbamates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate, and neodymium dibenzyl carbamate.

[0101] Examples of neodymium dithiocarbamates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, and neodymium dibenzyldithiocarbamate.

[0102] Examples of neodymium xanthates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthate, neodymium butyl xanthate, and neodymium benzyl xanthate.

[0103] Examples of neodymium diketonates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, neodymium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0104] Examples of neodymium alkoxides or aryloxides suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, neodymium nonylphenoxide, and neodymium naphthoxide.

[0105] Examples of suitable neodymium halides for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium fluoride, neodymium chloride, neodymium bromide, and neodymium iodide. Suitable neodymium pseudohalides include, but are not limited to, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, and neodymium ferrocyanide. Suitable neodymium oxyhalides include, but are not limited to, neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. A Lewis base (e.g., tetrahydrofuran ("THF")) may be used to facilitate solubilization of this class of neodymium compounds in an inert organic solvent. When using lanthanide halides, lanthanide oxyhalides, or other lanthanide compounds containing halogen atoms, the lanthanide compound may optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0106] As used herein, the term "organolanthanide compound" refers to any lanthanide compound containing at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, compounds containing cyclopentadienyl ("cyclopentadienyl, Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Organolanthanide compounds suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, where Ln represents a lanthanide atom and R represents a hydrocarbyl or substituted hydrocarbyl group. In one or more embodiments, the hydrocarbyl or substituted hydrocarbyl groups useful in certain embodiments of the polymerization process may contain heteroatoms such as nitrogen atoms, oxygen atoms, boron atoms, silicon atoms, sulfur atoms, and phosphorus atoms.

[0107] As mentioned above, the lanthanide-based catalyst system used in certain embodiments of the polymerization process includes an alkylating agent. According to one or more embodiments of the polymerization process, the alkylating agent (which may also be referred to as a hydrocarbylating agent) includes organometallic compounds capable of transferring one or more hydrocarbyl groups to another metal. Generally, these agents include organometallic compounds of electropositive metals, such as Group 1, Group 2, and Group 3 metals (Groups IA, IIA, and IIIA metals). Alkylating agents useful in certain embodiments of the polymerization process include, but are not limited to, organoaluminum compounds and organomagnesium compounds. As used herein, the term "organoaluminum compound" refers to any aluminum-containing compound having at least one aluminum-carbon bond. In one or more embodiments, an organoaluminum compound that is soluble in a hydrocarbon solvent may be used. As used herein, the term "organomagnesium compound" refers to any magnesium-containing compound having at least one magnesium-carbon bond. In one or more embodiments, an organomagnesium compound that is soluble in a hydrocarbon solvent may be used. As described in more detail below, certain suitable alkylating agents may be in the form of a halide compound. Wherein the alkylating agent comprises a halogen atom, the alkylating agent can also optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0108] In one or more embodiments, the organoaluminum compounds utilized include those represented by the general formula AlRanX3-n, where each Ra is independently a monovalent organic group bonded to an aluminum atom through a carbon atom, each X is independently a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and n is an integer ranging from 1 to 3. In one or more embodiments, each Ra is independently a hydrocarbyl or substituted hydrocarbyl group, including, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl groups, each group containing from 1 carbon atom or the appropriate minimum number of atoms to form a group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may optionally contain heteroatoms including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0109] Examples of the types of organoaluminum compounds represented by the general formula AlRanX- for use as alkylating agents in the process of the first embodiment include, but are not limited to, trihydrocarbylaluminum, dihydrocarbylaluminum hydrides, hydrocarbylaluminum dihydrides, dihydrocarbylaluminum carboxylates, hydrocarbylaluminum bis(carboxylates), dihydrocarbylaluminum alkoxides, hydrocarbylaluminum dialkoxides, dihydrocarbylaluminum halides, hydrocarbylaluminum dihalides, dihydrocarbylaluminum aryloxides, and hydrocarbylaluminum diaryloxide compounds.

[0110] Examples of trihydrocarbylaluminum compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-t-butylaluminum, tri-n-pentylaluminum, trineopentylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tris(2-ethylhexyl)aluminum, tricyclohexylaluminum, tris(1-methylcyclopentyl)aluminum, triphenylaluminum, tri-p-tolylaluminum, tris(2,6-dimethylphenyl)aluminum, tribenzylaluminum, diethylphenylaluminum, diethyl-p-tolylaluminum, diethylbenzylaluminum, ethyldiphenylaluminum, ethyldi-p-tolylaluminum, and ethyldibenzylaluminum.

[0111] Examples of dihydrocarbylaluminum hydride compounds suitable for use as alkylating agents in the process of the first embodiment include diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, and phenylisobutylaluminum hydride. Examples of aluminum hydride include, but are not limited to, aluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride.

[0112] Examples of hydrocarbylaluminum dihydrides suitable for use as alkylating agents in the process include, but are not limited to, ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0113] Examples of dihydrocarbylaluminum halide compounds suitable for use as alkylating agents in the process of the first embodiment include diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, phenylethylaluminum chloride, phenyl-n-propylaluminum chloride, phenylisopropylaluminum chloride, phenyl-n-butylaluminum chloride, phenylisobutylaluminum chloride, and phenylisobutylaluminum chloride. Aluminum chloride, phenyl-n-octyl aluminum chloride, p-tolylethyl aluminum chloride, p-tolyl-n-propyl aluminum chloride, p-tolyl isopropyl aluminum chloride, p-tolyl-n-butyl aluminum chloride, p-tolyl isobutyl aluminum chloride, p-tolyl-n-octyl aluminum chloride, benzyl ethyl aluminum chloride, benzyl-n-propyl aluminum chloride, benzyl isopropyl aluminum chloride, benzyl-n-butyl aluminum chloride, benzyl isobutyl aluminum chloride, and benzyl-n-octyl aluminum chloride.

[0114] Examples of hydrocarbylaluminum dihalide compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride.

[0115] Examples of other organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment, represented by the general formula AlRanX3-n, include dimethylaluminum hexanoate, diethylaluminum octoate, diisobutylaluminum 2-ethylhexanoate, dimethylaluminum neodecanoate, diethylaluminum stearate, diisobutylaluminum oleate, methylaluminum bis(hexanoate), ethylaluminum bis(octoate), isobutylaluminum bis(2-ethylhexanoate), methylaluminum bis(neodecanoate), ethylaluminum bis(stearate), isobutylaluminum bis(oleate), dimethyl ... Examples of suitable aluminum methoxides include, but are not limited to, dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dimethylaluminum phenoxide, diethylaluminum phenoxide, diisobutylaluminum phenoxide, methylaluminum dimethoxide, ethylaluminum dimethoxide, isobutylaluminum dimethoxide, methylaluminum diethoxide, ethylaluminum diethoxide, isobutylaluminum diethoxide, methylaluminum diphenoxide, ethylaluminum diphenoxide, and isobutylaluminum diphenoxide.

[0116] Another class of organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment are the aluminoxanes. Suitable aluminoxanes include oligomeric linear aluminoxanes, which can be represented by the general formula:

[0117] [ka] and oligomeric cyclic aluminoxanes which can be represented by the following general formula:

[0118] [ka] In the formula, x is an integer ranging from 1 to 100 (e.g., 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100), or from 10 to 50 (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50), y is an integer ranging from 2 to 100 (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100), or from 3 to 20 (e.g., 3, 5, 10, 15, or 20), and each R is independently a monovalent organic group bonded to the aluminum atom via a carbon atom. In certain embodiments, each R is independently a hydrocarbyl or substituted hydrocarbyl group, including but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl groups, each group preferably containing 1 carbon atom or the appropriate minimum number of atoms to form a group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may also contain heteroatoms, including but not limited to nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. As used herein, the number of moles of aluminoxane refers to the number of moles of aluminum atoms, not the number of moles of oligomeric aluminoxane molecules. This practice is commonly used in the art of catalyst systems utilizing aluminoxanes.

[0119] Aluminoxanes can be prepared by reacting a trihydrocarbylaluminum compound with water, which can be carried out by known methods such as, for example, (1) dissolving the trihydrocarbylaluminum compound in an organic solvent followed by contact with water, (2) reacting the trihydrocarbylaluminum compound with crystalline water, for example contained in a metal salt, or with water adsorbed on an inorganic or organic compound, or (3) reacting the trihydrocarbylaluminum compound with water in the presence of the monomer or monomer solution to be polymerized.

[0120] Examples of aluminoxane compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, methylaluminoxane ("methylaluminoxane, MAO"), modified methylaluminoxane ("modified methylaluminoxane, MMAO"), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane, and 2,6-dimethylphenylaluminoxane. In certain preferred embodiments of the process of the first embodiment, the alkylating agent comprises MAO. The modified methylaluminoxane can be prepared by converting 20 to 80 percent of the methyl groups of the methylaluminoxane to C2-C6 alkyl groups by using techniques known to those skilled in the art. 12 Hydrocarbyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , or C 12 ), preferably by substituting an isobutyl group.

[0121] According to certain embodiments of the polymerization process, aluminoxanes can be used alone or in combination with other organoaluminum compounds. In one embodiment, methylaluminoxane and at least one organoaluminum compound other than aluminoxane, such as organoaluminum compounds represented by AlRanX3-n, are used in combination as alkylating agents. According to this and other embodiments, the alkylating agent comprises dihydrocarbylaluminum hydride, dihydrocarbylaluminum halide, aluminoxane, or combinations thereof. For example, according to one embodiment, the alkylating agent comprises diisobutylaluminum hydride, diethylaluminum chloride, methylaluminoxane, or combinations thereof. U.S. Patent No. 8,017,695, the entirety of which is incorporated herein by reference, provides other examples of aluminoxanes and organoaluminum compounds that can be used in combination.

[0122] As mentioned above, suitable alkylating agents for use in the process of the first embodiment include organomagnesium compounds. According to one or more embodiments, suitable organomagnesium compounds include those represented by the general formula MgRb2, where each Rb is independently a monovalent organic group bonded to a magnesium atom via a carbon atom. In one or more embodiments, each Rb is independently a hydrocarbyl or substituted hydrocarbyl group, including but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, aryl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each group preferably containing from 1 carbon atom or the appropriate minimum number of atoms to form a group up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). The hydrocarbyl or substituted hydrocarbyl groups may also optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms.

[0123] Examples of organomagnesium compounds suitable for use as alkylating agents in the process of the first embodiment, represented by the general formula MgRb2, include, but are not limited to, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

[0124] Another class of organomagnesium compounds suitable for use as an alkylating agent according to certain embodiments of the polymerization process is represented by the general formula RcMgXc, where Rc is a monovalent organic group bonded to the magnesium atom through a carbon atom, and X is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group. In one or more embodiments, Rc is a hydrocarbyl or substituted hydrocarbyl group, including, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, aryl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each group containing from 1 carbon atom or the appropriate minimum number of atoms to form the group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may also contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. In one embodiment, Xc is a carboxylate, alkoxide, or aryloxide group, each group containing 1 to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms).

[0125] Examples of organomagnesium compounds of the type suitable for use as alkylating agents in certain embodiments, represented by the general formula RcMgXc, include, but are not limited to, hydrocarbyl magnesium hydrides, hydrocarbyl magnesium halides, hydrocarbyl magnesium carboxylates, hydrocarbyl magnesium alkoxides, and hydrocarbyl magnesium aryloxides.

[0126] Examples of organomagnesium compounds suitable for use as alkylating agents in certain embodiments represented by the general formula RcMgXc include methyl magnesium hydride, ethyl magnesium hydride, butyl magnesium hydride, hexyl magnesium hydride, phenyl magnesium hydride, benzyl magnesium hydride, methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, butyl magnesium bromide, hexyl magnesium bromide, phenyl magnesium bromide, benzyl magnesium bromide. Magnesium hexanoate, methyl magnesium hexanoate, ethyl magnesium hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate, phenyl magnesium hexanoate, benzyl magnesium hexanoate, methyl magnesium ethoxide, ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium ethoxide, phenyl magnesium ethoxide, benzyl magnesium ethoxide, methyl magnesium phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, and benzyl magnesium phenoxide.

[0127] As mentioned above, the lanthanide-based catalyst system used in the polymerization process of certain embodiments includes a halogen source. As used herein, the term "halogen source" refers to any material that includes at least one halogen atom. According to one or more embodiments, all or a portion of the halogen source may be optionally provided by the lanthanide compound, the alkylating agent, or both the lanthanide compound and the alkylating agent. In other words, the lanthanide compound can function as both the lanthanide compound and all or at least a portion of the halogen source. Similarly, the alkylating agent can function as both the alkylating agent and all or at least a portion of the halogen source.

[0128] According to certain embodiments, at least a portion of the halogen source may be present in the catalyst system in the form of separate and different halogen-containing compounds. Various compounds or mixtures thereof containing one or more halogen atoms may be used as halogen sources. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine, and iodine. Combinations of two or more halogen atoms may also be utilized. Halogen-containing compounds that are soluble in organic solvents, such as aromatic, aliphatic, and cycloaliphatic hydrocarbon solvents disclosed herein, are suitable for use as halogen sources in the process of the first embodiment. In addition, hydrocarbon-insoluble halogen-containing compounds that can be suspended in the polymerization system to form catalytically active species are also useful in certain embodiments of the process of the first embodiment.

[0129] Examples of types of halogen-containing compounds suitable for use in the process of the first embodiment include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, and organometallic halides. In certain preferred embodiments of the process of the first embodiment, the halogen-containing compound comprises an organometallic halide.

[0130] Examples of elemental halogens suitable for use as the halogen source in the process of the first embodiment include, but are not limited to, fluorine, chlorine, bromine, and iodine.Some specific examples of suitable mixed halogens include, but are not limited to, iodine monochloride, iodine monobromide, iodine trichloride, and iodine pentafluoride.

[0131] Examples of hydrogen halides suitable for use as the halogen source in the disclosed processes include, but are not limited to, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0132] Examples of organic halides suitable for use as a halogen source in the process of the first embodiment include, but are not limited to, t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

[0133] Examples of inorganic halides suitable for use as a halogen source in the process of the first embodiment include, but are not limited to, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, arsenic trichloride, arsenic tribromide, arsenic triiodide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, and tellurium tetraiodide.

[0134] Examples of metal halides suitable for use as a halogen source in the process of the first embodiment include, but are not limited to, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum triiodide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium triiodide, gallium trifluoride, indium trichloride, indium tribromide, indium triiodide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zinc dichloride, zinc dibromide, zinc diiodide, and zinc difluoride.

[0135] Examples of organometallic halides suitable for use as a halogen source in the process of the first embodiment include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methylaluminum dichloride, ethylaluminum di ... dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, isobutylaluminum Examples of suitable halogen sources include, but are not limited to, magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin bromide, di-t-butyl tin dichloride, di-t-butyl tin dibromide, dibutyl tin dichloride, dibutyl tin dibromide, tributyl tin chloride, and tributyl tin bromide. According to one embodiment, the halogen source comprises an organometallic halide. For example, according to a particular embodiment, the halogen source comprises diethyl aluminum chloride, which, as described above, can also function as an alkylating agent in a lanthanide-based catalyst system. Thus, according to a particular embodiment of the polymerization process, the halogen source may be provided in whole or in part by the alkylating agent in the catalyst system disclosed herein.

[0136] The lanthanide-based catalyst system used in certain embodiments of the polymerization process may be formed by combining or mixing the aforementioned catalyst components. The terms "catalyst composition" and "catalyst system" as referred to herein include a simple mixture of components, a composite of various components resulting from physical or chemical attraction, a chemical reaction product of the components, or a combination of the foregoing. The terms "catalyst composition" and "catalyst system" may be used interchangeably herein.

[0137] Nickel and other transition metal based catalyst systems As previously mentioned, the catalyst system used in the polymerization of 1,4-polybutadiene (i.e., prior to hydrogenation) may utilize a nickel-based catalyst system including (i) a nickel compound, optionally in combination with an alcohol, (ii) an organoaluminum, organomagnesium, organozinc compound, or combinations thereof, and (iii) a fluorine-containing compound or complexes thereof. The specific compounds used in each of (i), (ii), and (iii) may vary.

[0138] According to certain embodiments, the nickel compound used in the nickel-based catalyst system may vary. The nickel atom of the nickel-containing compound may be in various oxidation states, including but not limited to 0, +2, +3, and +4 oxidation states. Suitable nickel-containing compounds for use in the nickel-based catalyst system according to the process of the first embodiment include, but are not limited to, nickel carboxylates, nickel carboxylate borates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudohalides, nickel oxyhalides, and organonickel compounds. In a preferred embodiment, when a nickel-based catalyst system is used, the nickel compound is nickel carboxylate.

[0139] Suitable nickel carboxylates can include nickel formate, nickel acetate, nickel acrylate, nickel methacrylate, nickel valerate, nickel gluconate, nickel citrate, nickel fumarate, nickel lactate, nickel maleate, nickel oxalate, nickel 2-ethylhexanoate, nickel neodecanoate, nickel naphthenate, nickel stearate, nickel oleate, nickel benzoate, and nickel picolinate.

[0140] Suitable nickel carboxylate borates can include compounds defined by the formula (RCOONiO)3B or (RCOONiO)2B(OR), where each R, which can be the same or different, is a hydrogen atom or a monovalent organic group. In one embodiment, each R can be a hydrocarbyl group, such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl groups, each group preferably containing from 1 carbon atom (or the minimum number of carbon atoms suitable for forming a group) up to about 20 carbon atoms. These hydrocarbyl groups can contain heteroatoms, such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Nickel carboxylate borates can include those disclosed in U.S. Pat. No. 4,522,988, which is incorporated herein by reference. Specific examples of nickel carboxylate borates include nickel(II) neodecanoate borate, nickel(II) hexanoate borate, nickel(II) naphthenate borate, nickel(II) stearate borate, nickel(II) octoate borate, nickel(II) 2-ethylhexanoate borate, and mixtures thereof.

[0141] Suitable nickel organophosphates may include nickel dibutyl phosphate, nickel dipentyl phosphate, nickel dihexyl phosphate, nickel diheptyl phosphate, nickel dioctyl phosphate, nickel bis(1-methylheptyl)phosphate, nickel bis(2-ethylhexyl)phosphate, nickel didecyl phosphate, nickel didodecyl phosphate, nickel dioctadecyl phosphate, nickel dioleyl phosphate, nickel diphenyl phosphate, nickel bis(p-nonylphenyl)phosphate, nickel butyl(2-ethylhexyl)phosphate, nickel(1-methylheptyl)(2-ethylhexyl)phosphate, and nickel(2-ethylhexyl)(p-nonylphenyl)phosphate.

[0142] Suitable nickel organic phosphonates include nickel butyl phosphonate, nickel pentyl phosphonate, nickel hexyl phosphonate, nickel heptyl phosphonate, nickel octyl phosphonate, nickel (1-methylheptyl) phosphonate, nickel (2-ethylhexyl) phosphonate, nickel decyl phosphonate, nickel dodecyl phosphonate, nickel octadecyl phosphonate, nickel oleyl phosphonate, nickel phenyl phosphonate, nickel (p-nonylphenyl) phosphonate, nickel butyl butyl phosphonate, nickel pentyl pentyl phosphonate, nickel hexyl hexyl phosphonate, nickel heptyl heptyl phosphonate, nickel octyloctyl phosphonate, nickel (1-methylheptyl) (1-methylheptyl) phosphonate, phosphonate, nickel (2-ethylhexyl) (2-ethylhexyl) phosphonate, nickel decyl decyl phosphonate, nickel dodecyl dodecyl phosphonate, nickel octadecyl octadecyl phosphonate, nickel oleyl oleyl phosphonate, nickel phenyl phenyl phosphonate, nickel (p-nonylphenyl) (p-nonylphenyl) phosphonate, nickel butyl (2-ethylhexyl) phosphonate, nickel (2-ethylhexyl) butyl phosphonate, nickel (1-methylheptyl) (2-ethylhexyl) phosphonate, nickel (2-ethylhexyl) (1-methylheptyl) phosphonate, nickel (2-ethylhexyl) (p-nonylphenyl) phosphonate, and nickel (p-nonylphenyl) (2-ethylhexyl) phosphonate.

[0143] Suitable nickel organophosphinates include nickel butyl phosphinate, nickel pentyl phosphinate, nickel hexyl phosphinate, nickel heptyl phosphinate, nickel octyl phosphinate, nickel (1-methylheptyl) phosphinate, nickel (2-ethylhexyl) phosphinate, nickel decyl phosphinate, nickel dodecyl phosphinate, nickel octadecyl phosphinate, nickel oleyl phosphinate, nickel phenyl phosphinate, nickel (p-nonylphenyl) phosphinate, nickel dibutyl phosphinate, nickel dipentyl phosphinate, nickel dihexyl phosphinate. , nickel diheptyl phosphinate, nickel dioctyl phosphinate, nickel bis(1-methylheptyl)phosphinate, nickel bis(2-ethylhexyl)phosphinate, nickel didecyl phosphinate, nickel didodecyl phosphinate, nickel dioctadecyl phosphinate, nickel dioleyl phosphinate, nickel diphenyl phosphinate, nickel bis(p-nonylphenyl)phosphinate, nickel butyl(2-ethylhexyl)phosphinate, nickel(1-methylheptyl)(2-ethylhexyl)phosphinate, and nickel(2-ethylhexyl)(p-nonylphenyl)phosphinate.

[0144] Suitable nickel carbamates can include nickel dimethyl carbamate, nickel diethyl carbamate, nickel diisopropyl carbamate, nickel dibutyl carbamate, and nickel dibenzyl carbamate.

[0145] Suitable nickel dithiocarbamates include nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel diisopropyldithiocarbamate, nickel dibutyldithiocarbamate, and nickel dibenzyldithiocarbamate.

[0146] Suitable nickel xanthates include nickel methyl xanthate, nickel ethyl xanthate, nickel isopropyl xanthate, nickel butyl xanthate, and nickel benzyl xanthate.

[0147] Suitable nickel diketonates include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylacetonate, and nickel 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0148] Suitable nickel alkoxides or aryloxides can include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel 2-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, and nickel naphthoxide.

[0149] Suitable nickel halides include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide. Nickel pseudohalides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide, and nickel ferrocyanide. Nickel oxyhalides include nickel oxyfluoride, nickel oxychloride, and nickel oxybromide. When nickel halide, nickel oxyhalide, or other nickel-containing compounds contain labile fluorine or chlorine atoms, the nickel-containing compounds can also function as fluorine-containing or chlorine-containing compounds. Lewis bases such as alcohols can be used as solubilizing agents for this class of compounds.

[0150] The term "organic nickel compound" may refer to any nickel compound that contains at least one nickel-carbon bond. Organonickel compounds include bis(cyclopentadienyl)nickel (also called nickelocene), bis(pentamethylcyclopentadienyl)nickel (also called decamethylnickelocene), bis(tetramethylcyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(isopropylcyclopentadienyl)nickel, bis(pentadienyl)nickel, bis(2,4-dimethylpentadienyl)nickel, (cyclopentadienyl)(pentadienyl)nickel, bis(1,5-cyclooctadiene)nickel, bis(allyl)nickel, bis(methallyl)nickel, and bis(crotyl)nickel.

[0151] According to certain embodiments, the organoaluminum, organomagnesium, organozinc compounds, or combinations thereof used in the (ii) component of the nickel-based catalyst system can be changed. In a preferred embodiment, when the polymerization process utilizes a nickel-based catalyst system, component (ii) is an organoaluminum or organomagnesium compound, more preferably an organoaluminum compound. If the organoaluminum, organomagnesium, or organozinc compound contains labile fluorine, it can also function as a fluorine-containing compound (without the need for a separate fluorine-containing compound). In certain embodiments, the organoaluminum, organomagnesium, or organozinc compound does not contain chlorine or bromine atoms.

[0152] Compounds suitable for use as the organoaluminum or organomagnesium compounds in nickel-based catalyst systems are discussed above in the section on lanthanide-based catalyst systems.

[0153] According to certain embodiments, the fluorine-containing compound used in the nickel-based catalyst system may vary. Suitable fluorine-containing compounds may include various compounds or mixtures thereof that contain one or more labile fluorine atoms. In one or more embodiments, the fluorine-containing compound may be soluble in a hydrocarbon solvent. In other embodiments, a hydrocarbon-insoluble fluorine-containing compound that can be suspended in the polymerization medium to form catalytically active species may be useful.

[0154] Suitable types of fluorine-containing compounds include, but are not limited to, elemental fluorine, halogen fluorides, hydrogen fluoride, organic fluorides, inorganic fluorides, metal fluorides, organometallic fluorides, and mixtures thereof. In one or more embodiments, complexes of fluorine-containing compounds with Lewis bases such as ethers, alcohols, water, aldehydes, ketones, esters, nitriles, or mixtures thereof may be used. Specific examples of these complexes include complexes of boron trifluoride with Lewis bases of hydrogen fluoride.

[0155] Halofluorides can include iodine monofluoride, iodine trifluoride, and iodine pentafluoride.

[0156] Organic fluorides can include t-butyl fluoride, allyl fluoride, benzyl fluoride, fluoro-di-phenylmethane, triphenylmethyl fluoride, benzylidene fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methylfluoroformate.

[0157] Inorganic fluorides can include phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxyfluoride, boron trifluoride, silicon tetrafluoride, arsenic trifluoride, selenium tetrafluoride, and tellurium tetrafluoride.

[0158] Metal fluorides can include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

[0159] Examples of organometallic fluorides include dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquifluoride, ethylaluminum sesquifluoride, isobutylaluminum sesquifluoride, methylmagnesium fluoride, ethylmagnesium fluoride, butylmagnesium fluoride, phenylmagnesium fluoride, benzylmagnesium fluoride, trimethyltin fluoride, triethyltin fluoride, di-t-butyltin difluoride, dibutyltin difluoride, and tributyltin fluoride.

[0160] As mentioned above, when the polymerization process utilizes a nickel-based catalyst system, the nickel compound may be used in combination with an alcohol. A variety of alcohols and mixtures may be used. In one or more embodiments, the alcohol comprises a monohydric alcohol (i.e., one that contains one hydroxyl group), while in other embodiments, the alcohol comprises a polyhydric alcohol (i.e., one that contains two or more hydroxyl groups), including dihydric alcohols, which may be referred to as glycols or diols, trihydric alcohols, which may be referred to as glycerol, and polyhydric alcohols. In one or more embodiments, the alcohol comprises a primary and / or secondary alcohol. Primary and secondary alcohols include alcohols in which the α-carbon (i.e., the carbon adjacent to the carbon containing the hydroxyl group) is primary or secondary. In certain preferred embodiments, when a nickel-based catalyst system is used, a monohydric alcohol, preferably hexanol, is utilized.

[0161] The alcohol may comprise an aliphatic alcohol, including a straight chain or branched chain alcohol, in other embodiments, the alcohol may comprise a cyclic alcohol, in other embodiments, an aromatic alcohol, in other embodiments, a heterocyclic alcohol, and in other embodiments, a polycyclic alcohol.

[0162] In these or other embodiments, the alcohols may be saturated, while in other embodiments they may be unsaturated. In certain embodiments, useful alcohols include those that are soluble or at least partially soluble in the reaction medium in which the polymerization is carried out.

[0163] In one or more embodiments, useful alcohols may be defined by the formula R-OH, where R is a monovalent organic group and -OH is a hydroxyl group. The monovalent organic group may include hydrocarbyl or substituted hydrocarbyl groups, such as alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, alkenyl groups, cycloalkenyl groups, substituted cycloalkenyl groups, aryl groups, aryl groups, substituted aryl groups, aralkyl groups, alkaryl groups, alkynyl groups, and the like. Substituents include groups in which the hydrogen atoms of the group are themselves replaced with monovalent organic groups. These hydrocarbyl groups may contain heteroatoms, such as, but not limited to, nitrogen, oxygen, silicon, tin, sulfur, boron, and phosphorus atoms. In certain embodiments, the hydrocarbyl group may not contain halogen atoms, such as chlorine or bromine atoms. In certain embodiments, the monovalent organic group may contain one or more hydroxyl groups attached thereto. As a result, the alcohol may contain two or more hydroxyl groups. In other embodiments, the hydrocarbyl groups do not contain heteroatoms.

[0164] In one or more embodiments, useful alcohols include those having from 1 to about 40 carbon atoms, in other embodiments from about 2 to about 26 carbon atoms, in other embodiments from about 4 to about 18 carbon atoms, and in other embodiments from about 6 to about 12 carbon atoms.

[0165] Exemplary aliphatic alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, isobutanol, n-pentanol, n-hexanol, 2-ethylhexanol, n-heptanol, octanol, decanol, and mixtures thereof.

[0166] Exemplary cyclic alcohols include cyclohexanol, methanol, t-butylcyclohexanol, cyclopentanol, cycloheptanol, cyclooctanol, and mixtures thereof.

[0167] Exemplary unsaturated alcohols include allyl alcohol, and mixtures thereof.

[0168] Exemplary aromatic alcohols include substituted phenols, phenol, benzyl alcohol, and mixtures thereof.

[0169] Exemplary heterocyclic alcohols include furfuryl alcohol, and mixtures thereof.

[0170] Exemplary polycyclic alcohols include sterols, and mixtures thereof.

[0171] The aforementioned catalyst composition may have high catalytic activity for polymerizing conjugated dienes into stereospecific polydienes over a wide range of catalyst concentrations and catalyst component ratios. It is believed that the catalyst components may interact to form active catalyst species. It is also believed that the optimal concentration of any one catalyst component may depend on the concentration of the other catalyst components.

[0172] In one or more embodiments, the molar ratio of (ii) component to nickel-containing compound can vary from about 1:1 to about 200:1, in other embodiments from about 3:1 to about 30:1, and in other embodiments from about 5:1 to about 15:1. As used herein, the term molar ratio refers to the equivalent ratio of the relevant constituents of the components, e.g., the ratio of equivalents of aluminum atoms on the aluminum-containing compound to equivalents of nickel atoms on the nickel-containing compound. In other words, when a bifunctional or polyfunctional compound (e.g., a compound containing two or more carboxylic acid groups) is used, fewer moles of the compound are required to achieve the desired equivalent ratio.

[0173] In one or more embodiments, the molar ratio of the fluorine-containing compound to the nickel-containing compound (F / Ni) can vary from about 7:1 to about 500:1, in other embodiments from about 7.5:1 to about 450:1, and in other embodiments from about 8:1 to about 400:1.

[0174] In one or more embodiments, the molar ratio of alcohol to nickel-containing compound (-OH / Ni) can vary from about 0.4:1 to about 80:1, in other embodiments from about 0.5:1 to about 75:1, and in other embodiments from about 0.7:1 to about 65:1. As used herein, the term molar ratio refers to the ratio of equivalents of the relative components of the components, e.g., the ratio of equivalents of chlorine atoms of a chlorine-containing compound to equivalents of nickel atoms of a nickel-containing compound.

[0175] In general, nickel-based catalyst systems may be formed by combining or mixing catalyst components. It is believed that an active catalytic species results from this combination, but the various catalyst components or the degree of interaction or reaction between the components is not very precisely known. Thus, the term "catalyst system" is used to encompass a simple mixture of the components, a complex of the various components resulting from physical or chemical attractions, a chemical reaction product of the components, or a combination of the above.

[0176] The nickel-based catalyst system can be formed by using one of the following methods. In one or more embodiments, the nickel-based catalyst system can be formed in situ by adding the catalyst components to a solution containing monomer and solvent (or simply bulk monomer) in either a stepwise or simultaneous manner. In one embodiment, (ii) a mixture of the components, the nickel-containing compound, and the alcohol (if present) is formed. This mixture may be formed in a solvent. This mixture and the fluorine-containing compound may then be added to the monomer to be polymerized.

[0177] In one or more embodiments, the selected catalyst components of the nickel-based catalyst system may be premixed outside the polymerization system at a suitable temperature, which may be from about −20° C. to about 80° C., and the resulting catalyst system may be aged for a period ranging from a few seconds to a few days and then added to the monomer.

[0178] In one or more embodiments, the mixture of component (ii), nickel-containing compound, and alcohol (if present) is formed in the presence of a small amount of monomer and optionally a solvent. That is, the selected catalyst components may be formed in the presence of a small amount of conjugated diene monomer at a suitable temperature, which may be from about 20° C. to about 80° C. The amount of conjugated diene monomer that may be used to form this mixture may range from about 1 to about 500 moles, in other embodiments from about 5 to about 250 moles, and in other embodiments from about 10 to about 100 moles, per mole of nickel-containing compound. The resulting composition may be aged for a period ranging from a few seconds to a few days, and then added to the remainder of the conjugated diene monomer to be polymerized together with the fluorine-containing compound.

[0179] As described in the above method, when a solution of the nickel-based catalyst system or one or more of its catalyst components is prepared outside the polymerization system, an organic solvent or carrier may be used. The organic solvent may function to dissolve the catalyst composition or components, or the solvent may function as a carrier in which the catalyst composition or components may be suspended. The organic solvent may be inert to the catalyst composition. Useful solvents include aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and / or mixtures of two or more thereof. Non-limiting examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, diethylbenzene, and mesitylene. Non-limiting examples of aliphatic hydrocarbon solvents include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, and petroleum spirits. Non-limiting examples of cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Commercial mixtures of the above hydrocarbons may also be used.

[0180] Various hydrogenation methods are contemplated as suitable for hydrogenating 1,4-polybutadiene to form the partially hydrogenated 1,4-polybutadiene of the present disclosure. In embodiments, the hydrogenation reaction pressure may be from about 100 kPa to about 2500 kPa. In certain embodiments, the hydrogenation reaction temperature may be from about 20° C. to about 200° C. The hydrogenation reaction time depends on the degree of saturation achieved and the amount of initial unsaturation. In one or more embodiments, the hydrogenation reaction time may be from about 0.5 hours to about 5 hours.

[0181] In certain embodiments, the hydrogenation is carried out in solution in an inert hydrocarbon, hi other embodiments, the hydrogenation is carried out using a heterogeneous hydrogenation catalyst.

[0182] In an embodiment, the hydrogenation catalyst is a metal catalyst.

[0183] In certain embodiments, the metal catalyst for hydrogenation may include aluminum, such as an organoaluminum compound, which may be the same or similar to the organoaluminum compounds described above with respect to the catalyst used for the polymerization of 1,4-polybutadiene (i.e., prior to hydrogenation).

[0184] In certain embodiments, the metal catalyst for hydrogenation may include a transition metal compound such as nickel, ruthenium, rhodium, palladium, iridium, platinum, or a combination thereof.

[0185] The transition metal atom in the transition metal compound can be in various oxidation states, including, but not limited to, 0, +2, +3, and +4 oxidation states. Transition metal compounds include, but are not limited to, metal carboxylates, metal carboxylate borates, metal organophosphates, metal organophosphonates, metal organophosphinates, metal carbamates, metal dithiocarbamates, metal xanthates, metal β-diketonates, metal alkoxides or aryloxides, metal halides, metal pseudohalides, metal oxyhalides, and organometallic compounds.

[0186] The nickel compounds used in the hydrogenation can be the same or similar to those described above with respect to the catalysts used in the polymerization of 1,4-polybutadiene. Without wishing to limit the practice of the methods disclosed herein, the discussion herein focuses on nickel compounds, but one of ordinary skill in the art will be able to select similar compounds based on other transition metals.

[0187] In some embodiments, the hydrogenation catalyst may comprise at least one nickel compound and at least one aluminum compound. For hydrogenation catalysts comprising nickel and aluminum, the aluminum may also comprise an organoaluminum compound. The nickel and aluminum may be included in various amounts. For example, the aluminum and nickel may be added in an Al / Ni molar ratio of 1:1 to 5:1, or 2:1 to 4:1. EXAMPLES

[0188] The polymers described herein are further described in the following examples, which are not intended to limit the polymers.

[0189] Measurements The number average molecular weight (Mn) and weight average molecular weight (Mw) were determined by gel permeation chromatography using a TOSOH Esosec HLC-8320 GPC system and a TOSOH TSKgel GMHxl-BS column with THF as the solvent. The system was calibrated using polystyrene standards.

[0190] Cis content, vinyl content, and hydrogenation level were measured in tetrachloroethane-d2 at 80°C. 1 Determined by 1 H-nuclear magnetic resonance spectroscopy.

[0191] "Enthalpy of fusion ΔH m " and "glass transition temperature T g " was measured by differential scanning calorimetry. The differential scanning calorimetry method involved a starting temperature of 23°C, heating to 200°C at a ramp rate of 10°C / min, cooling to -120°C, and reheating to 200°C at a ramp rate of 10°C / min.

[0192] Example 1 - Synthesis of high cis 1,4-polybutadiene To a nitrogen purged reactor were added 113.09 g of anhydrous hexane and 219.90 g of 21.2 wt% 1,3-butadiene in hexane. 0.25 mL of 1.0 M diisobutylaluminum in hexane and 0.452 M neodymium finishing catalyst in hexane (COMCAT Nd-FC from Comar Chemicals) were added sequentially to the mixture in the reactor. The mixture was placed in a stirring bath at 50° C. After stirring for 60 minutes, the polymerization was stopped by charging the polymerization mixture with 0.1 ml of isopropanol to produce Polymer A, high cis 1,4-polybutadiene, the properties of which are shown in Table 1.

[0193] [Table 1]

[0194] Example 2 - Hydrogenation of high cis 1,4-polybutadiene 20 mL of polymer A in hexane from Example 1 was introduced into each of the three optimized sample reactors of the off-chain synthesis unit under nitrogen atmosphere, and the reactors were sealed. The reactors were purged three times with 345 kPa hydrogen, and the reactor jackets were heated to 50°C. Into a nitrogen-purged dry bottle, 11.5 mL of hexane and 0.63 mL of 1.03 M trityl aluminum were added, followed by 0.70 mL of nickel octanoate (1.59 wt% nickel in hexane), to obtain Ni / Al catalyst (Al / Ni=3.3 / 1.0). The reactors were pressurized to 517 kPa with hydrogen, and 1.0 mL of Ni / Al catalyst was transferred to each reactor. After 15-180 minutes of hydrogenation reaction, hydrogen was released from the reactors, the polymers were coagulated, and drum-dried at 120°C to produce hydrogenated polymers HA, HB, and HC, hydrogenated high cis 1,4-polybutadiene. The properties of polymer A and the hydrogenated polymers HA, HB, and HC are shown in Table 2.

[0195] [Table 2]

[0196] The hydrogenated polymers HA, HB, and HC, having a degree of hydrogenation of 9%, 25%, and 35%, respectively, exhibited lower first enthalpies of fusion ΔH compared to polymer A. m1 (J / g), indicating resistance to crystallite formation of cis-1,4-butadiene units. As illustrated in Table 2, the hydrogenated high cis-1,4-polybutadiene has improved resistance to crystallite formation of cis-1,4-butadiene units, even at relatively low levels of hydrogenation (e.g., 10% or less).

[0197] The hydrogenated polymers HB and HC have a higher high-temperature melting enthalpy ΔH compared to the hydrogenated polymer HA. m2(J / g), indicating an increase in the formation of crystallites resulting from hydrogenation. As illustrated in Table 2, as the degree of hydrogenation of the high cis 1,4-polybutadiene increases, the hydrogenated high cis 1,4-polybutadiene exhibits an increase in the formation of crystallites resulting from hydrogenation.

[0198] The hydrogenated polymers HA, HB, and HC have glass transition temperatures T similar to those of polymer A. g As illustrated in Table 2, the hydrogenated high cis 1,4-polybutadiene has a relatively low glass transition temperature T g , which can be useful for obtaining good tire tread wear and snow traction.

[0199] The embodiments may be further described with respect to the following clauses. 1. A polymer comprising partially hydrogenated 1,4-polybutadiene having a cis content of about 50% to about 96%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%, wherein the partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of about 3% to about 50%. 2. The polymer of clause 1, wherein the partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of about 5% to about 50%. 3. The polymer according to clause 1 or 2, wherein the degree of hydrogenation is from about 10% to about 50%, or from 15% to about 50%, or from about 20% to about 50%. 4. Hydrogenated 1,4-polybutadiene has a glass transition temperature T of about -115°C to about -95°C. g 4. The polymer according to any one of clauses 1 to 3, having the following structure: 5. The hydrogenated 1,4-polybutadiene is melted at a first melting temperature T m1 5. The polymer according to any one of clauses 1 to 4, having the following structure: 6. The polymer of any one of clauses 1-5, wherein the hydrogenated 1,4-polybutadiene has a second melting temperature of about 100° C. to about 140° C. 7. The hydrogenated 1,4-polybutadiene has a first enthalpy of fusion ΔH of about 3 J / g to about 50 J / g when measured at a temperature of about -30°C to about 0°C. m17. The polymer according to any one of clauses 1 to 6, having the following structure: 8. The hydrogenated 1,4-polybutadiene has a first enthalpy of fusion ΔH of about 0 J / g to about 45 J / g when measured at a temperature of about -30°C to about 0°C. m1 8. The polymer according to any one of clauses 1 to 7, having the following structure: 9. Hydrogenated 1,4-polybutadiene has a second enthalpy of fusion ΔH of about 0.5 J / g to about 20 J / g when measured at a temperature of up to about 140° C. m2 9. The polymer according to any one of clauses 1 to 8, having the following structure: 10. Hydrogenated 1,4-polybutadiene has a second enthalpy of fusion ΔH of about 0 J / g to about 20 J / g when measured at a temperature up to about 140° C. m2 10. The polymer according to any one of clauses 1 to 9, having the following structure: 11. The hydrogenated 1,4-polybutadiene has a weight average molecular weight M of about 100,000 g / mol to about 500,000 g / mol. w 11. The polymer according to any one of clauses 1 to 10, having the following structure: 12. A polymer chain attached to a residue of a functionalized compound having the following formula (I):

[0200] [ka] wherein X is a group reactive with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and anhydride; R1 is a C1-C 20 and each R' is selected from the group consisting of C1 to C 20 R" is selected from the group consisting of C1 to C6 20 and each polymer chain is attached to a residue of a functionalizing compound via an X group. 13. The polymer according to any one of clauses 1 to 12, wherein X in formula (I) is an epoxy group. 14. The polymer according to any one of clauses 1 to 13, wherein X in formula (I) is a glycidoxy group and the polymer chain is attached to a carbon atom from an epoxy group. 15. The polymer according to any one of clauses 1 to 14, wherein X in formula (I) is a cyano group. 16. A rubber composition comprising the polymer according to any one of clauses 1 to 15, a reinforcing filler, and a curing agent. 17. The rubber composition according to any one of clauses 1 to 16, wherein the rubber composition comprises from about 20 phr to about 50 phr of the polymer according to clause 1. 18. The rubber composition of any one of clauses 1-17, wherein the reinforcing filler comprises carbon black, silica, or a combination thereof, and the curative comprises sulfur. 19. The rubber composition according to any one of clauses 1 to 18, wherein the reinforcing filler comprises from about 1 phr to about 60 phr of carbon black. 20. The rubber composition according to any one of clauses 1 to 19, wherein the reinforcing filler comprises from about 25 phr to about 150 phr of silica. 21. The rubber composition of any one of clauses 1-20, further comprising a natural rubber, a synthetic rubber, or a combination thereof. 22. The rubber composition of any one of clauses 1-21, wherein the synthetic rubber comprises polybutadiene, polyisoprene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or combinations thereof. 23. The rubber composition according to any one of clauses 1 to 22, wherein the rubber composition comprises from about 1 phr to about 90 phr of natural rubber, synthetic rubber, or a combination thereof. 24. A method comprising: polymerizing a solution comprising 1,3-butadiene to obtain 1,4-polybutadiene having a cis content of about 50% to about 99.5%, a vinyl content of about 0.1% to about 1%, and a trans content of about 1% to about 10%, wherein the polymerization is catalyzed with a lanthanide metal complex or a nickel metal complex; and hydrogenating the 1,4-polybutadiene to form a hydrogenated 1,4-polybutadiene having a degree of hydrogenation of about 3% to about 50%, wherein the hydrogenation is catalyzed with a metal catalyst. 25. The method of any one of clauses 1 to 24, wherein the partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of about 5% to about 50%. 26. The method of any one of clauses 1 to 25, wherein the hydrogenated 1,4-polybutadiene has a cis content of about 50% to about 95%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%. 27. The method of any one of clauses 1-26, wherein the lanthanide metal complex comprises one or more of lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and didymium. 28. The method of any one of clauses 1 to 27, wherein the lanthanide metal complex comprises neodymium. 29. The method of any one of clauses 1-28, wherein the nickel metal complex comprises one or more of nickel carboxylates, nickel carboxylate borates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudohalides, nickel oxyhalides, and organonickel compounds. 30. The method of any one of clauses 1 to 29, wherein the nickel metal complex comprises a nickel carboxylate. 31. The method of any one of clauses 1 to 30, wherein the metal catalyst comprises nickel, aluminum, ruthenium, rhodium, palladium, iridium, platinum, or a combination thereof.

[0201] It will be apparent that modifications and variations are possible without departing from the scope of the present disclosure, as defined in the appended claims. More specifically, although certain aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to those aspects.

[0202] Patent application

Claims

1. A polymer comprising: a partially hydrogenated 1,4-polybutadiene having a cis content of about 50% to about 96%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%, The partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of from about 3% to about 50%.

2. 10. The polymer of claim 1, wherein the partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of from about 5% to about 50%.

3. 3. The polymer of claim 1 or 2, wherein the degree of hydrogenation is from about 10% to about 50%, or from 15% to about 50%, or from about 20% to about 50%.

4. The hydrogenated 1,4-polybutadiene has a glass transition temperature T ｇ The polymer according to any one of claims 1 to 3, having the formula:

5. The hydrogenated 1,4-polybutadiene has a first melting temperature T ｍ１ The polymer according to any one of claims 1 to 4, having the formula:

6. The polymer of any one of claims 1 to 5, wherein the hydrogenated 1,4-polybutadiene has a second melting temperature of from about 100°C to about 140°C.

7. The hydrogenated 1,4-polybutadiene has a first enthalpy of fusion ΔH of about 3 J / g to about 50 J / g when measured at a temperature of about −30° C. to about 0° C. ｍ１ The polymer according to any one of claims 1 to 6, having the formula:

8. The hydrogenated 1,4-polybutadiene has a first enthalpy of fusion ΔH of about 0 J / g to about 45 J / g when measured at a temperature of about −30° C. to about 0° C. ｍ１ The polymer according to any one of claims 1 to 6, having the formula:

9. The hydrogenated 1,4-polybutadiene has a second enthalpy of fusion ΔH of about 0.5 J / g to about 20 J / g when measured at a temperature up to about 140° C. ｍ２ The polymer according to any one of claims 1 to 8, having the formula:

10. The hydrogenated 1,4-polybutadiene has a second enthalpy of fusion ΔH of about 0 J / g to about 20 J / g when measured at a temperature up to about 140° C. ｍ２ The polymer according to any one of claims 1 to 8, having the formula:

11. The hydrogenated 1,4-polybutadiene has a weight average molecular weight M of about 100,000 g / mol to about 500,000 g / mol. ｗ The polymer according to any one of claims 1 to 10, having the formula:

12. having a polymer chain attached to a residue of a functionalized compound having the formula (I): 【Chemistry 1】 wherein X is a group reactive with a living end polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and anhydride; R １ But, C １ ~C ２０ is selected from the hydrocarbylenes Each R' is C １ ~C ２０ is selected from alkoxy or carboxy; R'' is C １ ~C ２０ Alkyl, alkoxy, or carboxy of C ６ ~C ２ aryl selected from aryl of The polymer of any one of claims 1 to 11, wherein each polymer chain is attached to the residue of the functionalizing compound via the X group.

13. The polymer of claim 12, wherein X in formula (I) is an epoxy group.

14. 14. The polymer of claim 12 or 13, wherein X in formula (I) is a glycidoxy group and the polymer chain is attached to a carbon atom from an epoxy group.

15. The polymer according to any one of claims 12 to 14, wherein X in formula (I) is a cyano group.

16. A rubber composition comprising: A polymer according to claim 1; A reinforcing filler; and a curing agent.

17. The rubber composition of claim 16, wherein the rubber composition comprises from about 20 phr to about 50 phr of the polymer of claim 1.

18. 18. The rubber composition of claim 16 or 17, wherein the reinforcing filler comprises carbon black, silica, or a combination thereof, and the curative comprises sulfur.

19. 20. The rubber composition of claim 18, wherein said reinforcing filler comprises from about 1 phr to about 60 phr of carbon black.

20. 20. The rubber composition of claim 18 or 19, wherein said reinforcing filler comprises from about 25 phr to about 150 phr of silica.

21. The rubber composition of any one of claims 16 to 20, further comprising a natural rubber, a synthetic rubber, or a combination thereof.

22. 22. The rubber composition of claim 21, wherein the synthetic rubber comprises polybutadiene, polyisoprene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or combinations thereof.

23. 23. The rubber composition of claim 21 or 22, wherein the rubber composition comprises from about 1 phr to about 90 phr of the natural rubber, the synthetic rubber, or a combination thereof.

24. 1. A method comprising: polymerizing a solution comprising 1,3-butadiene to obtain 1,4-polybutadiene having a cis content of about 50% to about 99.5%, a vinyl content of about 0.1% to about 1%, and a trans content of about 1% to about 10%, said polymerization being catalyzed by a lanthanide metal complex or a nickel metal complex; and hydrogenating the 1,4-polybutadiene to form a hydrogenated 1,4-polybutadiene having a degree of hydrogenation of about 3% to about 50%, wherein the hydrogenation is catalyzed with a metal catalyst.

25. The method of claim 24, wherein the partially hydrogenated 1,4-polybutadiene has a degree of hydrogenation of from about 5% to about 50%.

26. 26. The method of claim 24 or 25, wherein the hydrogenated 1,4-polybutadiene has a cis content of about 50% to about 95%, a vinyl content of about 0% to about 1%, and a trans content of about 1% to about 10%.

27. 27. The method of any one of claims 24 to 26, wherein the lanthanide metal complex comprises one or more of lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and didymium.

28. 28. The method of claim 27, wherein the lanthanide metal complex comprises neodymium.

29. 27. The method of any one of claims 24 to 26, wherein the nickel metal complex comprises one or more of nickel carboxylates, nickel carboxylate borates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudohalides, nickel oxyhalides, and organonickel compounds.

30. 30. The method of claim 29, wherein the nickel metal complex comprises a nickel carboxylate.

31. The method of any one of claims 24 to 30, wherein the metal catalyst comprises nickel, aluminum, ruthenium, rhodium, palladium, iridium, platinum, or a combination thereof.

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