WO2014120433A1

WO2014120433A1 - Preparation of bottlebrush polymers via ring-opening metathesis polymerization

Info

Publication number: WO2014120433A1
Application number: PCT/US2014/011457
Authority: WO
Inventors: Ian C. STEWART; David T. Harris
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2013-01-30
Filing date: 2014-01-14
Publication date: 2014-08-07

Abstract

This invention relates to a reaction product obtained by ring-opening metathesis polymerization of norbornene ketones functionalized with the residual portion of a vinyl terminated macromonomer.

Description

PREPARATION OF BOTTLEBRUSH POLYMERS VIA RING-OPENING

METATHESIS POLYMERIZATION

PRIORITY CLAIM

This application claims priority to and the benefit of US Provisional Application No.

61/758,535, filed January 30, 2013 and EP 13160933.1 filed March 25, 2013.

FIELD OF THE INVENTION

This invention relates to the preparation of highly-branched bottlebrush polymers derived from vinyl-terminated polymers via ring-opening metathesis polymerization.

BACKGROUND OF THE INVENTION

Metathesis is generally thought of as the interchange of radicals between two compounds during a chemical reaction. There are several varieties of metathesis reactions, such as ring opening metathesis, acyclic diene metathesis, ring closing metathesis, and cross metathesis. These reactions, however, have had limited success with the metathesis of functionalized olefins.

Methods for the production of polyolefins with end-functionalized groups are typically multi-step processes that often create unwanted by-products and waste of reactants and energy.

R. T. Mathers and G. W. Coates Chem. Commun., 2004, pp. 422-423 disclose examples of using cross-metathesis to functionalize polyolefins containing pendant vinyl groups to form polar- functionalized products with a graft-type structure.

D. Astruc et al. J. Am. Chem. Soc. 2008, 130, pp. 1495-1506, and D. Astruc et al. Angew. Chem. Int. Ed., 2005, 44, pp. 7399-7404 disclose examples of using cross metathesis to functionalize non-polymeric molecules containing vinyl groups.

For reviews of methods to form end-functionalized polyolefins, see: (a) S. B. Amin and T. J. Marks, Angew. Chem. Int. Ed, 2008, 47, pp. 2006-2025; (b) T. C. Chung Prog. Polym. Scl, 2002, 27, pp. 39-85; and (c) R. G. Lopez, F. D'Agosto, C. Boisson Prog. Polym. Scl, 2007, 32, pp. 419-454.

USSN 12/487,739, filed June 19, 2009 discloses certain vinyl terminated oligomers and polymers that are functionalized, optionally, for use in lubricant applications.

USSN 12/143,663, filed on June 20, 2008 discloses certain vinyl terminated oligomers and polymers that are functionalized in USSN 12/487,739, filed June 19, 2009. US 8,283,428 and USSN 13/629,323, filed 9/27/2012, provide polymacromonomers useful for functionalization.

USSN 12/488,093, filed June 19, 2009 discloses end functionalized polyolefins prepared from vinyl terminated polyolefins by cross metathesis.

Additional references of interest include U.S. Patent Nos. 4,988,764; 6,225,432; 6,1 11,027; 7, 183,359; 6, 100,224; 5,616, 153; PCT Publication Nos. WO 03/025084; WO 03/025038; WO 03/025037; WO 03/025036; WO 99/016845 and Amelia M. Anders on- Wilfe et al, "Synthesis and Ring-Opening Metathesis Polymerization of Norbornene-Terminated Syndiotactic Polypropylene", Macromolecules, 2012, 45 (19), pp. 7863-7877, published (web) 9/19, 2012.

Thus, metathesis reactions can provide functionalized polyolefins that have end- functionalization. However, to date it has not been feasible to polymerize polyolefins having end-functionalization to each other.

Thus, a need exists for a method to prepare polyolefins that utilize end- functionalization to provide new polymers with unique physical properties.

SUMMARY OF THE INVENTION

This invention relates to the reaction product obtained by contacting: 1) a metathesis catalyst, and 2) a C2 to a C40 vinyl or vinylene containing monomer, with 3) a composition represented by the formula:

where VTM is the residual terminal portion of a vinyl terminated macromonomer and

R³ is a CI to a C40 hydrocarbyl group, each R is, independently, H or a CI to C40 hydrocarbyl group (preferably a substituted or unsubstituted alkyl or substituted or unsubstituted aryl) and R⁷ is a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, X is C or a heteroatom (such as N, O, S, or P) and z is 0 or 1. In one aspect, the reaction product can be characterized as a composition having the formula:

wherein VTM is the residual terminal portion of a vinyl terminated macromonomer; each R¹, R², R⁴ and R⁵, independently, a C2 to C40 hydrocarbyl group, (such as a residual portion of a vinyl C2 to a C40 monomer or vinylidene C3 to a C40 monomer);

R³ is a CI to a C40 hydrocarbyl group;

each R is, independently, H or a CI to C40 hydrocarbyl group;

R⁷ is a substituted or unsubstituted alkyl or substituted or unsubstituted aryl;

X is C or a heteroatom (such as N, O, S, or P);

z is 0 or 1 ; and

n is from 2 to 2000.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 provides intrinsic viscosity versus molecular weight of Example 10 product measured by MALLS/3D analysis.

Figure 2 provides intrinsic viscosity versus molecular weight of Example 11 product measured by MALLS/3D analysis.

Figure 3 provides intrinsic viscosity versus molecular weight of Example 12 product measured by MALLS/3D analysis.

Figure 4 provides intrinsic viscosity versus molecular weight of Example 13 product measured by MALLS/3D analysis.

Definitions

In the structures depicted throughout this specification and the claims, a solid line indicates a bond, and an arrow indicates that the bond may be dative.

As used herein, the new notation for the Periodic Table Groups is used as described in Chemical and Engineering News , 63(5), p. 27 (1985).

The term "substituted" means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group. For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group and ethyl alcohol is an ethyl group substituted with an -OH group.

The terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" are used interchangeably throughout this document. Likewise, the terms "functional group," "group," and "substituent" are also used interchangeably in this document. For purposes of this disclosure, "hydrocarbyl radical" is defined to be radicals of carbon and hydrogen, that may be linear, branched, or cyclic (aromatic or non-aromatic); and may include substituted hydrocarbyl radicals as defined herein. In an embodiment, a functional group may comprise a hydrocarbyl radical, a substituted hydrocarbyl radical, or a combination thereof.

Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with a heteroatom or heteroatom containing group, or with atoms from Groups 13, 14, 15, 16, and 17 of the Periodic Table of Elements, or a combination thereof, or with at least one functional group, such as halogen (CI, Br, I, F), NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at least one heteroatom has been inserted within the hydrocarbyl radical, such as halogen (CI, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂, PbR*₂, and the like, where R* is, independently, hydrogen or a hydrocarbyl radical, or any combination thereof.

An "olefin," alternatively referred to as "alkene," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, including, but not limited to, ethylene, propylene, and butene, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. A "polymer" has two or more of the same or different mer units. A "homopolymer" is a polymer having mer units that are the same. A "copolymer" is a polymer having two or more mer units that are different from each other. A "terpolymer" is a polymer having three mer units that are different from each other. "Different" as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. An oligomer is a polymer having a low molecular weight. In some embodiments, an oligomer has an Mn of 21,000 g/mol or less (e.g., 2,500 g/mol or less); in other embodiments, an oligomer has a low number of mer units (such as 75 mer units or less).

An "alpha-olefin" is an olefin having a double bond at the alpha (or 1-) position. A "linear alpha-olefin" or "LAO" is an olefin with a double bond at the alpha position and a linear hydrocarbon chain. A "polyalphaolefin" or "PAO" is a polymer having two or more alpha-olefin units. For the purposes of this disclosure, the term "a-olefin" includes C2-C20 olefins. Non-limiting examples of a-olefins include ethylene, propylene, 1-butene, 1- pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.

For purposes herein, a polymer or polymeric chain comprises a concatenation of carbon atoms bonded to each other in a linear or a branched chain, which is referred to herein as the backbone of the polymer (e.g., polyethylene). The polymeric chain may further comprise various pendent groups attached to the polymer backbone which were present on the monomers from which the polymer was produced. These pendent groups are not to be confused with branching of the polymer backbone, the difference between pendent side chains and both short and long chain branching being readily understood by one of skill in the art.

An "anionic ligand" is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.

A "scavenger" is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments, a co-activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound, also referred to as an alkylated invention compound.

A propylene polymer is a polymer having at least 50 mol% of propylene. As used herein, Mn is number average molecular weight as determined by proton nuclear magnetic resonance spectroscopy (^H NMR) where the data is collected at 120°C in a 5 mm probe using a spectrometer with a frequency of at least 400 MHz. Data is recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 120 transients. Unless stated otherwise, Mw is weight average molecular weight as determined by gel permeation chromatography (GPC), Mz is z average molecular weight as determined by GPC as described in the VINYL TERMINATED MACROMONOMERS section below, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD) is defined to be Mw (GPC) divided by Mn (GPC). Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz, are g/mol.

The following abbreviations may be used through this specification: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu is normal butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is triisobutyl n-octylaluminum, MAO is methylalumoxane, pMe is para-methyl, Ar* is 2,6-diisopropylaryl, Bz is benzyl, THF is tetrahydrofuran, RT is room temperature which is defined as 25°C unless otherwise specified, VTM is vinyl terminated macromonomer, and tol is toluene.

DETAILED DESCRIPTION OF THE INVENTION

This inventions relates to the reaction product obtained by contacting a by contacting a metathesis catalyst and a C2 to a C40 vinyl or vinylene containing monomer with a composition represented by the formula:

where VTM is the residual terminal portion of a vinyl terminated macromonomer and R³ is a CI to a C40 hydrocarbyl group, each R is, independently, H or a CI to C40 hydrocarbyl group (preferably a substituted or unsubstituted alkyl or substituted or unsubstituted aryl) and R⁷ is a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, X is C or a heteroatom (such as N, O, S, or P) and z is 0 or 1.

In one aspect, the reaction product can be characterized as a composition represented by the formula

R³ is a CI to a C40 hydrocarbyl group;

each R is, independently, H or a CI to C40 hydrocarbyl group;

X is C or a heteroatom (such as N, O, S, or P);

z is 0 or 1 ; and

n is from 2 to 2000.

Process to Functionalize Monomers and Polymers

Olefin cross metathesis with a VTM, vinyl or vinylidene monomer and an alkyl en- one, preferably catalyzed by a ruthenium metathesis catalyst, outlined below, provides access to polar-functionalized VTMs, polar-functionalized vinyl monomers or polar-functionalized vinylidene monomers (noted as Polymer in the scheme below), which are then converted into norbornene-terminated polymers using a Diels Alder reaction, typically with a Ti catalyst and a cyclopentadiene or substituted cyclopentadiene. Notably, TiCl2(OiPr)₂ provides a balance of reactivity, maximizing conversion while minimizing byproduct formation.

where Polymer is a vinyl monomer (such as n-C16), a vinylidene monomer, or a VTM (such an atactic homo-polypropylene VTM, preferably an aPP having an Mn from 570 to 20,000, alternately from 3700 to 20,000g/mol), each R is independently H, an alkyl (substituted or unsubstituted) or an aryl (substituted or unsubstituted) group, and Cat. Ru is a ruthenium metathesis catalyst.

Useful substituted cyclopentadienes include those substituted at one, two, three or more positions with the same or different CI to C12 alkyl group (preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof), a heteroatom (preferably N, S, O, or P), or heteroatom containing group (preferably an N, O, S, or P containing group, preferably represented by the formula XR_n, where X is a heteroatom (preferably N, S, O, or P), R is H or a CI to C12 alkyl, and n is 1 or 2, preferably the CI to C12 alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof). Useful cyclopentadienes also include those where one carbon in the C5 ring has been replaced by a heteroatom (preferably N, O or S), such as such as substituted or unsubstituted furans, pyrroles, and the like. Useful cyclopentadienes include those represented b the formula (3):

where z is 0 or 1, X is carbon or a heteroatom (preferably C, N, S, O or P, preferably C, O, S or N, preferably C, N or S); each R is, independently, H or a CI to C12 alkyl group (preferably an alkyl selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), or R may be XR_n, (where X is a heteroatom (such as N, O, S, or P), R is H or a CI to C12 alkyl, and n is 1 or 2, preferably the CI to C12 alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof).

Useful alkyl-en-ones include alkyl-en-ones where the alkyl has from 3 to 12 carbon atoms (preferably propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof), such as but-3-en-2-one, prop-2-en-one, pent-4-en-one, hex-5-en-one, oct-7- en-one, non-8-en-one, dec-9-en-one, undec-9-en-one, dodec-9-en-one and the like. Preferred alkyl en-ones are represented by the formula:

where each R is independently H, an alkyl (substituted or unsubstituted) or an aryl (substituted or unsubstituted) group, preferably the substituted or unsubstituted alkyl group has from 1 to 40 carbon atoms, preferably from 2 to 20 carbon atoms, preferably the alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof, and preferably the substituted or unsubstituted aryl group has from 5 to 40 carbon atoms, preferably from 6 to 20 carbon atoms.

With the polar-functionalized VTMs, polar-functionalized vinyl monomers or polar- functionalized vinylidene monomers, ring-opening metathesis polymerization (ROMP) is then performed using a metathesis catalyst (preferably a ruthenium-based catalyst), optionally in the presence of a chain transfer agent (such as 3-hexene), to control molecular weight. When these polymers are characterized by !fi NMR and GPC 3D, the latter shows extensive branching, but, nota bene, the linear viscosity standards used herein are based on polypropylene, not the exact polymer backbone.

Useful chain transfer agents include any C4 to C40 olefin (preferably having an internal or alpha double bond, preferably an internal double ), such a 3-hexene, 2-butene, 2- hexene, 2-octene, 3-octene, 4-octene, 5-octene, 2-pentene, 3-pentene, and the like.

In an embodiment, this invention also relates to the reaction product obtained by contacting a cyclopentadiene (substituted or unsubstituted) with a titanium catalyst and an enone terminated VTM, vinyl, and or vinylidene monomer. Useful substituted cyclopentadienes include those substituted at one, two, three or more positions with the same or different CI to C12 alkyl group (preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), a heteroatom (preferably N, S, O, or P), or heteroatom containing group (preferably a N, O, S, or P containing group, preferably represented by the formula XR_n, where R is H or a CI to C12 alkyl, and n is 1 or 2, preferably the CI to C 12 alkyl is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, and dodecyl, and isomers thereof). Useful cyclopentadienes also include those where one carbon in the C5 ring has been replaced by a heteroatom (preferably N, O or S), such as such as substituted or unsubstituted furans, pyrroles, and the like. Particularly useful cyclopentadienes include those represented by the formula (3) above. Useful enone terminated VTM, enone terminated vinyl monomer, and/or enone terminated vinylidene monomer (also referred to as polar-functionalized VTM, polar- functionalized vinyl monomers and/or polar-functionalized vinylidene monomer) include those having an Mw of 100 to 500,000 Daltons, preferably from 100 to 250,000 Da., preferably 500 to 100,000 Da.

The reactants are typically combined in a reaction vessel at a temperature of 20°C to

200°C (preferably 50°C to 160°C, preferably 60°C to 140°C) and a pressure of 0 to 1000 MPa (preferably 0.5 to 500 MPa, preferably 1 to 250 MPa) for a residence time of 0.5 seconds to 30 hours (preferably 1 second to 5 hours, preferably 1 minute to 1 hour).

Typically, in the first reaction to produce the polar functionalized VTM, vinyl or vinylidene monomer, VTM, vinyl monomer and/ or vinylidene monomer are reacted with a cross metathesis catalyst and an alkyl-en-one. Typically, 0.00001 to 1.0 moles, preferably 0.0001 to 0.05 moles, preferably 0.0005 to 0.01 moles of metathesis catalyst are charged to the reactor per mole of monomer (e.g. one or more of vinyl monomer, VTM, and vinylene monomer) charged and at least 1 mole of alkyl ene one is charged per mole of VTM, preferably from 2: 1 to 150: 1, preferably from 5: 1 to 100: 1 moles of alkyl-en-one are charged to the reactor per mole of monomer (e.g. one or more of vinyl monomer, VTM, and vinylene monomer) charged.

Typically, in the second reaction (to make norbornene containing Polymer) polar- functionalized VTM, polar-functionalized vinyl monomers and/or polar-functionalized vinylidene monomers are reacted with cyclopentadiene and a Ti catalyst. Typically 0.0001 to 2.0 moles, preferably 0.001 to 1.0 moles, preferably 0.04 to 0.5 moles of Ti catalyst are charged to the reactor per mole of polar-functionalized VTM, polar-functionalized vinyl monomers and/or polar-functionalized vinylidene monomers charged and at least 1 mole of substituted or unsubstituted cyclopentadiene one is charged per mole of per mole of polar- functionalized VTM, polar-functionalized vinyl monomers and/or polar-functionalized vinylidene monomers charged, preferably from 2: 1 to 150: 1, preferably 4: 1 to 100: 1 moles of substituted or unsubstituted cyclopentadiene are charged to the reactor per mole of polar- functionalized VTM, polar-functionalized vinyl monomers and/or polar-functionalized vinylidene monomers charged.

Typically, in the third reaction, norbornene containing polymer is reacted with a metathesis catalyst, optionally in the presence of a chain transfer agent, and typically 0.0001 to 1.0 moles, preferably 0.001 to 0.05 moles, preferably 0.005 to 0.01 moles of metathesis catalyst are charged to the reactor per mole of norbornene containing polymer charged. The process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 vol% or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants; e.g., propane in propylene).

Suitable diluents/solvents for the process include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene, and xylene. In a preferred embodiment, aliphatic hydrocarbon solvents are preferred, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents.

In another embodiment, the process is a slurry process. As used herein the term "slurry polymerization process" means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).

In a preferred embodiment, the feed concentration for the process is 60 vol% solvent or less, preferably 40 vol% or less, preferably 20 vol% or less.

The process may be batch, semi -batch or continuous. As used herein, the term continuous means a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe or pump).

This invention further relates to a process, preferably an in-line process, preferably a continuous process, to produce functionalized bottlebrush polymers.

A "reaction zone" also referred to as a "polymerization zone" is defined as an area where activated catalysts and monomers are contacted and a polymerization reaction takes place. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. Room temperature is 23°C unless otherwise noted.

Vinyl Terminated Macromonomers

A "vinyl terminated macromonomer," as used herein, refers to one or more of:

(i) a vinyl terminated polymer having at least 5% allyl chain ends (preferably 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, or 99%);

(ii) a vinyl terminated polymer having an Mn of at least 160 g/mol, preferably at least 200 g/mol (measured by NMR) comprising of one or more C₄ to C₄Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;

(iii) a copolymer having an Mn of 300 g/mol or more (measured by NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C₄Q higher olefin, and (b) from 0.1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iv) a copolymer having an Mn of 300 g/mol or more (measured by !fi NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C₄ olefin, (b) from 0.1 mol% to 20 mol% of propylene; and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

(v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by NMR) comprising 10 mol% to 90 mol% propylene and 10 mol% to 90 mol% of ethylene, wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X = (-0.94*(mol% ethylene incorporated) + 100), when 10 mol% to 60 mol% ethylene is present in the co-oligomer, 2) X = 45, when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer, and 3) X = (1.83* (mol% ethylene incorporated) -83), when 70 mol% to 90 mol% ethylene is present in the co-oligomer;

(vi) a propylene oligomer, comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, less than 100 ppm aluminum, and/or less than 250 regio defects per 10,000 monomer units;

(vii) a propylene oligomer, comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of 150 g/mol to 20,000 g/mol, preferably 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;

(viii) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% C₄ to olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;

(ix) a propylene oligomer, comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of 150 g/mol to 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0;

(x) a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, an Mn of 500 g/mol to 70,000 g/mol, alternately to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, and less than 1400 ppm aluminum;

(xi) vinyl terminated polyethylene having: (a) at least 60% allyl chain ends; (b) a molecular weight distribution of less than or equal to 4.0; (c) a g'(_vi_s) of greater than 0.95; and (d) an Mn (^lR NMR) of at least 20,000 g/mol; and

(xii) vinyl terminated polyethylene having: (a) at least 50% allyl chain ends; (b) a molecular weight distribution of less than or equal to 4.0; (c) a g'(_vi_s) of 0.95 or less; (d) an

Mn (!H NMR) of at least 7,000 g/mol; and (e) a Mn (GPC)/Mn (^lR NMR) in the range of from 0.8 to 1.2.

It is understood by those of ordinary skill in the art that when the VTM's, as described here, are reacted with another material the "vinyl" (e.g. the allyl chain end) is involved in the reaction and has been transformed. Thus, the language used herein describing that a fragment of the final product (typically referred to as PO in the formulae herein) is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon, is meant to refer to the fact that the VTM has been incorporated in the product. Similarly stating that a product or material comprises a VTM means that the reacted form of the VTM is present, unless the context clearly indicates otherwise (such as a mixture of ingredients that do not have a catalytic agent present).

In some embodiments, the vinyl terminated macromonomer has an Mn of at least 200 g/mol, (e.g., 200 g/mol to 100,000 g/mol, e.g., 200 g/mol to 75,000 g/mol, e.g., 200 g/mol to 60,000 g/mol, e.g., 300 g/mol to 60,000 g/mol, or e.g., 750 g/mol to 30,000 g/mol) (measured by !fi NMR) and comprises one or more (e.g., two or more, three or more, four or more, and the like) C₄ to C₄Q (e.g., C₄ to C30, C₄ to C20, or C₄ to C^, e.g., butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) olefin derived units, where the vinyl terminated macromonomer comprises substantially no propylene derived units (e.g., less than 0.1 wt% propylene, e.g., 0 wt%); and wherein the vinyl terminated macromonomer has at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) allyl chain ends (relative to total unsaturation); and optionally, an allyl chain end to vinylidene chain end ratio of 1 : 1 or greater (e.g., greater than 2: 1, greater than 2.5: 1 , greater than 3 : 1 , greater than 5: 1 , or greater than 10: 1); and even further optionally, e.g., substantially no isobutyl chain ends (e.g., less than 0.1 wt% isobutyl chain ends). In some embodiments, the vinyl terminated macromonomers may also comprise ethylene derived units, e.g., at least 5 mol% ethylene (e.g., at least 15 mol% ethylene, e.g., at least 25 mol% ethylene, e.g., at least 35 mol% ethylene, e.g., at least 45 mol% ethylene, e.g., at least 60 mol% ethylene, e.g., at least 75 mol% ethylene, or e.g., at least 90 mol% ethylene). Such vinyl terminated macromonomers are further described in USSN 13/072,288.

In some embodiments, the vinyl terminated macromonomers may have an Mn (measured by ^lK NMR) of greater than 200 g/mol (e.g., 300 g/mol to 60,000 g/mol, 400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300 g/mol to 15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000 g/mol), and comprise:

(a) from 20 mol% to 99.9 mol% (e.g., from 25 mol% to 90 mol%, from 30 mol% to 85 mol%, from 35 mol% to 80 mol%, from 40 mol% to 75 mol%, or from 50 mol% to 95 mol%) of at least one C₅ to C₄Q (e.g., to C20) higher olefin;

(b) from 0.1 mol% to 80 mol% (e.g., from 5 mol% to 70 mol%, from 10 mol% to 65 mol%, from 15 mol% to 55 mol%, from 25 mol% to 50 mol%, or from 30 mol% to 80 mol%) of propylene; and

wherein the vinyl terminated macromonomer has at least 40% allyl chain ends (e.g., at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation; and, optionally, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1; and further optionally, an allyl chain end to vinylidene chain end ratio of greater than 2: 1 (e.g., greater than 2.5: 1, greater than 3 : 1, greater than 5: 1, or greater than 10: 1); and even further optionally, an allyl chain end to vinylene ratio is greater than 1 : 1 (e.g., greater than 2: 1 or greater than 5: 1). Such macromonomers are further described in USSN 13/072,249.

In another embodiment, the vinyl terminated macromonomer has an Mn of 300 g/mol or more (measured by ^lH NMR, e.g., 300 g/mol to 60,000 g/mol, 400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300 g/mol to 15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000 g/mol), and comprises:

(a) from 80 mol% to 99.9 mol% of at least one C₄ olefin, e.g., 85 mol% to 99.9 mol%, e.g., 90 mol% to 99.9 mol%;

(b) from 0.1 mol% to 20 mol% of propylene, e.g., 0.1 mol% to 15 mol%, e.g., 0.1 mol% to 10 mol%; and

wherein the vinyl terminated macromonomer has at least 40% allyl chain ends (e.g., at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation, and in some embodiments, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and in further embodiments, an allyl chain end to vinylidene group ratio of more than 2: 1, more than 2.5: 1, more than 3 : 1, more than 5: 1, or more than 10: 1. Such macromonomers are also further described in USSN 13/072,249.

In other embodiments, the vinyl terminated macromonomer is a propylene co- oligomer having an Mn of 300 g/mol to 30,000 g/mol as measured by NMR (e.g., 400 g/mol to 20,000 g/mol, e.g., 500 g/mol to 15,000 g/mol, e.g., 600 g/mol to 12,000 g/mol, e.g., 800 g/mol to 10,000 g/mol, e.g., 900 g/mol to 8,000 g/mol, e.g., 900 g/mol to 7,000 g/mol), comprising 10 mol% to 90 mol% propylene (e.g., 15 mol% to 85 mol%, e.g., 20 mol% to 80 mol%, e.g., 30 mol% to 75 mol%, e.g., 50 mol% to 90 mol%) and 10 mol% to 90 mol% (e.g., 85 mol% to 15 mol%, e.g., 20 mol% to 80 mol%, e.g., 25 mol% to 70 mol%, e.g., 10 mol% to 50 mol%) of one or more alpha-olefin comonomers (e.g., ethylene, butene, hexene, or octene, e.g., ethylene), wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X = (-0.94 (mol% ethylene incorporated) + 100 {alternately 1.20(- 0.94 (mol% ethylene incorporated) + 100), alternately 1.50(-0.94 (mol% ethylene incorporated) + 100)}), when 10 mol% to 60 mol% ethylene is present in the co-oligomer; 2) X = 45 (alternately 50, alternately 60), when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer; and 3) X = (1.83* (mol% ethylene incorporated) -83, {alternately 1.20 [1.83* (mol% ethylene incorporated) -83], alternately 1.50 [1.83* (mol% ethylene incorporated) -83]}), when 70 mol% to 90 mol% ethylene is present in the co- oligomer. Such macromonomers are further described in USSN 12/143,663.

In other embodiments, the vinyl terminated macromonomer is a propylene oligomer, comprising more than 90 mol% propylene (e.g., 95 mol% to 99 mol%, e.g., 98 mol% to 9 mol%) and less than 10 mol% ethylene (e.g., 1 mol% to 4 mol%, e.g., 1 mol% to 2 mol%), wherein the oligomer has: at least 93% allyl chain ends (e.g., at least 95%, e.g., at least 97%, e.g., at least 98%); a number average molecular weight (Mn) of 400 g/mol to 30,000 g/mol, as measured by ^lR NMR (e.g., 500 g/mol to 20,000 g/mol, e.g., 600 g/mol to 15,000 g/mol, e.g., 700 g/mol to 10,000 g/mol, e.g., 800 g/mol to 9,000 g/mol, e.g., 900 g/mol to 8,000 g/mol, e.g., 1,000 g/mol to 6,000 g/mol); an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 1400 ppm aluminum, (e.g., less than 1200 ppm, e.g., less than 1000 ppm, e.g., less than 500 ppm, e.g., less than 100 ppm). Such macromonomers are further described in USSN 12/143,663.

In other embodiments, the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (e.g., 60 mol% to 90 mol%, e.g., 70 mol% to 90 mol%) propylene and from 10 mol% to 50 mol% (e.g., 10 mol% to 40 mol%, e.g., 10 mol% to 30 mol%) ethylene, wherein the oligomer has: at least 90% allyl chain ends (e.g., at least 91%, e.g., at least 93%, e.g., at least 95%, e.g., at least 98%); an Mn of 150 g/mol to 20,000 g/mol, as measured by ^lR NMR (e.g., 200 g/mol to 15,000 g/mol, e.g., 250 g/mol to 15,000 g/mol, e.g., 300 g/mol to 10,000 g/mol, e.g., 400 g/mol to 9,500 g/mol, e.g., 500 g/mol to 9,000 g/mol, e.g., 750 g/mol to 9,000 g/mol); and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.3: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol% (e.g., at less than 1 mol%, e.g., less than 0.5 mol%, e.g., at 0 mol%). Such macromonomers are further described in USSN 12/143,663. In other embodiments, the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (e.g., at least 60 mol%, e.g., 70 mol% to 99.5 mol%, e.g., 80 mol% to 99 mol%, e.g., 90 mol% to 98.5 mol%) propylene, from 0.1 mol% to 45 mol% (e.g., at least 35 mol%, e.g., 0.5 mol% to 30 mol%, e.g., 1 mol% to 20 mol%, e.g., 1.5 mol% to 10 mol%) ethylene, and from 0.1 mol% to 5 mol% (e.g., 0.5 mol% to 3 mol%, e.g., 0.5 mol% to 1 mol%) C₄ to Ci2 olefin (such as butene, hexene, or octene, e.g., butene), wherein the oligomer has: at least 90% allyl chain ends (e.g., at least 91%, e.g., at least 93%, e.g., at least 95%, e.g., at least 98%); a number average molecular weight (Mn) of 150 g/mol to 15,000 g/mol, as measured by ^lR NMR (e.g., 200 g/mol to 12,000 g/mol, e.g., 250 g/mol to 10,000 g/mol, e.g., 300 g/mol to 10,000 g/mol, e.g., 400 g/mol to 9500 g/mol, e.g., 500 g/mol to 9,000 g/mol, e.g., 750 g/mol to 9,000 g/mol); and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0. Such macromonomers are further described in USSN 12/143,663.

In other embodiments, the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (e.g., at least 60 mol%, e.g., 70 mol% to 99.5 mol%, e.g., 80 mol% to 99 mol%, e.g., 90 mol% to 98.5 mol%) propylene, from 0.1 mol% to 45 mol% (e.g., at least 35 mol%, e.g., 0.5 mol% to 30 mol%, e.g., 1 mol% to 20 mol%, e.g., 1.5 mol% to 10 mol%) ethylene, and from 0.1 mol% to 5 mol% (e.g., 0.5 mol% to 3 mol%, e.g., 0.5 mol% to 1 mol%) diene (such as C₄ to alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene), wherein the oligomer has at least 90% allyl chain ends (e.g., at least 91%, e.g., at least 93%, e.g., at least 95%, e.g., at least 98%); a number average molecular weight (Mn) of 150 g/mol to 20,000 g/mol, as measured by ^lR NMR (e.g., 200 g/mol to 15,000 g/mol, e.g., 250 g/mol to 12,000 g/mol, e.g., 300 g/mol to 10,000 g/mol, e.g., 400 g/mol to 9,500 g/mol, e.g., 500 g/mol to 9,000 g/mol, e.g., 750 g/mol to 9,000 g/mol); and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0. Such macromonomers are further described in USSN 12/143,663.

In other embodiments, the vinyl terminated macromonomer is a propylene homo- oligomer, comprising propylene and less than 0.5 wt% comonomer, e.g., 0 wt% comonomer, wherein the oligomer has:

i) at least 93% allyl chain ends (e.g., at least 95%, e.g., at least 96%, e.g., at least 97%, e.g., at least 98%, e.g., at least 99%);

ii) a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, as measured by ^lR NMR (e.g., 500 g/mol to 15,000 g/mol, e.g., 700 g/mol to 10,000 g/mol, e.g., 800 g/mol to 8,000 g/mol, e.g., 900 g/mol to 7,000 g/mol, e.g., 1,000 g/mol to 6,000 g/mol, e.g., 1,000 g/mol to 5,000 g/mol);

iii) an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.3 : 1.0; and

iv) less than 1400 ppm aluminum, (e.g., less than 1200 ppm, e.g., less than 1000 ppm, e.g., less than 500 ppm, e.g., less than 100 ppm). Such macromonomers are also further described in USSN 12/143,663.

The vinyl terminated macromonomers may be homopolymers, copolymers, terpolymers, and so on. Any vinyl terminated macromonomers described herein has one or more of:

(i) an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.3 : 1.0;

(ii) an allyl chain end to vinylidene chain end ratio of greater than 2: 1 (e.g., greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1);

(iii) an allyl chain end to vinyl ene ratio that is greater than 1 : 1 (e.g., greater than 2: 1 or greater than 5: 1); and

(iv) at least 5% allyl chain ends (preferably at least 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, or 99%) up to 100% allyl chain ends.

Vinyl terminated macromonomers generally have a saturated chain end (or terminus) and/or an unsaturated chain end or terminus. The unsaturated chain end of the vinyl terminated macromonomer comprises an "allyl chain end" or a "3-alkyl" chain end.

An allyl chain end is represented by CH^CH-CH^., as shown in the formula:

where M represents the polymer chain. "Allylic vinyl group," "allyl chain end," "vinyl chain end," "vinyl termination," "allylic vinyl group," and "vinyl terminated" are used interchangeably in the following description. The number of allyl chain ends, vinylidene chain ends, vinylene chain ends, and other unsaturated chain ends is determined using ^lR NMR at 120°C using deuterated tetrachloroethane as the solvent on an at least 250 MHz NMR spectrometer, and in selected cases, confirmed by ¹³C NMR. Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra, while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100°C on a BRUKER spectrometer operating at 500 MHz for proton and 125 MHz for carbon) for vinyl terminated oligomers in J. American Chemical Soc, 114, 1992, pp. 1025-1032 that are useful herein. Allyl chain ends are reported as a molar percentage of the total number of moles of unsaturated groups (that is, the sum of allyl chain ends, vinylidene chain ends, vinylene chain ends, and the like).

A 3-alkyl chain end (where the alkyl is a Q to C38 alkyl), also referred to as a "3- alkyl vinyl end group" or a "3-alkyl vinyl termination," is represented by the formula:

3-alkyl vinyl end group where "····" represents the polyolefin chain and R^b is a Q to C38 alkyl group, or a Q to C20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like. The amount of 3-alkyl chain ends is determined using ¹³C NMR as set out below.

1³C NMR data is collected at 120°C at a frequency of at least 100 MHz, using a

BRUKER 400 MHz NMR spectrometer. A 90 degree pulse, an acquisition time adjusted to give a digital resolution between 0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time with continuous broadband proton decoupling using swept square wave modulation without gating is employed during the entire acquisition period. The spectra is acquired with time averaging to provide a signal to noise level adequate to measure the signals of interest. Samples are dissolved in tetrachloroethane-d2 at concentrations between 10 wt% to 15 wt% prior to being inserted into the spectrometer magnet. Prior to data analysis spectra are referenced by setting the chemical shift of the TCE solvent signal to 74.39 ppm. Chain ends for quantization were identified using the signals shown in the table below. N-butyl and n- propyl were not reported due to their low abundance (less than 5%) relative to the chain ends shown in the table below.

The "allyl chain end to vinylidene chain end ratio" is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylidene chain ends. The "allyl chain end to vinylene chain end ratio" is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends. Vinyl terminated macromonomers typically also have a saturated chain end. In polymerizations where propylene is present, the polymer chain may initiate growth in a propylene monomer, thereby generating an isobutyl chain end. An "isobutyl chain end" is defined to be an end or terminus of a polymer, represented as shown in the formula below:

isobutyl chain end where M represents the polymer chain. Isobutyl chain ends are determined according to the procedure set out in WO 2009/155471. The "isobutyl chain end to allylic vinyl group ratio" is defined to be the ratio of the percentage of isobutyl chain ends to the percentage of allyl chain ends. The "isobutyl chain end to alpha bromo carbon ratio" is defined to be the ratio of the percentage of isobutyl chain ends to the percentage of brominated chain ends (at 34 ppm).

In polymerizations comprising C₄ or greater monomers (or "higher olefin" monomers), the saturated chain end may be a C₄ or greater (or "higher olefin") chain end, as shown in the formula below:

higher olefin chain end where M represents the polymer chain and n is an integer selected from 4 to 40. This is especially true when there is substantially no ethylene or propylene in the polymerization. In an ethylene/(C₄ or greater monomer) copolymerization, the polymer chain may initiate growth in an ethylene monomer, thereby generating a saturated chain end which is an ethyl chain end. Preferably, the VTM's useful herein are polymers as first described in US 2009/0318644 (referred to therein as vinyl terminated "macromers" or "macromonomers"). Vinyl and Vinylene Monomers

Vinyl and vinylene monomers useful herein include those represented by the formulae:

wherein R¹, R², R⁴ and R⁵ are each, independently, a hydrogen atom or a CI to a C40 hydrocarbyl moiety.

Useful monomers include, for example, ethylene, propylene and/or C4 to C40 olefins, preferably ethylene and/or C5 to C25 olefins, or preferably ethylene and/or C6 to CI 8 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. Exemplary, C4 to C40 olefin monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1 -hydroxy -4-cyclooctene, l-acetoxy-4- cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives.

In another embodiment, the monomer can be a vinyl terminated macromonomer

(VTM) as described herein.

Alkene Metathesis Catalysts

An alkene metathesis catalyst is a compound that catalyzes the reaction between a first olefin (typically vinyl) with a second olefin (typically vinyl or vinylene) to produce a product, typically with the elimination of ethylene.

In a preferred embodiment, the alkene metathesis catalyst useful herein is represented by the Formula (I):

where:

M is a Group 8 metal, preferably Ru or Os, preferably Ru;

X and X¹ are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X¹ may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;

L and L¹ are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L¹ may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

L and X may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

L¹ and X¹ may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

R and R¹ are, independently, hydrogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C4 to C30 aryl);

R¹ and L¹ or X¹ may be joined to form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; and

R and L or X may be joined to form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

Preferred alkoxides include those where the alkyl group is a phenol, substituted phenol (where the phenol may be substituted with up to 1, 2, 3, 4, or 5 to hydrocarbyl groups) or a to C^o hydrocarbyl, preferably a Q to alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

Preferred triflates are represented by the Formula (II):

O Formula (II)

where R² is hydrogen or a Q to C30 hydrocarbyl group, preferably a to alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

Preferred N-heterocyclic carbenes are represented by the Formula (III) or the Formula (IV):

Formula (III) or Formula (IV)

where:

each R⁴ is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, phenol, substituted phenol, or CH₂C(CH₃)₃; and

each R⁵ is hydrogen, a halogen, or a Q to hydrocarbyl group, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or phenyl.

In other useful embodiments, one of the N groups bound to the carbene in formula

(III) or (IV) is replaced with an S, O, or P atom, preferably an S atom.

Other useful N-heterocyclic carbenes include the compounds described in Hermann, W. A. Chem. Eur. J., 1996, 2, pp. 772 and 1627; Enders, D. et al. Angew. Chem. Int. Ed., 1995, 34, p. 1021; Alder R. W., Angew. Chem. Int. Ed., 1996, 35, p. 1121; and Bertrand, G. et al, Chem. Rev., 2000, 100, p. 39.

In a preferred embodiment, the alkene metathesis catalyst is one or more of tricyclohexylphosphine[ 1,3 -bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] [3 -phenyl- 1H- inden- 1 -ylidene]ruthenium(II) dichloride, tricyclohexylphosphine[3 -phenyl- lH-inden- 1 - ylidene][l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II) dichloride, tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2- ylidene] [(phenylthio)methylene]ruthenium(II) dichloride, bis(tricyclohexylphosphine)-3 - phenyl- lH-inden-l-ylideneruthenium(II) dichloride, l,3-Bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride, and [1,3-Bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4- nitrophenolyl]-[3-phenyl-lH-inden-l-ylidene]ruthenium(II) chloride. In a preferred embodiment, the catalyst is l,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2- (i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride and/or Tricyclohexylphosphine[3-phenyl- lH-inden- 1 -ylidene] [1 ,3-bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene]ruthenium(II) dichloride.

In another embodiment, the alkene metathesis catalyst is represented by Formula (I) above, where: M is Os or Ru; R¹ is hydrogen; X and X¹ may be different or the same and are any anionic ligand; L and L¹ may be different or the same and are any neutral electron donor; and R may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl. R is preferably hydrogen, to C20 alkyl, or aryl. The Q to C20 alkyl may optionally be substituted with one or more aryl, halide, hydroxy, to C20 alkoxy, or C2 to C20 alkoxycarbonyl groups. The aryl may optionally be substituted with one or more to C20 alkyl, aryl, hydroxyl, to C₅ alkoxy, amino, nitro, or halide groups. L and L¹ are preferably phosphines of the formula PR³' R⁴' R⁵', where R³' is a secondary alkyl or cycloalkyl, and R⁴' and R⁵' are aryl, to CIQ primary alkyl, secondary alkyl, or cycloalkyl. R⁴' and R⁵' may be the same or different. L and L¹ are preferably the same and are - P(cyclohexyl)3, -P (cyclopentyl)₃, or -P(isopropyl)3. X and X¹ are most preferably the same and are chlorine.

In another embodiment of the present invention, the ruthenium and osmium carbene compounds have the Formula (V):

_R10

X

c

X¹

L¹

Formula (V)

where M is Os or Ru, preferably Ru; X, X ^l, L, and L¹ are as described above; and R⁹ and R¹⁰ may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl. The R⁹ and R¹⁰ groups may optionally include one or more of the following functional groups: alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups. Such compounds and their synthesis are described in U.S. Patent No. 6, 11 1, 121.

In another embodiment, the alkene metathesis catalyst useful herein may be any of the catalysts described in U.S. Patent Nos. 6,1 11, 121; 5,312,940; 5,342,909; 7,329,758; 5,831, 108; 5,969,170; 6,759,537; 6,921,735; and U.S. Patent Publication No. 2005-0261451 Al, including, but not limited to, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, benzy lidene [1,3- bis (2 ,4, 6-trimethy lpheny l)-2 - imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium, dichloro(o- isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium(II), (l,3-Bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium, l,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene) ruthenium(II), [l,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2- pyridiny l)propy lidene]ruthenium(II), [ 1 , 3 -B is(2 -methylpheny l)-2 - imidazolidinylidene]dichloro(phenylmethylene) (tricyclohexylphosphine)ruthenium(II), [1,3- Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene) (tricyclohexylphosphine)ruthenium(II), and [l,3-Bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)bis(3-bromopyridine)ruthenium(II).

In another embodiment, the alkene metathesis catalyst is represented by the formula:

R R Formula (VI) where:

M* is a Group 8 metal, preferably Ru or Os, preferably Ru;

X* and X¹* are, independently, any anionic ligand, preferably a halogen (preferably ), an alkoxide or an alkyl sulfonate, or X and X¹ may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;

L* is N, O, P, or S, preferably N or O;

R* is hydrogen or a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl; R¹*, R²*, R³*, R⁴*, R⁵*, R⁶*, R⁷*, and R⁸* are, independently, hydrogen or a C_{ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R¹*, R²*, R³*, and R⁴* are methyl;

each R⁹* and R¹³* are, independently, hydrogen or a Ci to C30 hydrocarbyl or substituted hydrocarbyl, preferably a C2 to hydrocarbyl, preferably ethyl;

R¹⁰*, R^{1 1}*, R¹²* are, independently hydrogen or a Q to C30 hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl;

each G, is, independently, hydrogen, halogen or to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C₄ to C30 aryl);

where any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

Preferably, any two adjacent R groups may form a fused ring having from 5 to 8 non hydrogen atoms. Preferably the non-hydrogen atoms are C and/or O. Preferably the adjacent R groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms. By adjacent is meant any two R groups located next to each other, for example R³* and R⁴* can form a ring and/or R¹ !* and R¹²* can form a ring.

In a preferred embodiment, the metathesis catalyst compound comprises one or more of: 2-(2,6-diethylphenyl)-3,5,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride; 2-(mesityl)-3, 3,5,5- tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride; 2-(2-isopropyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride; 2-(2,6-diethyl-4- fluorophenyl)-3,3,5,5-tetramethylpyrrolidine[2-(i-propoxy)-5-( ,N- dimethylaminosulfonyl)phenyl]methylene ruthenium dichloride, or mixtures thereof.

For further information on such alkene metathesis catalysts, please see USSN 12/939054, filed November 3, 2010, claiming priority to and the benefit of USSN 61/259,514, filed November 9, 2009.

The above named catalysts are generally available for Sigma-Aldrich Corp. (St. Louis, MO) or Strem Chemicals, Inc. (Newburyport, MA).

Hot Melt Adhesives

In a particular embodiment, the compositions of this invention can be used in a hot melt adhesive composition. Hot melt adhesives exist as a solid at ambient temperature and can be converted into a tacky liquid by the application of heat. Hot melt adhesives are typically applied to a substrate in molten form.

The adhesive composition includes the inventive polymer described herein. The polymer may be functionalized with maleic acid or maleic anhydride. Additional components may be combined with the polymers or formulations of the polymers to form the adhesive composition.

In one aspect, the adhesive composition can include one or more tackifiers. The tackifiers can include aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, hydrogenated rosin acids, hydrogenated rosin acids, hydrogenated rosin esters, derivatives thereof, and combinations thereof, for example. The adhesive composition may include from 0 to 90 percent by weight of the one or more tackifiers. More preferably, the adhesive composition includes 5 to 60 percent by weight of the one or more tackifiers, preferably 10 to 40 percent by weight, preferably 10 to 20 percent by weight.

In another aspect, the adhesive composition can include one or more waxes, such as polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, wax modifiers, and combinations thereof, for example. The adhesive composition may include from 0 to 75 percent by weight the one or more waxes. More preferably, the adhesive composition includes 1 to 15 percent by weight of the one or more waxes.

In yet another aspect, the adhesive composition can include 60 percent by weight or less, 30 percent by weight or less, 20 percent by weight or less, 15 percent by weight or less, 10 percent by weight or less or 5 percent by weight or less of one or more additives. The one or more additives can include plasticizers, oils, stabilizers, antioxidants, pigments, dyestuffs, antiblock additives, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, humectants, fillers, solvents, nucleating agents, surfactants, chelating agents, gelling agents, processing aids, cross-linking agents, neutralizing agents, flame retardants, fluorescing agents, compatibilizers, antimicrobial agents, and water, for example.

Exemplary oils may include aliphatic naphthenic oils, white oils, and combinations thereof, for example. The phthalates may include di-iso-undecyl phthalate (DIUP), di-iso- nonylphthalate (DI P), dioctylphthalates (DOP), combinations thereof, or derivatives thereof. Exemplary polymeric additives include homo poly-alpha-olefins, copolymers of alpha-olefins, copolymers and terpolymers of diolefins, elastomers, polyesters, block copolymers including diblocks and triblocks, ester polymers, alkyl acrylate polymers, and acrylate polymers. Exemplary plasticizers may include mineral oils, polybutenes, phthalates, and combinations thereof.

Blends of Functionalized Polyolefins In some embodiments, the polymers produced by this invention may be blended with of one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s). Typically the bottlebrush polymer is present at from 0.1 wt% to 99 wt% (typically 1 wt% to 60 wt%, preferably 5 wt% to 40 wt%, and ideally 10 wt% to 45 wt%) based upon the weight of the blend and the other polymers are present at 99.9 wt% to 1 wt% (typically 99 wt% to 40 wt%, preferably 95 wt% to 60 wt%, preferably 90 wt% to 65 wt%).

By thermoplastic polymer(s), is meant a polymer that can be melted by heat and then cooled without appreciable change in properties. Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more of the above. Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising propylene copolymerized with one or more C3 to C40 olefins, preferably a C3 to C20 alpha-olefin, more preferably C3 to CIQ alpha- olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C20 alpha-olefin, more preferably propylene and/or butene.

By elastomers, is meant all natural and synthetic rubbers, including those defined in ASTM D1566. Examples of preferred elastomers include, but are not limited to, ethylene propylene rubber, ethylene propylene diene monomer rubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS, SIBS, and the like, where S=styrene, I=isoprene, and B=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutylene and para- alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, polybutadiene rubber (both cis and trans).

In another embodiment, the polymers produced herein may further be combined with one or more of polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm³) linear low density polyethylene, ultra-low density polyethylene (density 0.86 to less than 0.90 g/cm³), very low density polyethylene (density 0.90 to less than 0.915 g/cm³), medium density polyethylene (density 0.935 to less than 0.945 g/cm³), high density polyethylene (density 0.945 to 0.98 g/cm³), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1 , isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols and/or polyisobutylene. Preferred polymers include those available from ExxonMobil Chemical Company in Baytown, Texas under the tradenames EXCEED™ and EXACT™.

Tackifiers may be blended with the polymers produced herein and/or with blends of the polymers produced by this invention (as described above). Examples of useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters. In some embodiments the tackifier is hydrogenated. In some embodiments the tackifier has a softening point (Ring and Ball, as measured by ASTM E-28) of 80°C to 140°C, preferably 100°C to 130°C. The tackifier, if present, is typically present at 1 wt% to 50 wt%, based upon the weight of the blend, more preferably 10 wt% to 40 wt%, even more preferably 20 wt% to 40 wt%.

In another embodiment, the functionalized (and optionally derivitized) polyolefins of this invention, and/or blends thereof, further comprise typical additives known in the art such as fillers, cavitating agents, antioxidants, surfactants, adjuvants, plasticizers, block, antiblock, color masterbatches, pigments, dyes, processing aids, UV stabilizers, neutralizers, lubricants, waxes, and/or nucleating agents. The additives may be present in the typically effective amounts well known in the art, such as 0.001 wt% to 10 wt%. Preferred fillers, cavitating agents and/or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay and the like. Preferred antioxidants include phenolic antioxidants, such as Irganox 1010, Irganox, 1076 both available from Ciba-Geigy. Preferred oils include paraffinic or naphthenic oils such as Primol 352, or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris, France. More preferred oils include aliphatic naphthenic oils, white oils, or the like.

In a particularly preferred embodiment, the functionalized (and optionally derivitized) polyolefins produced herein are combined with polymers (elastomeric and/or thermoplastic) having functional groups such as unsaturated molecules-vinyl bonds, ketones or aldehydes under conditions such that they react. Reaction may be confirmed by an at least 20% (preferably at least 50%, preferably at least 100%) increase in Mw as compared to the Mw of the functionalized polyolefin prior to reaction. Such reaction conditions may be increased heat (for example, above the Tm of the functionalized polyolefin), increased shear (such as from a reactive extruder), presence or absence of solvent. Conditions useful for reaction include temperatures from 150°C to 240°C and where the components can be added to a stream comprising polymer and other species via a side arm extruder, gravimetric feeder, or liquids pump. Useful polymers having functional groups that can be reacted with the functionalized polyolefins produced herein include polyesters, polyvinyl acetates, nylons (polyamides), polybutadiene, nitrile rubber, hydroxylated nitrile rubber.

Polymer Products

The polymer products produced herein typically have a weight average molecular weight (as measured by GPC) of at least 1000 g/mol, preferably at least 5,000 g/mol, preferably at least 10,000 g/mol, preferably at least 20,000 g/mol, preferably at least 30,000 g/mol and preferably have an Mw (GPC) of less than 2,000,000 g/mol, preferably less than 1 ,000,000 g/mol, preferably less than 500,000 g/mol.

Applications

The polymers of this invention (and blends thereof as described above) may be used in any known thermoplastic or elastomer application. Examples include uses in molded parts, films, tapes, sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoe soles, bumpers, gaskets, bellows, films, fibers, elastic fibers, nonwovens, spun bonds, corrosion protection coatings and sealants. The functionalized polymers of the invention can also be used as protective films, such as those described in U.S. Patent No. 7,323,239 and also as rosin tackifiers and as heat sealable films such as those described in U.S. Patent No. 4,921,749.

In another embodiment the polymers can be used as a compatibilizer for particulate materials, such as carbon black, silica, glass, etc. or other high surface tension materials when the material is being blended into another polymer (such as polystyrene, polyethylene, polypropylene, butyl rubber, SBR, natural rubber, and other polymers named as PM1 to PM10 above).

EXAMPLES

Product Characterization

Products were characterized by !fi NMR and ¹³C NMR as follows:

!H MR

Unless otherwise stated, ¾ NMR data was collected at either room temperature or 120°C in a 5 mm probe using a spectrometer with a frequency of at least 400 MHz. Data was recorded using a maximum pulse width of 45°, 8 seconds between pulses and signal averaging 32 transients. Samples were dissolved in benzene-d^ or toluene-dg at concentrations between 5 to 40 wt% prior to insertion in the spectrometer magnet. Prior to data analysis spectra were referenced by setting the chemical shift of the benzene solvent signal to 7.15 ppm or the least shifted toluene solvent signal to 2.08 ppm.

1³C MR

Unless otherwise stated, ¹³C NMR data was collected at room temperature using a spectrometer with a ¹³C frequency of at least 100 MHz. A 90 degree pulse, an acquisition time adjusted to give a digital resolution between 0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time with continuous broadband proton decoupling using swept square wave modulation without gating was employed during the entire acquisition period. Samples were dissolved in benzene-d6 or chloroform-d at concentrations between 10 to 40 wt% prior to being inserted into the spectrometer magnet.

Prior to data analysis spectra were referenced by setting the chemical shift of the benzene solvent signal to 128.06 ppm or the chloroform solvent signal to 77.16 ppm.

Gel Permeation Chromatography (GPC)

Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatograph (Polymer Laboratories), equipped with three in-line detectors (3D), a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel ΙΟμιη Mixed-B LS columns are used. The nominal flow rate is 0.5 ml/min, and the nominal injection volume is 300 μϊ_^. The various transfer lines, columns, viscometer and differential refractometer (the DRI detector) are contained in an oven maintained at 145°C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 μιη Teflon filter. The TCB is then degassed with an online degasser before entering the Size Exclusion Chromatograph. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous shaking for 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C. The injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample. The LS laser is turned on at least 1 to 1.5 hours before running the samples. The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I_DRJ, using the following equation:

^{C = K}DRI^IDRI /(dn/dc)

where Krjjy is a constant determined by calibrating the DRI, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and λ = 690 nm. (dn/dc) is determined by GPC-DRI. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):

K₀c _ 1

+ 2A₂c

AR(Q) ΜΡ(Θ)

Here, AR(9) is the measured excess Rayleigh scattering intensity at scattering angle Θ, c is the polymer concentration determined from the DRI analysis, is the second virial coefficient, and for purposes of this invention = 0.0006. Ρ(θ) is the form factor for a monodisperse random coil, and K₀ is the optical constant for the system:

4π²η² (dn / dc)²

λ⁴Ν_Α where is Avogadro's number, and (dn/dc) is the refractive index increment for the system determined by GPC-DRI. The refractive index, n = 1.500 for TCB at 145°C and λ = 657 nm.

A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, n_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation:

η₈ = ο[η] + 0.3(ο[η])²

where c is concentration and was determined from the DRI output.

The branching index (g'_vi_s) is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosi the sample is calculated by:

where the summations are over the chromatographic slices, i, between the integration limits. The branching index g'_vj_s is defined as:

where, for purpose of this invention and claims thereto, a = 0.705 k = 0.0002288. M_v is the viscosity-average molecular weight based on molecular weights determined by LS analysis. See Macromolecules, 2001, 34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181- 7183, for guidance on selecting a linear standard having similar molecular weight and comonomer content, and determining k coefficients and a exponents. Z average branching index (g'zave) is calculated using Ci = polymer concentration in the slice i in the polymer peak times the mass of the slice squared, Mi².

All molecular weights are weight average unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted.

The ruthenium catalyst employed in examples below (referred to as "Zhan IB") is l,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-( ,N- dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (CAS Number: 918870- 76-5) Example 1.

In a nitrogen- filled glovebox, a 100 mL round bottom flask at room temperature was charged with 1-octadecene (3.21 mL, 10.1 mmol), 3-buten-2-one (MVK) (3.53 mL, 50.3 mmol), toluene (50 mL), and a magnetic stirbar. The solution was stirred and heated to 50°C. Zhan-IB catalyst (38 mg, 0.5 mol) was then added as a solution in toluene (1 mL) and vigorous gas evolution was observed. The flask was loosely capped and allowed to stir at 50°C for 16 h. The mixture was concentrated under a constant flow of nitrogen yielding an off-white solid. The resulting solid was dissolved in pentane and filtered through a plug of layered celite/silica/celite, leaving a colorless filtrate. This solution was concentrated under reduced pressure yielding a white solid. (2.50 g, 85%)

Example 2.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with vinyl terminated atactic homopolypropylene (aPP) (936 mg, 1.63 mmol, Mn = 571, vinyl = 98%, based on total unsaturations), 3-buten-2-one (MVK) (0.66 mL, 8.2 mmol), toluene (15.3 mL), and a magnetic stirbar. The solution was stirred and heated to 60°C. Zhan-IB catalyst (12.4 mg, 0.016 mmol) was then added as a solution in toluene (1 mL) and vigorous gas evolution was observed. The vial was loosely capped and allowed to stir at 60°C for 16 h. The mixture was concentrated under a constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite, leaving a colorless filtrate. This solution was concentrated under reduced pressure yielding a colorless oil. (834 mg, 83%)

Example 3.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with vinyl terminated aPP (885 mg, 0.26 mmol, Mn = 3571, vinyl = 95%, based on total unsaturations), 3-buten-2-one (MVK) (0.63 mL, 7.8 mmol), toluene (15.5 mL), and a magnetic stirbar. The solution was stirred and heated to 60°C. Zhan-IB catalyst (12 mg, 0.015 mmol) was then added as a solution in toluene (1 mL) and vigorous gas evolution was observed. The vial was loosely capped and allowed to stir at 60°C for 16 h. The mixture was concentrated under a constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite, leaving a colorless filtrate. This solution was concentrated under reduced pressure yielding a colorless oil. (829 mg, 93%)

Example 4.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with vinyl terminated aPP (3.1 g, 0.20 mmol, Mn = 14,894, vinyl = 71%, based on total unsaturations), 3-buten-2-one (MVK) (0.99 mL, 12.2 mmol), toluene (15 mL), and a magnetic stirbar. The solution was stirred and heated to 60°C. Zhan-IB catalyst (18 mg, 0.025 mmol) was then added as a solution in toluene (1 mL) and vigorous gas evolution was observed. The vial was loosely capped and allowed to stir at 60°C for 16 h. The mixture was concentrated under a constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite, leaving a colorless filtrate. This solution was concentrated under reduced pressure yielding a colorless oil. (2.2 g, 71%)

Example 5. l-(3-h

In a nitrogen-filled glovebox, a 50 mL round bottom flask at room temperature was charged with 3-eicosen-2-one (1.216 g, 4.12 mmol), cyclopentadiene (954 mg, 10.3 mmol), dichloromethane (15 mL), and a magnetic stirbar. The mixture was stirred, and diisopropoxytitanium(IV) chloride (48 mg, 0.2 mmol) was added as a solid. The flask was capped and allowed to stir for 36 h at room temperature. The flask was removed from the glovebox and water (2 mL) was added and the mixture was allowed to stir for 30 minutes. Stirring was stopped and the resulting biphasic mixture was allowed to stand and separate. The organic layer was separated, and the aqueous layer was extracted with dichloromethane (DCM) (3x10 mL). The combined organic solution was dried with MgS04, filtered, and concentrated under a constant flow of nitrogen. The residue was further concentrated in a vacuum oven for 3 days at 60°C yielding a colorless oil (1.231 g, 83%). ^lR NMR (400 MHz, C₆D₆) δ 6.1 (dd, 1H, J=5.7,3.1), 5.8 (dd, 1H, J=5.7, 2.8), 2.8 (m, 1H), 2.4 (m, 1H), 2.0 (dd, 1H, J=4.4, 3.5), 1.9 (m, 1H), 1.7 (bs, 2H), 1.4-1.2 (m, 30H), 0.9 (t, 3H, J=13.7).

Example 6.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with enone-terminated aPP from Example 2 (628 mg, 1.02 mmol), cyclopentadiene (196 mg, 2.04 mmol), dichloromethane (10 mL), and a magnetic stirbar. The mixture was stirred, and diisopropoxytitanium(IV) chloride (24 mg, 0.1 mmol) was added as a solid. The flask was capped and allowed to stir for 36 h at room temperature. The flask was removed from the glovebox and water (2 mL) was added and the mixture was allowed to stir for 30 minutes. Stirring was stopped and the resulting biphasic mixture was allowed to stand and separate. The organic layer was separated, and the aqueous layer was extracted with DCM (3x5 mL). The combined organic solution was dried with MgSC^, filtered, and concentrated under a constant flow of nitrogen. The residue was further concentrated in a vacuum oven for 3 days at 60°C yielding a colorless oil (578 mg, 83%). %). ^lH NMR (400 MHz, C₆D₆) δ 6.1 (d, 1H, J=12.6), 5.8 (d, 1 H, J=22.8), 2.8 (bs, 1H), 2.4 (bs, 1H), 2.3-2.0 (m, 2H), 1.8-0.8 (m, 80H).

Example 7.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with enone-terminated aPP from Example 3 (310 mg, 0.08 mmol), cyclopentadiene (40 mg, 0.43 mmol), toluene (10 mL), and a magnetic stirbar. The mixture was stirred, and diisopropoxytitanium(IV) chloride (2 mg, 8 x 10^"3 mmol) was added as a solid. The flask was capped and allowed to stir for 36 h at room temperature. The flask was removed from the glovebox and water (2 mL) was added and the mixture was allowed to stir for 30 minutes. Stirring was stopped and the resulting biphasic mixture was allowed to stand and separate. The organic layer was separated, and the aqueous layer was extracted with toluene (3x5 mL). The combined organic solution was dried with MgSC^, filtered, and concentrated under a constant flow of nitrogen. The residue was further concentrated in a vacuum oven for 3 days at 60°C yielding a colorless oil (227 mg, 72%). Ή NMR (400 MHz, C₆D₆) δ 6.1 (d, 1H, J=17.3), 5.8 (d, 1 H, J=24.8), 2.8 (bs, 1H), 2.4 (m, 1H), 2.2-2.1 (m, 3H), 1.8-0.8 (m, 480H). Example 8.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with enone terminated aPP from Example 4 (700 mg, 0.046 mmol), cyclopentadiene (16 mg, 0.175 mmol), toluene (10 mL), and a magnetic stirbar. The mixture was stirred, and diisopropoxytitanium(IV) chloride (1 mg, 4 x 10^-3 mmol) was added as a solid. The flask was capped and allowed to stir for 36 h at room temperature. The flask was removed from the glovebox and water (2 mL) was added and the mixture was allowed to stir for 30 minutes. Stirring was stopped and the resulting biphasic mixture was allowed to stand and separate. The organic layer was separated, and the aqueous layer was extracted with toluene (3x5 mL). The combined organic solution was dried with MgSC^, filtered, and concentrated under a constant flow of nitrogen. The residue was further concentrated in a vacuum oven for 3 days at 60°C yielding a colorless oil (663 mg, 95%). ^lH NMR (400 MHz, C₆D₆) δ 6.1 (d, 1H, J=17.3), 5.8 (d, 1 H, J=24.6), 2.8 (bs, 1H), 2.4 (m, 1H), 1.9-1.5 (m, 1000H), 1.5-0.8 (m, 1800H), 0.4 (bs, 3H).

Example 9.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with 2-acetyl-5-norbornene (471 mg, 3.5 mmol), cis-3-hexene (14.5 mg, 0.17 mmol), toluene (17 mL), and a magnetic stirbar. The solution was stirred, and Zhan-IB catalyst (13 mg, 0.017 mmol) was added as a solution in toluene (1 mL). The flask was loosely capped and allowed to stir for 16 h. The mixture was concentrated under constant flow of nitrogen yielding an orange oil. The resulting oil was immiscible in pentane, redissolved in toluene and filtered through a plug of layered celite/silica/celite. This solution was concentrated to approximately 0.5 mL under reduced pressure and then 20 mL of methanol were added while the solution was stirred. The suspension was allowed to stand and settle for 4 days and the liquid was then decanted. The solid was redissolved in toluene and filtered again through a plug of layered celite/silica/celite. The filtrate was then concentrated, yielding a light tan oil. (98 mg, 21%)

Example 10.

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with l-(3-hexadecylbicyclo[2.2.1]hept-5-en-2-yl)ethanone (1.231 g, 3.4 mmol), cis- 3-hexene (21 μί, 0.17 mmol), toluene (18 mL), and a magnetic stirbar. The solution was stirred, and Zhan-IB catalyst (20 mg, 0.017 mmol) was added as a solution in toluene (1 mL). The flask was loosely capped and allowed to stir for 16 h. The mixture was concentrated under constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered twice through plugs of layered celite/silica/celite. This solution was concentrated under reduced pressure yielding a yellow oil (1.02 g, 82%). ^lR NMR (400 MHz, C₆D₆) δ 5.4 (br, 2H), 3.2 (br, 1H), 2.8 (br, 1H), 2.6 (br, 1H), 2.4 (br, 1H), 2.1 (br, 2H), 2.0 (br, 2H), 1.6 (br, 2H), 1.4 (br, 31H), 0.9 (br, 3H); ¹³C NMR (125 MHz, C^D₆) δ 67.1, 32.2, 30.1, 29.7, 23.0, 14.2 (carbonyl not observed due to low signal to noise ratio).

Example 11. RO

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with the product of Example 6 (578 mg, 0.85 mmol), cis-3-hexene (5.3 μί, 0.04 mmol), toluene (10 mL), and a magnetic stirbar. The solution was stirred, and Zhan-IB catalyst (6.4 mg, 8 x 10^~3 mmol) was added as a solution in toluene (1 mL). The flask was loosely capped and allowed to stir for 16 h. The mixture was concentrated under constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite. This solution was concentrated under reduced pressure. The residue was further concentrated in a vacuum oven for 6 h at 60°C yielding a yellow oil (344 mg, 60%). ^lH NMR (400 MHz, C₆D₆) δ 5.4 (br, 2H), 3.3 (br, 1H), 2.9 (br, 1H), 2.6 (br, 2H), 2.2 (br), 1.8 (br), 1.5-0.8 (br); 13c NMR (125 MHz, C₆D₆) δ 66.5, 47.4, 46.9, 32.0, 27.9, 25.6, 23.6, 23.0, 20.6, 14.3 (carbonyl not observed due to low signal to noise ratio).

Figure 2 provides intrinsic viscosity versus molecular weight of Example 1 1 product measured by MALLS/3D analysis.

Example 12. RO

In a nitrogen- filled glovebox, a 20 mL scintillation vial at room temperature was charged with the product of Example 7 (227 mg, 0.062 mmol), cis-3-hexene (0.4 μί, 0.003 mmol), toluene (10 mL), and a magnetic stirbar. The solution was stirred, and Zhan-IB catalyst (0.47 mg, 6 x 10^~4 mmol) was added as a solution in toluene (1 mL). The flask was loosely capped and allowed to stir for 16 h. The mixture was concentrated under constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite. This solution was concentrated under reduced pressure. The residue was further concentrated in a vacuum oven for 6 h at 60°C yielding a yellow oil (161 mg, 71%). lH NMR (400 MHz, C₆D₆) δ 5.5 (br, 2H), 3.3 (br, 1H), 2.8 (br, 1H), 2.6 (br, 2H), 2.2 (br), 1.8 (br), 1.5-0.8 (br); C NMR (125 MHz, C₆D₆) δ 47.1, 46.3, 46.1, 45.6, 44.5, 44.3, 27.8, 27.4, 25.2, 21.5, 21.1, 20.7, 20.3, 19.6, 14.2 (carbonyl not observed due to low signal to noise ratio).

Example 13. RO

In a nitrogen-filled glovebox, a 20 mL scintillation vial at room temperature was charged with the product of Example 8 (663 mg, 0.033 mmol), cis-3-hexene (0.2 μί, 0.002 mmol), toluene (10 mL), and a magnetic stirbar. The solution was stirred, and Zhan-IB catalyst (0.25 mg, 3 x 10^~4 mmol) was added as a solution in toluene (1 mL). The flask was loosely capped and allowed to stir for 16 h. The mixture was concentrated under constant flow of nitrogen yielding an orange oil. The resulting oil was dissolved in pentane and filtered through a plug of layered celite/silica/celite. This solution was concentrated under reduced pressure. The residue was further concentrated in a vacuum oven for 6 h at 60°C yielding a yellow oil (545 mg, 82%). Ή NMR (400 MHz, C₆D₆) δ 5.5 (br), 2.2 (br), 1.8 (br), 1.5-0.8 (br).

Figure 4 provides intrinsic viscosity versus molecular weight of Example 13 product measured by MALL S/3 D analys is .

All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text, provided however that any priority document not named in the initially filed application or filing documents is NOT incorporated by reference herein.

Claims

CLAIMS;

1. A composition represented by the formula (la) or (lb):

where VTM is the residual terminal portion of a vinyl terminated macromonomer and is a CI to a C40 hydrocarbyl group, each R is, independently, H or a CI to C40 hydrocarbyl group and R⁷ is a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, X is C or a heteroatom (such as N, O, S, or P) and z is 0 or 1.

2. The composition of claim 1 , wherein the residual portion of the vinyl terminated macromonomer is derived from 1-octadecene.

3. The composition of claim 1 or 2, wherein the VTM is one or more of:

(i) a vinyl terminated polymer having at least 5% allyl chain ends;

(ii) a vinyl terminated polymer having an Mn at least 160 g/mol (measured by NMR) comprising of one or more C₄ to C_4Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;

(iii) a copolymer having an Mn of 300 g/mol or more (measured by Ή NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C₄Q higher olefin, and (b) from 0.1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iv) a copolymer having an Mn of 300 g/mol or more (measured by NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C₄ olefin, (b) from 0.1 mol% to 20 mol% of propylene; and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

(v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by NMR) comprising 10 mol% to 90 mol% propylene and 10 mol% to 90 mol% of ethylene, wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X =

(-0.94*(mol% ethylene incorporated) + 100), when 10 mol% to 60 mol% ethylene is present in the co-oligomer, 2) X = 45, when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer, and 3) X = (1.83 * (mol% ethylene incorporated) -83), when 70 mol% to 90 mol% ethylene is present in the co-oligomer;

(vii) a propylene oligomer, comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of 150 g/mol to 20,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;

(x) a homo-oligomer, comprising propylene, wherein the oligomer has: at least 93% allyl chain ends, an Mn of 500 g/mol to 70,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, and less than 1400 ppm aluminum;

(xii) vinyl terminated polyethylene having: (a) at least 50% allyl chain ends; (b) a molecular weight distribution of less than or equal to 4.0; (c) a g'(_vi_s) of 0.95 or less; (d) an Mn (!H NMR) of at least 7,000 g/mol; and (e) a Mn (GPC)/Mn (^lR NMR) in the range of from 0.8 to 1.2.

4. A composition comprising the reaction product of: a C3 to C40 vinyl or a vinylene containing monomer, a ruthenium catalyst, and a composition represented by the formula:

where VTM is the residual terminal portion of a vinyl terminated macromonomer and is a CI to a C40 hydrocarbyl group, each R is, independently, H or a CI to C40 hydrocarbyl group (preferably a substituted or unsubstituted alkyl or substituted or unsubstituted aryl) and R⁷ is a substituted or unsubstituted alkyl or substituted or unsubstituted aryl, X is C or a heteroatom (such as N, O, S, or P) and z is 0 or 1.

5. The composition of claim 4, wherein the residual portion of the vinyl terminated macromonomer is derived from 1-octadecene.

6. The composition of claim 4 or 5, wherein the VTM is one or more of:

(i) a vinyl terminated polymer having at least 5% allyl chain ends;

(ii) a vinyl terminated polymer having an Mn at least 160 g/mol (measured by NMR) comprising of one or more C₄ to C₄Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;

(iii) a copolymer having an Mn of 300 g/mol or more (measured by !fi NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C₄Q higher olefin, and (b) from 0. 1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iv) a copolymer having an Mn of 300 g/mol or more (measured by NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C₄ olefin, (b) from 0. 1 mol% to 20 mol% of propylene; and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

(v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by NMR) comprising 10 mol% to 90 mol% propylene and 10 mol% to 90 mol% of ethylene, wherein the oligomer has at least X% allyl chain ends (relative to total unsaturations), where: 1) X = (-0.94*(mol% ethylene incorporated) + 100), when 10 mol% to 60 mol% ethylene is present in the co-oligomer, 2) X = 45, when greater than 60 mol% and less than 70 mol% ethylene is present in the co-oligomer, and 3) X = (1.83 * (mol% ethylene incorporated) -83), when 70 mol% to 90 mol% ethylene is present in the co-oligomer; (vi) a propylene oligomer, comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of 500 g/mol to 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, less than 100 ppm aluminum, and/or less than 250 regio defects per 10,000 monomer units;

7. A composition represented by the formula:

wherein VTM is the residual terminal portion of a vinyl terminated macromonomer; each R¹, R², R⁴ and R⁵, independently, a C2 to C40 hydrocarbyl group, (such as a residual portion of a vinyl C2 to a C40 monomer or vinylidene C3 to a C40 monomer); R³ is a CI to a C40 hydrocarbyl group; each R is, independently, H or a CI to C40 hydrocarbyl group; R⁷ is a substituted or unsubstituted alkyl or aryl, X is C or a heteroatom (such as N, O, S, or P); z is 0 or 1 ; and n is from 2 to 2000.

8. The composition of claim 7, wherein the residual portion of the vinyl terminated macromonomer is derived from 1-octadecene.

9. The composition of claim 7 or 8, wherein the VTM is one or more of:

(i) a vinyl terminated polymer having at least 5% allyl chain ends;

(iii) a copolymer having an Mn of 300 g/mol or more (measured by NMR) comprising (a) from 20 mol% to 99.9 mol% of at least one C5 to C₄Q higher olefin, and (b) from 0. 1 mol% to 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;

(iv) a copolymer having an Mn of 300 g/mol or more (measured by Ή NMR), and comprises (a) from 80 mol% to 99.9 mol% of at least one C₄ olefin, (b) from 0. 1 mol% to 20 mol% of propylene; and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;

10. A process to prepare a the composition represented by formula (la) or (lb) in claims 1, 2 or 3, comprising the step of contacting a titanium catalyst and an enone terminated

VTM with a substituted a cyclopentadiene, a substituted cyclopentadiene or a cyclopentadiene represented by the formula:

where z is 0 or 1, X is carbon or a heteroatom (preferably C, N, S, O or P); each R is, independently, H or a Cl to C12 alkyl group, or R may be XR_n, (where X is a heteroatom (such as N, O, S, or P), R is H or a CI to C12 alkyl, and n is 1 or 2.

1 1. The process of claim 10, wherein the titanium catalyst is one of dichlorobis(isopropoxy)titanium, titanium tetrachloride, titanium tetrachloride dimethoxyethane complex, triethyl aluminum, tris(pentafluorophenyl)borane, trifluoromethanesulfonimide, trifluoromethanesulfonic acid, methanesulfonic acid, p- toluenesulfonic acid, tin tetrachloride, imidazolidinones, oxazaborolidinones, and alumina- or silica-supported aluminum or titanium reagents.

12. The process of claim 10 or 11, wherein the cyclopentadiene is substituted at one or more positions.

13. The process of claim 10, 11 or 12, wherein the enone has a molecular weight of from 100 to 500,000 Da.

14. A process to prepare in the composition of any of claims 4 through 8, comprising the step of contacting a metathesis catalyst with a C2 to a C40 vinyl or vinylene containing monom r, and a composition represented by the formula:

15. The process of claim 14, wherein the metathesis catalyst is a ruthenium catalyst.