Substantially linear polymers and methods of making and using same

This Application claims the benefit of U.S. Provisional Patent Application No. 60/712,866, filed on Aug. 31, 2005.

This invention was made with United States Government support under ATP Award No. 70NANB4H3014 awarded by the National Institute of Standards and Technology (NIST). The United States Government has certain rights in the invention.

The present invention relates to copolymers and terpolymers containing, inter alia, acyclic aliphatic olefins and polar monomers. The invention also relates to processing for making such copolymers and terpolymers.

Commercial processes for the copolymerization of ethylene with polar monomers such as acrylates, methacrylates, and vinyl acetate employ free radical processes in which the incorporation of the polar functionality is relatively random. The use of free radical initiators across the entire acrylic polymer market gives little or no control over polymer architecture (tacticity or crystallinity, blockiness, molecular weight, and molecular weight distribution) and thus limits the accessible range of materials performance properties. Because these free radical processes require extreme pressures, they are associated with high capital investment and manufacturing costs, and, of course, increased safety hazards.

There is a need for new molecular catalysts capable of copolymerizing acyclic aliphatic olefins with polar monomers under mild reaction conditions and in a stereoregular (“tactic”) fashion. Of the many approaches to modifying the properties of a polymer that are available, the incorporation of functional groups into an otherwise non-polar material is of paramount importance. Polar groups exercise control over important polymer properties such as toughness, adhesion, barrier properties, and surface properties. These polymer properties manifest themselves in the properties of materials incorporating the polymer, such as solvent resistance, miscibility with other polymers, and rheological properties, leading to product performance such as paintability, printability, gloss, hardness, and mar resistance. By incorporating polar groups into hydrocarbon polymers such as polyethylene, polypropylene and polystyrene, not only would the important properties related to crystallinity (modulus, strength, solvent resistance, etc.) be maintained, but new properties would also be expressed.

One method of making the copolymers is disclosed in U.S. Pat. No. 6,417,303 to Stibrany et al. Stibrany et al. disclose copolymers formed using a metal complex having the formula LMX 1 X 2 ; wherein L is a bidentate nitrogen-containing ligand with more than 2 nitrogens; M is copper, silver or gold; X 1 and X 2 are independently selected from the group consisting of halogens, hydride, triflate, acetate, trifluoroacetate, perfluorotetraphenylborate, tetrafluoroborate, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkoxy, aryl, and any other moiety into which a monomer can insert. Stibrany et al. further disclose that the copolymers may have segments formed from olefinic monomers and monomers having at least one hydrocarbyl polar functional group. The copolymers produced by Stibrany et al., however, were of low number average molecular weight (i.e., ≦26,200)

Another method of making copolymers is disclosed in European Patent Number EP 0 589 527 to Drent et al. Drent et al. disclose a group of palladium catalyst complexes comprising a palladium metal center complexed with an anion derived from an acid having a pK a of less than 3, and containing an atom of Group VA of the Periodic Table of Elements, wherein the Group VA atom is substituted with at least one aryl group, said aryl group being substituted with a polar group on the ortho position. Drent et al. further disclose copolymers of ethylene with acrylates or vinyl acetate prepared using the palladium catalyst complexes disclosed in European Patent Number EP 0 589 527. The copolymers produced by Drent et al., however, were of low number average molecular weight (i.e., ≦21,100). (See Drent, et al., Palladium catalysed copolymerization of ethene with alkylacrylates: polar comonomer built into the linear polymer chain , C HEM. COMMUN. , pp. 744-745 (2002)).

As the polymer chains grow longer, the strength of the polymer increases to a point. That is, after polymer chains have reached a certain length referred to as the “entanglement molecular weight”, additional chain lengthening has little effect on the strength of the polymer. This can be understood by imagining entangled chains. As the chains grow, their entanglement increases. At a certain length, they are so strongly entangled that any additional entanglement will not add significant strength to the system because the failure will occur within the chain rather than through chain slippage. Below the entanglement molecular weight the polymers may exhibit low strength due to a lack of sufficient chain entanglement.

Accordingly, there remains a need for substantially linear copolymers derived from acyclic aliphatic olefins and polar monomers and for methods of making the same. There also remains a need for methods of making substantially linear copolymers derived from acyclic aliphatic olefins and polar monomers, wherein the copolymers exhibit a high molecular weight and have high strength properties.

In one aspect of the present invention, there is provided a process for preparing a copolymer comprising contacting at least one acyclic aliphatic olefin monomer, at least one monomer having the formula

and a catalyst composition comprising a metal center, M, complexed with at least one ligand, wherein the at least one ligand has a structure according to the following formula

wherein Z is selected from a halogen, —CN, an aromatic hydrocarbyl group, —COY and —CO 2 Y; where Y is selected from hydrogen and R 19 ; where R 19 is selected from a hydrocarbyl group, an aromatic hydrocarbyl group and derivatives thereof, wherein J is selected from a hydrogen and an aliphatic hydrocarbyl group having up to 30 carbons; wherein M is selected from Ni and Pd; wherein X 1 , X 2 and X 3 are independently selected from a hydrocarbyl group, an aromatic hydrocarbyl group and derivatives thereof, wherein Q is selected from phosphorus, arsenic, nitrogen and antimony; wherein R 15 is selected from —SO 3 , —SO 2 N(R 18 ), —CO 2 , —PO 3 , —AsO 3 , —SiO 2 , —C(CF 3 ) 2 O; wherein R 18 is selected from a hydrogen, a halogen, a hydrocarbyl group, an aromatic hydrocarbyl group and a substituted hydrocarbyl group; wherein the copolymer has a number average molecular weight of ≧21,200 and wherein the copolymer comprises 1 to 99.9 mol % acyclic aliphatic olefin monomer units.

In another aspect of the invention, there is provided a process for preparing a terpolymer comprising contacting at least one acyclic aliphatic olefin monomer, at least one norbornene or substituted norbornene monomer, at least one monomer having the formula

and a catalyst composition comprising a metal center, M, complexed with at least one ligand, wherein the at least one ligand has a structure according to the following formula

wherein Z is selected from a halogen, —CN, an aromatic hydrocarbyl group, —COY and —CO 2 Y; where Y is selected from hydrogen and R 19 ; where R 19 is selected from a hydrocarbyl group, an aromatic hydrocarbyl group and derivatives thereof, wherein J is selected from a hydrogen and an aliphatic hydrocarbyl group having up to 30 carbons; wherein M is selected from Ni and Pd; wherein X 1 , X 2 and X 3 are independently selected from a hydrocarbyl group, an aromatic hydrocarbyl group and derivatives thereof, wherein Q is selected from phosphorus, arsenic, nitrogen and antimony; wherein R 15 is selected from —SO 3 , —SO 2 N(R 18 ), —CO 2 , —PO 3 , —AsO 3 , —SiO 2 , —C(CF 3 ) 2 O; wherein R 18 is selected from a hydrogen, a halogen, a hydrocarbyl group, an aromatic hydrocarbyl group and a substituted hydrocarbyl group; and, wherein the terpolymer comprises 0.1 to 50 mol % norbornene or substituted norbornene derived units.

In another aspect of the present invention, there is provided a copolymer derived from a palladium catalyzed polymerization, wherein the copolymer has a polymer chain comprising the formula:

wherein A is derived from an acyclic aliphatic olefin monomer; R 21 is selected from H and CH 3 ; G is selected from —OR 22 and —COOR 22 , where R 22 is a C 1-24 alkyl group; and wherein the copolymer has a number average molecular weight of ≧26,500 and f is 0.001 to 0.99.

In another aspect of the present invention, there is provided a terpolymer derived from a late transition metal catalyzed polymerization, wherein the terpolymer has a polymer chain comprising the formula:

wherein A is derived from an acyclic aliphatic olefin monomer; R 21 is selected from H and CH 3 ; G is selected from —OR 22 and —COOR 22 , where R 22 is a C 1-24 alkyl group; E is derived from a norbornene, a substituted norbornene, a styrene or a derivative of styrene; f is 0.001 to 0.99 and c is 0.001 to 0.5.

The term “copolymer” as used herein and in the appended claims refers to polymers prepared from at least two different monomers.

The term “terpolymer” as used herein and in the appended claims refers to polymers prepared from at least three different monomers.

In some embodiments of the present invention, Z is selected from a halogen, —CN, an aromatic hydrocarbyl group, —COY and —CO 2 Y; wherein Y is selected from hydrogen and R 19 ; where R 19 is selected from a hydrocarbyl group, an aromatic hydrocarbyl group and derivatives thereof. In some aspects of these embodiments, R 19 is selected from aliphatic hydrocarbyl groups having up to 30 carbon atoms and aromatic hydrocarbyl groups having up to 30 carbon atoms. In some aspects of these embodiments, R 19 is selected from an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, an alkylaryl group, a phenyl group, a biphenyl group, a carboxylate group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, a silyl group, and derivatives thereof. In some aspects of these embodiments, R 19 is selected from a C 1 -C 20 alkyl group, a C 3 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group, an aryl group, an arylalkyl group, an alkylaryl group, a phenyl group, a biphenyl group, a C 1 -C 20 carboxylate group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyloxy group, a C 2 -C 20 alkynyloxy group, an aryloxy group, a C 2 -C 20 alkoxycarbonyl group, a C 1 -C 20 alkylthio group, a C 1 -C 20 alkylsulfonyl group, a C 1 -C 20 alkylsulfinyl group, a silyl group, and derivatives thereof

In some embodiments of the present invention, J is selected from a hydrogen and an aliphatic hydrocarbyl group having up to 30 carbons. In some aspects of these embodiments, J is selected from a hydrogen and a C 1 -C 8 aliphatic hydrocarbyl group.

In some embodiments of the present invention, M is selected from Ni and Pd. In some aspects of these embodiments, M is Ni. In some aspects of these embodiments, M is Pd.

In some embodiments of the present invention, Q is selected from phosphorus, arsenic and antimony. In some aspects of these embodiments, Q is selected from phosphorus and arsenic. In some aspects of these embodiments, Q is phosphorus.

In some embodiments of the present invention, R 15 is selected from —SO 3 , —SO 2 N(R 18 ), —CO 2 , —PO 3 , —AsO 3 , —SiO 2 , —C(CF 3 ) 2 O. In some aspects of these alternatively R 15 is selected from —SO 3 and —SO 2 N(R 18 ). In some aspects of these embodiments, R 15 is —SO 3 . In some aspects of these embodiments, R 18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group. In some aspects of these embodiments, R 18 is selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, and silyl. In some aspects of these embodiments, R 18 is selected from a methyl group and a halogenated methyl group

In some embodiments of the present invention, X 1 , X 2 and X 3 are all different.

In some embodiments of the present invention, X 2 and X 3 are the same.

In some embodiments of the present invention, X 1 , X 2 and X 3 are independently selected from aliphatic hydrocarbyl groups and aromatic hydrocarbyl groups. In some aspects of these embodiments, X 1 , X 2 and X 3 are independently selected from aliphatic hydrocarbyl groups and aromatic hydrocarbyl groups having up to 30 carbon atoms. In some aspects of these embodiments, X 1 , X 2 and X 3 are independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, silyl, and derivatives thereof In some aspects of these embodiments, X 1 , X 2 and X 3 are independently selected from C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, silyl, and derivatives thereof.

In some embodiments of the present invention, X 2 and X 3 are independently selected from aryl groups with an ortho substituted phenyl. In some aspects of these embodiments, X 2 and X 3 are independently selected from aryl groups with an ortho substituted, substituted phenyl. In some aspects of these embodiments, X 2 and X 3 are independently selected from aryl groups with an ortho substituted, substituted phenyl having a formula 2,6-R 16 R 17 -phenyl; where R 16 and R 17 are independently selected from C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, silyl and derivatives thereof. In some aspects of these embodiments, X 2 and X 3 are aryl groups with an ortho substituted 2,6-dimethoxy phenyl.

In some embodiments of the present invention, the at least one ligand having the structure

is according to the formula:

wherein R 1 -R 14 are independently selected from a hydrogen; a halogen; and, a substituent selected from C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, silyl and derivatives thereof; wherein R 15 is selected from —SO 3 , —SO 2 N(R 18 ), —CO 2 , —PO 3 , —AsO 3 , —SiO 2 , —C(CF 3 ) 2 O; alternatively wherein R 15 is selected from —SO 3 and —SO 2 N(R 18 ); alternatively wherein R 15 is —SO 3 ; alternatively wherein R 15 is —SO 2 N(R 18 ); wherein R 18 is selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, silyl and derivatives thereof.

In some embodiments of the present invention, none of R 1 , R 5 , R 6 and R 10 is selected from CH 3 , CF 3 , F, SMe 2 , biphenyl and phenoxy.

In some embodiments of the present invention, two or more adjacent R groups selected from R 1 -R 5 may be linked to form a substituted or unsubstituted, saturated or unsaturated ring structure.

In some embodiments of the present invention, two or more adjacent R groups selected from R 6 -R 10 may be linked to form a substituted or unsubstituted, saturated or unsaturated ring structure.

In some embodiments of the present invention, two or more adjacent R groups selected from R 11 -R 14 may be linked to form a substituted or unsubstituted, saturated or unsaturated ring structure.

In some embodiments of the present invention, at least one of R 1 , R 5 , R 6 and R 10 may be selected from a phenyl and a derivative thereof. In some aspects of these embodiments, at least one of R 1 , R 5 , R 6 and R 10 is an ortho substituted phenyl. In some aspects of these embodiments, the ortho substituted phenyl is 2,6-R 16 R 17 -phenyl, wherein R 16 and R 17 are independently selected from hydrogen, halogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, silyl and derivatives thereof. In some aspects of these embodiments, the derivatives of the foregoing groups may include such groups optionally substituted with hydrocarbyl and/or heteroatom substituents selected from linear or branched C 1 -C 5 alkyl, linear or branched C 1 -C 5 haloalkyl, linear or branched C 2 -C 5 alkenyl and haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus and phenyl, optionally substituted with linear or branched C 1 -C 5 alkyl, linear or branched C 1 -C 5 haloalkyl and halogen. In some aspects of these embodiments, the cycloalkyl and cycloalkenyl groups may be monocyclic or multicyclic. In some aspects of these embodiments, the aryl groups may comprise a single ring (e.g., phenyl) or a fused ring system (e.g., naphthyl, anthracenyl). In some aspects of these embodiments, the cycloalkyl, cycloalkenyl and aryl groups may be taken together to form a fused ring system. In some aspects of these embodiments, each of the monocyclic and multicyclic ring systems may optionally be monosubstituted or multisubstituted with a substituent independently selected from hydrogen, linear and branched C 1 -C 5 alkyl, linear and branched C 1 -C 5 haloalkyl, linear and branched C 1 -C 5 alkoxy, chlorine, fluorine, iodine, bromine, C 5 -C 10 cycloalkyl, C 6 -C 15 cycloalkenyl and C 6 -C 30 aryl.

In some embodiments of the present invention, at least one of R 1 , R 5 , R 6 and R 10 is 2,6-dimethoxy phenyl.

In some embodiments of the present invention, the ligand having the structure

is selected from Structures I-XV presented in Table 1. In some aspects of these embodiments, the ligand is selected from Structures I, XI, and XIV. In some aspects of these embodiments, the ligand is selected from Structures I and XIV. In some aspects of these embodiments, the ligand is Structure I. In some aspects of these embodiments, the ligand is Structure XIV.

In some embodiments of the present invention, the catalyst composition is formed by a process comprising: combining a source of metal, M; and a compound according to the following formula [X 2 X 3 Q-X 1 —R 15 ] m [L] n ; wherein each L is independently selected from hydrogen, lithium, sodium, potassium, thallium, calcium and silver; alternatively each L is lithium; and, wherein m and n are selected to balance the charges.

In some embodiments of the present invention, the at least one monomer having the formula

is selected from C 1 -C 10 alkyl(meth)acrylates, styrene, and derivatives thereof.

In some embodiments of the present invention, the at least one acyclic aliphatic olefin is a C 2 -C 20 acyclic aliphatic olefin. In some aspects of these embodiments, the at least one acyclic aliphatic olefin is ethylene.

In some embodiments of the present invention, the copolymer contains 1 to 99.9 mol % acyclic aliphatic olefin monomer derived units. In some aspects of these embodiments, the copolymer contains 5 to 99.5 mol % acyclic aliphatic olefin monomer derived units. In some aspects of these embodiments, the copolymer contains 10 to 95 mol % acyclic aliphatic olefin monomer derived units. In some aspects of these embodiments, the copolymer contains 1 to 70 mol % acyclic aliphatic olefin monomer derived units. In some aspects of these embodiments, the copolymer contains 2 to 50 mol % acyclic aliphatic olefin monomer derived units. In some aspects of these embodiments, the copolymer contains 20 to 85 mol % acyclic aliphatic olefin monomer derived units.

In some embodiments of the present invention, the copolymer is a random copolymer.

In some embodiments of the present invention, the copolymer is substantially linear. That is, in some embodiments of the present invention, those portions of the copolymer derived from acyclic aliphatic olefin monomer units have a branch content of ≦15 branches/1,000 carbon atoms; alternatively between 0.5 and 15 branches/1,000 carbon atoms; alternatively ≦10 branches/1,000 carbon atoms; alternatively ≦5 branches/1,000 carbon atoms. In some aspects of these embodiments, the branches contain at least two carbon atoms. The branching content of the copolymer is determined by Carbon 13 NMR and the melting point temperature of the copolymer.

In some embodiments of the present invention, the polymerization temperature is 0 to 200° C. In some aspects of these embodiments, the polymerization temperature is 10 to 180° C. In some aspects of these embodiments, the polymerization temperature is 30 to 150° C. In some aspects of these embodiments, the polymerization temperature is 60 to 120° C.

In some embodiments of the present invention, the process for preparing a copolymer comprising contacting at least one acyclic aliphatic olefin monomer, at least one monomer having the formula

and a catalyst composition comprising a metal center, M, with at least one ligand, wherein the at least one ligand has a structure according to the following formula

provides copolymers having a number average molecular weight, M n , of ≧21,200; alternatively M n ≧22,000; alternatively M n ≧24,000; alternatively M n ≧25,000; alternatively M n ≧30,000; alternatively M n ≧40,000; alternatively M n ≧50,000; alternatively M n ≧70,000; alternatively M n ≧95,000; alternatively M n ≧100,000; alternatively M n ≧150,000; alternatively M n ≧200,000; alternatively M n ≧250,000; alternatively M n ≧300,000; alternatively M n ≧350,000; alternatively M n ≧400,000; alternatively M n ≧450,000; alternatively M n ≧500,000; alternatively M n ≧550,000; alternatively M n ≧600,000; alternatively M n ≧650,000; alternatively M n ≧700,000; alternatively M n ≧750,000; alternatively M n ≧800,000; alternatively M n ≧850,000; alternatively M n ≧900,000; alternatively M n ≧950,000; alternatively M n ≧1,000,000. In some aspects of these embodiments, the copolymer has a number average molecular weight, M n , of 24,000 to 5,000,000; alternatively M n , of 25,000 to 5,000,000; alternatively M n of 40,000 to 5,000,000; alternatively M n of 50,000 to 5,000,000; alternatively M n of 70,000 to 5,000,000; alternatively M n of 95,000 to 5,000,000; alternatively M n of 100,000 to 5,000,000; alternatively M n of 150,000 to 2,000,000; alternatively M n of 100,000 to 1,000,000; alternatively M n of 100,000 to 800,000; alternatively M n of 250,000 to 500,000.

In some embodiments of the present invention, the copolymer has a polymer chain according to the formula:

wherein A is derived from an acyclic aliphatic olefin monomer; R 21 is selected from H and CH 3 ; G is selected from —OR 22 and —COOR 22 , where R 22 is a C 1-24 alkyl group; f is 0.001 to 0.99; and, wherein the copolymer has a number average molecular weight, M n of ≧26,500. In some aspects of these embodiments, f is 0.005 to 0.95. In some aspects of these embodiments, f is 0.05 to 0.90. In some aspects of these embodiments, f is 0.3 to 0.99. In some aspects of these embodiments, f is 0.5 to 0.98. In some aspects of these embodiments, f is 0.15 to 0.8. In some aspects of these embodiments, the copolymer has a number average molecular weight, M n , of ≧30,000; alternatively M n ≧40,000; alternatively M n ≧50,000; alternatively M n ≧70,000; alternatively M n ≧95,000; alternatively M n ≧100,000; alternatively M n ≧150,000; alternatively M n ≧170,000; alternatively M n ≧200,000; alternatively M n ≧250,000; alternatively M n ≧300,000; alternatively M n ≧350,000; alternatively M n ≧400,000; alternatively M n ≧450,000; alternatively M n ≧500,000; alternatively M n ≧550,000; alternatively M n ≧600,000; alternatively M n ≧650,000; alternatively M n ≧700,000; alternatively M n ≧750,000; alternatively M n ≧800,000; alternatively M n ≧850,000; alternatively M n ≧900,000; alternatively M n ≧950,000; alternatively M n ≧1,000,000. In some aspects of these embodiments, the copolymer has a number average molecular weight, M n , of 26,500 to 5,000,000; alternatively M n of 40,000 to 5,000,000; alternatively M n of 50,000 to 5,000,000; alternatively M n of 70,000 to 5,000,000; alternatively M n of 95,000 to 5,000,000; alternatively M n of 100,000 to 5,000,000; alternatively M n of 150,000 to 2,000,000; alternatively M n of 100,000 to 1,000,000; alternatively M n of 100,000 to 800,000; alternatively M n of 250,000 to 500,000.

In some embodiments of the present invention, the terpolymer has a polymer chain according to the formula

wherein A is a derived from an acyclic aliphatic olefin monomer; R 21 is selected from H and CH 3 ; G is selected from —OR 22 and —COOR 22 , where R 22 is a C 1-24 alkyl group; E is selected from norbornene, substituted norbornene, styrene and styrene derivatives; wherein f is 0.001 to 0.99 and e is 0.001 to 0.5. In some aspects of these embodiments, f is 0.005 to 0.95, alternatively f is 0.05 to 0.90, alternatively f is 0.3 to 0.99, alternatively f is 0.5 to 0.98, alternatively f is 0.15 to 0.8. In some aspects of these embodiments, e is 0.01 to 0.25, alternatively e is 0.01 to 0.1.

Some embodiments of the present invention will now be described in detail in the following Examples. All fractions and percentages set forth below in the Examples are by weight unless otherwise specified. The chemical structures presented in Table 1 have been drawn according to the general rules for drawing Lewis structures of molecules as described in, for example, Brown, et al., Organic Chemistry , Brooks-Cole, 4th ed 2004.

EXAMPLES 1-16

Ligand Synthesis

Following the general procedure presented below using Component A and Component B identified in Table 1 in the amounts listed in Table 1, the Product Solids listed in Table 1 were prepared with the reported yield for examples 1-15, respectively.

Component A was added to a 100 mL flask (“Flask A”) then placed under vacuum and refilled with nitrogen and charged with 60 mL of tetrahydrofuran (THF). Flask A was then placed in an ice bath and allowed to cool to 0° C. 10.1 mL of 2.5 molar n-BuLi was then injected. Flask A was then placed in a dry ice/acetone bath and allowed to cool to about −78° C.

A separate 500 mL Schlenk flask (“Flask B”) was placed under vacuum. Flask B was purged with nitrogen and charged with ˜50 mL of THF. Flask B was then placed in a dry ice/acetone bath and allowed to cool to about −78° C. 1.10 mL of PCl 3 was then added to Flask B with agitation. The contents of Flask A were then slowly transferred to Flask B using a cannula with vigorous agitation.

A separate 100 mL flask (“Flask C”) was purged and filled with nitrogen. Flask C was then charged with ˜60 mL of THF and Component B. Flask C was then placed in a dry ice/acetone bath and allowed to cool with agitation to about −78° C. 10.1 mL of 2.5 molar n-BuLi was added to Flask C and allowed to react for about 15 minutes. The contents of Flask C were then transferred to Flask B, maintained at −78° C., using a cannula with continued vigorous agitation. Following the complete addition of the contents of Flask C into Flask B, Flask B was allowed to warm to room temperature for about 30 minutes. The contents of Flask B were then poured into a 500 mL recovery flask (Flask D) and the THF was removed, leaving a solid. The solid in Flask D was then mixed with distilled water and then transferred to a separation flask (Flask E). 100 mL of CH 2 Cl 2 was added to the contents of Flask E. Flask E was shaken to mix the two layers. About 5 mL of concentrated HCl was then added to Flask E. Flask E was shaken again. The mixture in Flask E was then allowed to settle, forming two layers—an organic phase on the bottom and a aqueous phase on the top. The organic layer was collected. The aqueous phase was washed with 50 mL of CH 2 Cl 2 . The organic wash material was collected and added to the previously collected organic layer material. The combined organic material was then contacted with MgSO 4 and rotovaped to dryness, leaving a solid. The solid was then washed first with diethyl ether and then with THF to remove impurities. The washed Product Solid was collected by filtration with the yield reported in Table 1.