Metallocene catalysts for producing vinyl-terminated polyalphaolefins and methods associated therewith

1 . A method comprising:

contacting a catalyst system with an olefinic feed comprising a C 3 -C 32 alpha olefin under polymerization reaction conditions, wherein the catalyst system comprises at least one activator and a metallocene compound represented by the formula:

wherein:

M is a group 4 transition metal;

T is a bridging group;

each X is independently a leaving group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;

R 1 and R 2 are independently hydrogen, or a C 1 -C 40 optionally substituted hydrocarbyl group, halide, or siloxyl group;

R 3 , R 4 , R 5 and R 6 are independently a C 1 -C 40 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, aminocarbyl, or siloxyl group; and

A is an aliphatic, aromatic or heteroaromatic ring, optionally bearing one or more additional fused rings which may be aliphatic, aromatic or heteroaromatic; and

obtaining a plurality of polyalphaolefins (PAOs) having at least 30 mol % vinyl-terminated PAOs, the vinyl-terminated PAOs having a terminal —CH═CH 2 group.

2 . The method of claim 1 , wherein at least a portion of the plurality of PAOs comprises one or more of trisubstituted vinylene groups, disubstituted vinylene groups, and vinylidene groups.

3 . The method of claim 1 , wherein at least 62 mol % of the PAOs are vinyl-terminated PAOs.

4 . The method of claim 1 , wherein the plurality of PAOs lacks a C 3 alpha olefin monomer.

5 . The method of claim 1 , wherein the plurality of PAOs comprises a C 3 alpha olefin, wherein the polymerization reaction conditions comprise a reaction temperature of about 80° C. or more.

6 . The method of claim 1 , wherein R 1 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, trimethylsilylmethyl or an isomer thereof, and wherein R 3 , R 4 , R 5 and R 6 are each methyl and R 2 is hydrogen.

7 . The method of claim 1 , wherein the feed comprises a C 3 -C 32 alpha olefin selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or isomers thereof having a terminal carbon-carbon double bond, and any combination thereof.

8 . The method of claim 1 , wherein when R 3 , R 4 , R 5 and R 6 are Me and the cyclopentadiene and A form an indenyl group, R 1 is not Me, Et or nPr or the 6 membered aromatic ring of the indenyl group is substituted, and when R 3 , R 4 , R 5 and R 6 are Me and the cyclopentadiene and A form a benz[e]indenyl ligand, the benz[e]indenyl ligand is substituted.

9 . The method of claim 1 , wherein R 2 is hydrogen.

10 . The method of claim 1 , wherein the metallocene compound is represented by the formula:

wherein R 7 , R 8 , R 9 , and R 10 are independently hydrogen or a C 1 -C 40 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, aminocarbyl, germylcarbyl, oxyhydrocarbyl, halide, or siloxyl group and optionally, R 7 and R 8 , or R 8 and R 9 , or R 9 and R 10 are joined together to form a fused carbocyclic ring.

11 . The method of claim 10 , wherein when R 3 , R 4 , R 5 and R 6 are Me, R 1 is not Me, Et, or nPr or at least one of R 2 , R 7 , R 8 , R 9 , or R 10 is not H.

12 . The method of claim 10 , wherein R 2 is hydrogen.

13 . The method of claim 1 , wherein the metallocene compound is represented by the formula:

wherein R 1 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl or C 6 -C 40 hydrocarbyl group, optionally substituted hydrocarbyl, halide, or siloxyl group.

14 . The method of claim 13 , wherein R 2 is hydrogen.

15 . The method of claim 1 , wherein at least 43.3 mol % of the PAOs are vinyl-terminated PAOs.

16 . A method comprising:

contacting a catalyst system with an olefinic feed comprising a C 3 -C 32 alpha olefin under polymerization reaction conditions, wherein the catalyst system comprises at least one activator and a metallocene compound represented by the formula:

wherein:

M is a group 4 transition metal;

T is a bridging group;

each X is independently a leaving group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;

R 1 and R 2 are independently hydrogen, or a C 1 -C 40 optionally substituted hydrocarbyl group, halide, or siloxyl group;

R 3 , R 4 , R 5 and R 6 are independently a C 1 -C 40 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, aminocarbyl, or siloxyl group; and

R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently hydrogen or a C 1 -C 40 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, aminocarbyl, germylcarbyl, oxyhydrocarbyl, halide, or siloxyl group, where at least one of R 1 , R 2 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is not H; and

obtaining a plurality of polyalphaolefins (PAOs) having at least 30 mol % vinyl-terminated PAOs, the vinyl-terminated PAOs having a terminal —CH═CH 2 group.

17 . The method of claim 16 , wherein R 2 is hydrogen.

18 . A method comprising:

contacting a catalyst system with an olefinic feed comprising a C 3 -C 32 alpha olefin under polymerization reaction conditions, wherein the catalyst system comprises at least one activator and a metallocene compound represented by the formula:

wherein:

M is a group 4 transition metal;

T is a bridging group;

each X is independently a leaving group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;

R 1 and R 2 are independently hydrogen, or a C 1 -C 40 optionally substituted hydrocarbyl group, halide, or siloxyl group;

R 3 , R 4 , R 5 and R 6 are independently a C 1 -C 40 optionally substituted hydrocarbyl, halocarbyl, silylcarbyl, aminocarbyl, or siloxyl group; and

R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently hydrogen or a C 1 -C 40 optionally substituted hydrocarbyl, halide, or siloxyl group; and

obtaining a plurality of vinyl terminated polyalphaolefins (PAOs) having at least 30 mol % vinyl-terminated PAOs, the vinyl-terminated PAOs having a terminal —CH═CH 2 group.

19 . The method of claim 18 , wherein R 2 is hydrogen.