Catalyst systems and processes for poly alpha-olefin having high vinylidene content

1. An unsaturated poly alpha-olefin (PAO) product comprising:

greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes contained therein;

0.1 mol % to 3.5 mol % of tri-substituted vinylenes;

3.0 mol % or less of di-substituted vinylenes;

3.0 mol % or less of vinyl groups; based on total moles of vinylidenes, tri-substituted vinylenes, di-substituted vinylenes, and vinylidenes contained therein;

and having an Mn of less than 5000 g/mol as determined by 1 H NMR.

2. The unsaturated poly alpha-olefin (PAO) product of claim 1 further comprising:

96.5 mol % to 99.9 mol % of vinylidenes; and

a number average molecular weight (Mn) of 1500 g/mol or less as measured by 1 H NMR.

3. The unsaturated poly alpha-olefin (PAO) product of claim 1 further comprising:

less than or equal to about 1.0 mol % di-substituted vinylenes, when present;

less than or equal to about 1.0 mol % vinyl groups when present; and

a number average molecular weight (Mn) of 1000 g/mol or less as measured by 1 H NMR.

4. The unsaturated poly alpha-olefin (PAO) product of claim 1 further comprising greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes contained therein, and from 98 mol % to 99.5 mol % of a combination of vinylidenes and tri-substituted vinylenes; 0.5 mol % to 2 mol % of a combination of di-substituted vinylenes and vinyl groups; and a number average molecular weight (Mn) of 800 g/mol or less as measured by 1 HNMR.

5. The unsaturated poly alpha-olefin product of claim 3 wherein the unsaturated poly alpha-olefin product is dimer.

6. The unsaturated poly alpha-olefin product of claim 4 wherein the unsaturated poly alpha-olefin product is dimer.

7. The unsaturated poly alpha-olefin (PAO) product of claim 1 wherein the PAO product comprises greater than or equal to about 90 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes contained therein and having an Mn of less than 5000 g/mol as determined by 1 H NMR.

8. A process for making a poly alpha-olefin, PAO, the process comprising:

contacting a feed comprising a C6-C32 alpha-olefin with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising vinylidenes, tri-substituted vinylenes, optionally di-substituted vinylenes, and optionally vinyls; and

obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes contained therein, 0.1 mol % to 3.5 mol % of tri-substituted vinylenes, 3.0 mol % or less of di-substituted vinylenes, 3.0 mol % or less of vinyl groups; based on total moles of vinylidenes, tri-substituted vinylenes, di-substituted vinylenes, and vinylidenes contained therein, and having an Mn of less than 5000 g/mol as determined by 1 H NMR,

wherein the conversion is about 10% or more and the polymerization reaction exhibits a selectivity toward greater than or equal to about 80 mol % vinylidenes, based on total moles of vinyls, vinylidenes, di-substituted vinylenes, and tri-substituted vinylenes in the unsaturated PAO product,

wherein the metallocene compound is represented by formula (F-MC):

wherein:

R 2 is hydrogen and one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6 hydrocarbyl group, and the other one of R 1 and R 3 is a hydrogen;

R 4 and R 5 taken together with the carbon atoms in the cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annulated to the cyclopentadienyl ring;

R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl, silylcarbyl, or germanyl group, and optionally at least three of R 12 , R 13 , R 14 , R 15 , and R 16 are not hydrogen;

M is a group 3, 4 or 5 transition metal having an integer coordination number of v; wherein v is 3, 4, or 5,

each X is independently a halogen, a hydride, an amide, an alkoxide, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and

m is an integer equal to v-2.

9. The process of claim 8 , wherein:

one of substituted hydrocarbyls R 1 and R 3 comprise an alpha Group 14 atom directly attached to the indenyl ring, a beta Group 14 atom attached to the alpha atom, and two or more, substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 8 hydrocarbyl groups attached to the beta atom.

10. The process of claim 8 , wherein the metallocene compound is represented by formula (II):

wherein:

R 1 and R 2 are hydrogen;

R 3 comprises R 23 and R 19 which comprise one or more Group 14 atoms;

R 20 , R 2 1 , and R 22 are independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group and at least two of R 20 , R 21 , and R 22 are independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group, wherein at least two of R 20 , R 21 , and R 22 are a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl group;

R 6 , R 7 , R 17 , and R 18 are each independently hydrogen; a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl group; or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annulated to the indenyl ring;

R 12 , R 13 , R 14 , R 15 and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 hydrocarbyl group;

each X is independently a halogen, a hydride, an amide, an alkoxide, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;

M is a group 3, 4 or 5 transition metal having an integer coordination number of v; wherein v is 3, 4, or 5, and

m is an integer equal to v-2.

11. The process of claim 9 , wherein:

one of substituted hydrocarbyls R 1 and R 3 comprise an alpha Group 14 atom directly attached to the indenyl ring, a beta Group 14 atom attached to the alpha atom, and two or more, substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 8 hydrocarbyl groups attached to the beta atom.

12. The process of claim 10 , wherein R 23 and R 19 comprise one or more silicon atoms.