Producing polyolefin products

1. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, comprising contacting ethylene and a comonomer with a catalyst system, wherein the catalyst system comprises a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:

(C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2

wherein each R 1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are >3; a+b =c+d =5; at least one R 1 and at least one R 2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1 and R 2 groups are optionally coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1 or R 2 group; and the second catalyst compound comprises the following formula:

wherein each R 3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5 are the same or different; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to an R 3 , R 4 , or R 5 group.

2. The method of claim 1 , wherein the value of a comonomer/ethylene incorporation ratio for the second catalyst is less than about 0.8 as large as comonomer/ethylene incorporation ratio of the first catalyst.

3. The method of claim 1 , wherein the value of the comonomer/ethylene incorporation ratio for the second catalyst is less than about 0.25 as large as a comonomer/ethylene incorporation ratio of the first catalyst.

4. The method of claim 1 , comprising continuously combining a catalyst component slurry with a catalyst component solution to form the commonly supported catalyst system.

5. The method of claim 4 , wherein the catalyst component slurry comprises the first catalyst compound and the catalyst component solution comprises the second catalyst compound.

6. The method of claim 1 , comprising adjusting a ratio of the comonomer to ethylene to control a composition distribution, a molecular weight distribution, a melt index (I 2 ), or a ratio of two melt indices, or any combinations thereof, of the polyolefin polymer.

7. A catalyst composition comprising a first catalyst compound and a second catalyst compound that are co-supported forming a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula:

(C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2

wherein each R 1 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R 2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are >3; a+b =c+d =5; at least one R 1 and at least one R 2 is a hydrocarbyl or substituted hydrocarbyl group; adjacent groups R 1 and R 2 groups are optionally coupled to form a ring; and each X is independently a leaving group selected from a labile hydrocarbyl, substituted hydrocarbyl, or heteroatom group, or a divalent radical that links to an R 1 or R 2 group; and the second catalyst compound comprises the following formula:

wherein each R 3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; R 4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteoatom group; each R 5 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R 3 , R 4 , and R 5 are the same or different; wherein R 3 , R 4 , or R 5 groups are optionally joined with R 3 , R 4 , or R 5 groups on an opposing cyclopentadienyl structure to form one or more bridges if the number of atoms connecting the two cyclopentadienyl rings is >3; and each X is independently a leaving group selected from a labile hydrocarbyl, a substituted hydrocarbyl, a heteroatom group, or a divalent radical that links to a R 3 , R 4 , or R 5 substituent.

8. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

9. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

10. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

wherein each R 4 is independently a methyl, ethyl, propyl, pentyl, hexyl, octyl, nonyl, dodecyl, phenethyl, or other hydrocarbyl.

11. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

12. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

13. The catalyst composition of claim 7 , wherein the second catalyst compound comprises at least one compound with the following formula:

14. The catalyst composition of claim 7 , wherein the first catalyst compound has the following formula:

15. The catalyst composition of claim 7 , wherein the first catalyst compound has the following formula:

16. The catalyst composition of claim 7 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10.

17. The catalyst composition of claim 7 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 3:1 to 1:3.

18. The catalyst composition of claim 7 , comprising an organometallic agent comprising a compound of the following formula: ER 6 n R 7 V-n , wherein E is Al, B, Mg, Ca, Zn, Si, Ti, Zr, Hf; each R 6 is independently H, or a hydrocarbyl; each R 7 is independently a H, a C1 to C20 hydrocarbon group, or a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus; V is the valence of E, and n is 1-V.

19. The catalyst composition of claim 7 , further comprising a catalyst compound of the following formula:

wherein M is Ti, Zr, or Hf;

wherein R 9 is H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group;

and wherein each R 9 are optionally joined together to form a ring; wherein each R 10 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group.

20. The catalyst composition of claim 7 , further comprising at least one Group 15 containing catalyst compound represented by the formula:

wherein:

M is a Group 4, 5, or 6 metal;

y is 0 or 1, wherein when y is 0, group L′ is absent;

n is the oxidation state of M;

m is the formal charge of the ligand represented by YZL and YZL′;

L, L′, Y and Z are each a Group 15 element;

each R 11 and R 12 is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group;

R 13 is absent or is H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group;

each R 14 and R 15 is independently a hydrocarbyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;

each R 16 and R 17 is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; and

R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.