Producing polyolefin products

Patent metadata

Field	Value
Publication number	US-2016347889-A1
Application number	US-201515116696-A
Country	US
Kind code	A1
Filing date	Feb 10, 2015
Priority date	Feb 11, 2014
Publication date	Dec 1, 2016
Grant date	—

Abstract

Catalyst systems and methods for making and using the same. A method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, includes contacting ethylene and a comonomer with a catalyst system. The catalyst system includes a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system. The first catalyst compound includes a compound with the general formula (C 5 H a R 1 b )(C 5 H c R 2 d )HfX 2 . The second catalyst compound includes at least one of the following general formulas: In both catalyst systems, the R groups can be independently selected from any number of substituents, including, for example, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group, among others.

First claim

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 may be 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 may be 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 . (canceled)

5 . (canceled)

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

7 . The method of claim 6 , wherein the catalyst component slurry comprises the first catalyst compound and the catalyst component solution comprises the second catalyst compound.

8 . (canceled)

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . (canceled)

13 . (canceled)

14 . (canceled)

15 . The method of claim 1 , comprising adjusting a ratio of the comonomer to ethylene within a polymerization reactor 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.

16 . (canceled)

17 . 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 may be 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 may be the same or different; wherein R 3 , R 4 , or R 5 groups may be 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.

18 . The catalyst composition of claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula:

19 . The catalyst composition of claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula:

20 . The catalyst composition of claim 17 , 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.

21 . The catalyst composition of claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula:

22 . The catalyst composition of claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula:

23 . The catalyst composition of claim 17 , wherein the second catalyst compound comprises at least one compound with the following formula:

24 . The catalyst composition of claim 17 , wherein the first catalyst compound has the following formula:

25 . The catalyst composition of claim 17 , wherein the first catalyst compound has the following formula:

26 . The catalyst composition of claim 17 , wherein the ratio of the first catalyst compound to the second catalyst compound is between about 10:1 to 1:10.

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

28 . (canceled)

29 . (canceled)

30 . (canceled)

31 . (canceled)

32 . (canceled)

Assignees

• Univation Techologies Llc
• Univation Tech Llc

Inventors

• Lue Ching-Tai
• Rix Francis C
• Harlan C Jeff
• Mccullough Laughlin G

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• B32B27/32

  comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)} · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F2500/01

  High molecular weight, e.g. >800,000 Da. · CPC title

• C08F2500/18

  Bulk density · CPC title