Spray-dried catalyst compositions and polymerization processes employing the same

Patent metadata

Field	Value
Publication number	US-9637567-B2
Application number	US-201214117272-A
Country	US
Kind code	B2
Filing date	Mar 28, 2012
Priority date	May 13, 2011
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

Spray-dried catalyst compositions comprising a transition metal complex and polymerization processes employing the same are disclosed herein. An embodiment provides a spray-dried catalyst composition comprising a transition metal catalyst component represented by the following formula: (I) and polymerization process employing the same.

First claim

What is claimed is:

1. A composition comprising:
a spray-dried catalyst composition comprising:
a transition metal catalyst component represented by the following formula:

wherein:
M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV];
X represents an atom or group covalently or ionically bonded to the metal M;
T is the oxidation state of the metal;
b is the valency of the atom or group X; and
R 1 to R 7 are each independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, hydrocarbyl substituted aryl, heterohydrocarbyl substituted aryl, benzyl, hydrocarbyl substituted benzyl, heterohydrocarbyl substituted benzyl and SiR′ 3 where each R′ is independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl; and when any two or more of R 1 to R 7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, aryl, hydrocarbyl substituted aryl, heterohydrocarbyl substituted aryl, benzyl, hydrocarbyl substituted benzyl or heterohydrocarbyl substituted benzyl the two or more can be linked to form one or more cyclic substituents;
an activator; and
a support, where the transition metal catalyst component and the activator are supported by the support and the spray-dried catalyst composition is a free flowing powder.

2. The composition according to claim 1 :
wherein R 5 of the transition metal catalyst component is represented by the following formula:

wherein R 7 of the transition metal catalyst is represented by the following formula:

wherein R 8 to R 17 of the transition metal catalyst are independently selected from the group consisting of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, and substituted heterohydrocarbyl, when any two or more of R 1 to R 4 , R 6 and R 8 to R 17 are hydrocarbyl, substituted hydrocarbyl, or substituted heterohydrocarbyl, the two or more can be linked to form one or more cyclic substituents.

3. The composition according to claim 2 , wherein R 1 to R 4 , R 6 , and R 8 to R 17 are each independently selected from the group consisting of hydrogen, halogen, and C 1 to C 8 hydrocarbyl.

4. The composition according to claim 2 , wherein R 10 and R 15 are each independently selected from group consisting of hydrogen, C 1 to C 8 hydrocarbyl, benzyl, fluorine, chlorine, bromine, and iodine.

5. The composition according to claim 2 , wherein R 1 , R 2 , R 3 , R 9 , R 11 , R 14 and R 16 are each hydrogen; and R 4 , R 6 , R 8 , R 10 , R 12 , R 13 , R 15 and R 17 are each represented by methyl.

6. The composition according to claim 1 , wherein the spray-dried catalyst composition further comprises a non-metallocene catalyst component, wherein the non-metallocene catalyst component is a Group-15 containing catalyst.

7. The composition according to claim 6 , wherein the non-metallocene catalyst component is represented by the following formula:
α a β b γ g MX n

wherein:
M is a metal atom;
X is independently selected from the group consisting of halogen ions, hydrides, C 1 to C 12 alkyls, C 2 to C 12 alkenyls, C 6 to C 12 aryls, C 7 to C 20 alkylaryls, C 1 to C 12 alkoxys, C 6 to C 16 aryloxys, C 7 to C 18 alkylaryloxys, halogenated C 1 to C 12 alkyls, halogenated C 2 to C 12 alkenyls, halogenated C 6 to C 12 aryls, halogenated C 7 to C 20 alkylaryls, halogenated C 1 to C 12 alkoxys, halogenated C 6 to C 16 aryloxys, halogenated C 7 to C 18 alkylaryloxys, C 1 to C 12 heteroatom-containing hydrocarbons, and substituted derivatives thereof;
β and γ are groups that each comprise at least one Group 14 to Group 16 atom;
α is a linking moiety that forms a chemical bond to each of β and γ; and
a, b, g, and n are each integers from 1 to 4.

8. The composition according to claim 7 , wherein M is zirconium or hafnium.

9. The composition according to claim 6 , wherein a mole ratio of the non-metallocene component to the transition metal catalyst component ranges from about 1:1 to about 5:1.

10. The composition according to claim 1 , wherein the spray-dried catalyst composition further comprises a metallocene catalyst component.

11. The composition according to claim 10 , wherein the metallocene catalyst component is represented by the following formula:
Cp A Cp B MX n
wherein:
M is a metal atom;
Cp A and Cp B are each individually substituted or unsubstituted cyclopentadienyl ligands;
X is a leaving group; and
N is zero or an integer from 1 to 4.

12. The composition according to claim 10 , wherein M is zirconium or hafnium.

13. A polymerization process comprising combining an olefin with the composition according to claim 1 .

14. The polymerization process according to claim 13 , wherein the olefin comprises ethylene.

15. The polymerization process according to claim 13 , wherein the olefin comprises propylene.

16. The polymerization process according to claim 13 , wherein the olefin comprises a C 4 to C 15 alpha olefin.

17. The polymerization process according to claim 13 , wherein the polymerization process occurs in a gas phase reactor.

18. The polymerization process according to claim 13 , wherein the polymerization process occurs at a temperature of about 30° C. to about 120° C.

Assignees

• Mariott Wesley R
• Cao Phuong A
• Zilker Jr Daniel P
• Oskam John H
• Mure Cliff R
• Univation Tech Llc

Inventors

• Mariott Wesley R
• Cao Phuong A
• Zilker Jr Daniel P
• Oskam John H
• Mure Cliff R

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F4/7042 Primary

  NNN · CPC title

• B01J31/403

  containing iron group metals or copper · CPC title

• C08F4/61904

  in combination with another component of C08F4/60 · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title