Pyridyldiamide metal catalysts and processes to produce polyolefins

Patent metadata

Field	Value
Publication number	US-9321858-B2
Application number	US-201414258121-A
Country	US
Kind code	B2
Filing date	Apr 22, 2014
Priority date	Apr 23, 2013
Publication date	Apr 26, 2016
Grant date	Apr 26, 2016

Abstract

Disclosed are new classes of pyridyldiamide catalyst components useful in olefin polymerization, an example of which includes:

wherein M is a hafnium or zirconium; R 1 and R 11 are selected from phenyl and substituted phenyl, wherein the substitutions are selected from C 1 to C 5 hydrocarbyls, preferably C 2 to C 4 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring; R 2′ and R 2″ are selected independently from hydrogen and C 1 to C 6 hydrocarbyls, preferably hydrogen; R 10 is a hydrocarbyl bridging group; R 3 , R 4 , and R 5 are independently selected from hydrogen, hydrocarbyls, and substituted hydrocarbyls; and R 6 , R 7 , R 8 , and R 9 are independently selected from hydrogen, hydrocarbyls, and substituted hydrocarbyls; wherein R 6 and R 7 form an aromatic ring or R 7 is hydrogen and R 6 is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl, preferably methyl.

First claim

The invention claimed is:

1. A pyridyldiamide metal catalyst component having the general formula (5) or (6):

wherein:
M is a Group 3-12 metal;
Q 1 is a three atom bridging group by the formula -G 1 -G 2 -G 3 -, each of which may be independently substituted with R 30 and R 31 groups, where G 2 is a group 15 or 16 atom, G 1 and G 3 are each a group 14, 15 or 16 atom, where G 1 , G 2 and G 3 , or G 1 and G 2 , or G 1 and G 3 , or G 2 and G 3 may form a singular or multi ring system, and if any of G 1 and/or G 3 is a group 14 atom then R 30 and R 31 are bound to such G atom(s), and if any of G 1 , G 2 and/or G 3 is a group 15 atom then R 30 is bound to such G atom(s), where each R 30 and R 31 is, independently, hydrogen or a C 1 to C 20 or C 50 or C 100 hydrocarbyl group;
Q 2 is a group that forms a bond with M, including but not limited to a group 16 element (such as O or S) or NR 17 or PR 17 , where R 17 is selected from hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl;
Q 3 is -(TT)- or -(TTT)-, where each T is carbon or a heteroatom, and each carbon or heteroatom may independently be substituted by hydrogen or one or more R 30 groups, and as part of the “—C-Q 3 =C—” fragment forms a 5- or 6-membered cyclic group or a polycyclic group including the 5 or 6 membered cyclic group;
R 1 is selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;
R 6 is selected from groups containing 1 to 12 carbons;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group, and n is 0, 1, 2, 3, or 4; and
L′ is neutral Lewis base, and w is 0, 1, 2, 3, or 4.

2. The pyridyldiamide metal catalyst component of claim 1 , wherein R 1 is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C 1 to C 5 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.

3. The pyridyldiamide metal catalyst component of claim 1 , wherein R 11 is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C 1 to C 5 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.

4. The pyridyldiamide metal catalyst component of claim 1 , wherein R 6 is selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl.

5. The pyridyldiamide metal catalyst component of claim 1 , wherein M is hafnium or zirconium.

6. A process to produce olefins comprising combining the pyridyldiamide metal catalyst component of claim 1 with any one of or combination of ethylene and C 3 to C 12 olefins at a temperature from 60° C. to 140° C.

7. A process to produce polypropylene using a pyridyldiamide metal catalyst component, comprising combining propylene, and optionally ethylene or C 4 to C 12 olefins, with an activator and the catalyst component of claim 1 .

8. The pyridyldiamide metal catalyst component of claim 1 , wherein the catalyst component is represented by the formula (7):

wherein:
M is a Group 3, 4 or 5 metal;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 and R 4 , and/or R 4 and R 5 ) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
R 6 is selected from C 1 to C 12 hydrocarbyls;
R 7 , R 8 , and R 9 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 and R 7 and/or R 8 and R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group, and n is 0, 1, 2, 3, or 4; and
L′ is neutral Lewis base, and w is 0, 1, 2, 3 or 4.

9. The pyridyldiamide metal catalyst component of claim 8 , wherein R 1 is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C 1 to C 5 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.

10. The pyridyldiamide metal catalyst component of claim 8 , wherein R 11 is selected from phenyl and substituted phenyl, wherein the substitutions are selected from C 1 to C 5 hydrocarbyls, and can reside in any of the ortho, meta, para positions on the phenyl ring.

11. The pyridyldiamide metal catalyst component of claim 8 , wherein M is hafnium or zirconium.

12. A process to produce olefins comprising combining the pyridyldiamide metal catalyst component of claim 8 with any one of or combination of ethylene and C 3 to C 12 olefins at a temperature from 60° C. to 140° C.

13. A process to produce polypropylene using a pyridyldiamide metal catalyst component, comprising combining propylene, and optionally ethylene or C 4 to C 12 olefins, with a catalyst component and activator, the catalyst component comprising (8):

wherein:
M is a Group 3, 4 or 5 metal;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, silyl, or substituted silyl groups;
R 2′ and R 2″ a

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Hagadorn John R
• Borisov Ilya S
• Golenishchev Arkady K
• Uborsky Dmitry V
• Voskoboynikov Alexander Z
• Samsonov Oleg V
• Sharikov Michail I

Classifications

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C08F10/00 Primary

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

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title