Quinolinyldiamido transition metal complexes, production and use thereof

Patent metadata

Field	Value
Publication number	US-10815318-B2
Application number	US-201916273631-A
Country	US
Kind code	B2
Filing date	Feb 12, 2019
Priority date	Jun 30, 2016
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Quinolinyldiamido transition metal complexes are disclosed for use in alkene polymerization to produce multimodal polyolefins.

First claim

What is claimed is:

1. A quinolinyldiamido transition metal complex represented by Formula II:

wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 metal;
X is an anionic leaving group;
L is a neutral Lewis base;
R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2;
n+m is not greater than 4; and
any adjacent R groups (e.g., R 1 & R 2 , R 2 & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted 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;
any two X groups may be joined together to form a dianionic group;
any two L groups may be joined together to form a bidentate Lewis base; and
an X group may be joined to an L group to form a monoanionic bidentate group,
E is carbon, silicon, or germanium;
R 7 through R 9 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and
any two R groups 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 12 is selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen,
R 10 and R 11 are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls,
where R 10 and R 11 are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

2. A quinolinyldiamido transition metal complex represented by Formula (II):

wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
X is an anionic leaving group;
L is a neutral Lewis base;
R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups;
R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;
n is 1 or 2;
m is 0, 1, or 2
n+m is not greater than 4; and
any two adjacent R groups (e.g. R 1 & R 2 , R 2 & R 3 , etc.) may be joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic ring, or unsubstituted 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;
any two X groups may be joined together to form a dianionic group;
any two L groups may be joined together to form a bidentate Lewis base; and
an X group may be joined to an L group to form a monoanionic bidentate group,
E is carbon, silicon, or germanium;
R 7 and R 8 are independently selected from the group consisting of hydrocarbyls and substituted hydrocarbyls,
R 9 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and
and any two R groups 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,
where R 7 and R 8 are joined to form a substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings.

3. The complex of claim 1 , wherein E is carbon.

4. The complex of claim 2 , wherein E is carbon.

5. The complex of claim 2 , wherein M is Ti, Zr, of Hf.

6. The complex of claim 1 , wherein M is Ti, Zr, or Hf.

7. The complex of claim 1 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

8. The complex of claim 2 , wherein R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, and halogen.

9. The complex of claim 1 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide.

10. The complex of claim 2 , wherein each L is independently selected from Et 2 O, MeOtBu, Et 3 N, PhNMe 2 , MePh 2 N, tetrahydrofuran, and dimethylsulfide.

11. The complex of claim 1 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

12. The complex of claim 2 , wherein each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

13. The complex of claim 1 , wherein R 1 is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

14. The complex of claim 2 , wherein R 1 is 2,6-diisopropylphenyl, 2,4,6-triisoproplphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

15. The complex of claim 1 , wherein R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorphenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

16. The complex of claim 2 , wherein R 13 is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

17. The complex of claim 1 , wherein R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

18. The complex of claim 2 , wherein R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.

19. The complex of claim 2 , wherein R 10 and R 11 are 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.

20. The complex of claim 2 , wherein R 10 and R 11 are joined to form a substituted or unsubstituted saturated hydrocarbyl ring, where the ring has 6 ring atoms and where substitutions on the ring can join to form additional rings.

21. A catalyst system comprising an activator and the transition metal complex of claim 1 .

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Palafox Patrick J
• Jiang Peijun
• Gao Yaohua
• Chen Xin
• Goryunov Georgy P
• Sharikov Mikhail I
• Uborsky Dmitry V
• Voskoboynikov Alexander Z

Classifications

• C07F7/003 Primary

  without C-Metal linkages · CPC title

• C08F10/02

  Ethene · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F2500/03

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

• C08F210/02

  Ethene · CPC title