Solubility improvement of non-metallocene transition metal complexes in aliphatic hydrocarbon solvents

Patent metadata

Field	Value
Publication number	US-11739169-B2
Application number	US-202117226659-A
Country	US
Kind code	B2
Filing date	Apr 9, 2021
Priority date	Apr 24, 2020
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

It has become desirable to limit or exclude aromatic solvents, such as toluene, from polymerization reactions. For polymerization reactions employing a non-metallocene transition metal complex as a precursor to a polymerization catalyst, exclusion of aromatic solvents may be difficult due to the limited solubility of such complexes in aliphatic hydrocarbon solvents. Aliphatic hydrocarbon solutions suitable for conducting olefin polymerization reactions, particularly solution polymerization reactions, may comprise: a non-metallocene transition metal complex dissolved in an aliphatic hydrocarbon solvent at a concentration ranging from about 2 mM to about 20 mM at 25° C. in the presence of an organoaluminum compound. A molar ratio of aluminum of the organoaluminum compound to transition metal of the transition metal complex is about 1:1 or greater, and the organoaluminum compound comprises at least about 8 carbons per aluminum.

First claim

The invention claimed is:

1. A solution comprising:
a non-metallocene transition metal complex dissolved in an aliphatic hydrocarbon solvent at a concentration ranging from about 2 mM to about 20 mM at 23° C. in the presence of an organoaluminum compound;
wherein a molar ratio of aluminum of the organoaluminum compound to transition metal of the non-metallocene transition metal complex is about 1:1 or greater, and the organoaluminum compound comprises at least about 8 carbons per aluminum; and
wherein the non-metallocene transition metal complex has an aliphatic hydrocarbon solubility of less than 2 mM in an absence of the organoaluminum compound.

2. The solution of claim 1 , wherein a reaction product of the non-metallocene transition metal complex and the organoaluminum compound or an adduct of the non-metallocene transition metal complex and the organoaluminum compound is dissolved in the aliphatic solvent.

3. The solution of claim 1 , wherein the non-metallocene transition metal complex has a structure represented by LM(X) 2 ;
wherein M is a transition metal, L is a dianionic ligand coordinated to M, and X is an anionic group containing six or fewer non-hydrogen atoms, or two Xs are joined to form a ring defining a chelating ligand, a diene ligand or an alkylidene ligand.

4. The solution of claim 3 , wherein each X is a C 1 -C 6 hydrocarbyl group.

5. The solution of claim 3 , wherein each X is a methyl group.

6. The solution of claim 1 , wherein the non-metallocene transition metal complex comprises at least one complex selected from the group consisting of a pyridyldiamide, a quinolinoyldiamide, a bis(phenolate), and a heterocyclic amide complex.

7. The solution of claim 1 , wherein the solution comprises at most about 5 ppm aromatic solvent.

8. The solution of claim 7 , wherein the aromatic solvent comprises toluene.

9. The solution of claim 1 , wherein the organoaluminum compound comprises at least one compound selected from the group consisting of a trialkylaluminum, a bis(dialkylaluminum) oxide, a dialkylaluminum hydride, a dialkylaluminum alkoxide, an alkylaluminum bisalkoxide, an aluminum trisalkoxide, a dialkylaluminum halide, an alkylaluminum dihalide, and any combination thereof.

10. The solution of claim 1 , wherein the organoaluminum compound comprises at least one compound selected from the group consisting of a trialkylaluminum, a bis(dialkylaluminum)oxide, a dialkylaluminum hydride, and any combination thereof.

11. The solution of claim 1 , wherein the organoaluminum compound comprises two or more alkyl groups, and the alkyl groups are C 3 or larger.

12. The solution of claim 1 , wherein the organoaluminum compound comprises at least 12 carbons per aluminum.

13. The solution of claim 1 , wherein the aliphatic hydrocarbon solvent comprises a linear, branched, cyclic, or branched cyclic aliphatic hydrocarbon having 9 or fewer carbons.

14. The solution of claim 1 , wherein the aliphatic hydrocarbon solvent is methylcyclohexane, isohexane, or any combination thereof.

15. The solution of claim 1 , wherein the solution consists essentially of the non-metallocene transition metal complex, the aliphatic hydrocarbon solvent, and the organoaluminum compound.

16. A catalyst system comprising:
the solution of claim 1 ; and
at least one activator effective to activate the non-metallocene transition metal complex.

17. The catalyst system of claim 16 , wherein the at least one activator comprises an activator selected from the group consisting of an alumoxane, a non-coordinating anion activator, and any combination thereof.

18. The catalyst system of claim 16 , wherein the at least one activator comprises a non-coordinating anion activator, and the non-coordinating anion activator comprises an anion portion selected from the group consisting of tetrakis(perfluorophenyl)borate, tetrakis(perfluoronaphthyl)borate, and tetrakis(perfluorobiphenyl)borate.

19. The catalyst system of claim 16 , wherein the catalyst system comprises at most about 5 ppm aromatic solvent.

20. The catalyst system of claim 19 , wherein the aromatic solvent comprises toluene.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Jiang Peijun
• Rix Francis C
• Harlan Charles J
• Canich Jo Ann M

Classifications

• C08F4/65912 Primary

  in combination with an organoaluminium compound · CPC title

• C08F4/62003

  the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond · CPC title

• C08F4/642

  Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/64003

  the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title