Phosphaguanidine group IV metal olefin polymerization catalysts

Patent metadata

Field	Value
Publication number	US-11066495-B2
Application number	US-201716337588-A
Country	US
Kind code	B2
Filing date	Sep 29, 2017
Priority date	Sep 30, 2016
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

Embodiments are directed to phosphaguanidine metal complexes of formula I and using those complexes in α-olefin polymerization systems.

First claim

The invention claimed is:

1. A polymerization catalyst system comprising the phosphaguanidine complex according to formula I:

where
R 1 and R 5 are independently selected from hydride, aliphatic, heteroaliphatic, aromatic, and heteroaromatic moieties;
R 2 and R 4 are independently selected from aliphatic moieties, heteroaliphatic moieties, aromatic moieties, and heteroaromatic moieties;
R 3 is a lone pair of electrons;
M is selected from titanium, zirconium, and hafnium;
each X is selected from aliphatic moieties, aromatic moieties, NR N 2 moieties and halogen atoms, wherein R N is selected from alkyl, aryl, or heteroaryl moieties; and
each dotted line optionally defines a bridging connection.

2. The polymerization catalyst system according to claim 1 , wherein the polymerization catalyst system comprises a chain transfer agent.

3. The polymerization catalyst system according to claim 1 , wherein the chain transfer agent in the polymerization catalyst system is diethyl zinc.

4. The polymerization catalyst system according to claim 1 , wherein:
each X is selected from methyl, trimethylsilylmethylene, benzyl, chloro, and NMe 2 ;
R 2 and R 4 include the same or different moieties chosen from unsubstituted phenyl, substituted phenyl, substituted cyclohexyl groups, or unsubstituted cyclohexyl groups;
R 3 is a lone pair of electrons; and
R 1 and R 5 are independently selected from hydride, alkyl, methyl, ethyl, iso-propyl, cyclohexyl tert-butyl, adamantyl, neopentyl, phenethyl, benzyl, phenyl, and substituted phenyl moieties.

5. The polymerization catalyst system according to claim 1 , wherein the phosphaguanidine complex comprises the structure of formula II:

wherein
each X independently is selected from alkyl moieties, trimethylsilylmethylene, benzyl, chloro, and —NMe 2 ;
R 2 and R 4 is selected from phenyl, substituted phenyl, heteroaromatic groups, alkyl groups, and heteroalkyl groups;
R 3 is a lone pair of electrons;
R 1 and R 6 include the same or different moieties selected from hydride, alkyl, methyl, ethyl, iso-propyl, cyclohexyl tert-butyl, adamantyl, neopentyl, phenethyl, benzyl, substituted and non-substituted phenyl moieties, or substituted and non-substituted heteroaromatic groups; and
n is 0, 1, or 2.

6. The polymerization catalyst system according to claim 1 , wherein the phosphaguanidine complex comprises the structure of formula III:

wherein
each X independently is selected from methyl, trimethylsilylmethylene, benzyl, chloro, and —NMe 2 ;
R 2 and R 4 are independently selected from phenyl, substituted phenyl, cyclohexyl and substituted cyclohexyl;
R 3 is a lone pair of electrons;
R 1 and R 7 are independently selected from hydride, methyl, ethyl, iso-propyl, cyclohexyl tert-butyl, adamantyl, neopentyl, phenethyl, benzyl, and substituted phenyl moieties, and non-substituted phenyl moieties; and
n is 0, 1, or 2.

7. The polymerization catalyst system according to claim 1 , wherein polymerization catalyst system further comprises a co-catalyst.

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Christianson Matthew D
• Froese Robert D J

Classifications

• C07F9/5036

  Phosphines containing the structure -C(=X)-P or NC-P · CPC title

• C08F210/16 Primary

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

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F10/14 Primary

  Monomers containing five or more carbon atoms · CPC title

• C08F4/64044

  NN · CPC title