Bis-phosphaguanidine and poly-phosphaguanidine ligands with group IV metal catalysts produced therefrom

Patent metadata

Field	Value
Publication number	US-11028190-B2
Application number	US-201716337602-A
Country	US
Kind code	B2
Filing date	Sep 28, 2017
Priority date	Sep 30, 2016
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

Embodiments are directed to bis- and poly-phosphaguanidine compounds, and the metal-ligand complexes formed therefrom, wherein the metal complexes can be used as procatalysts in polyolefin polymerization. Formulas (I) (II) and (III).

First claim

The invention claimed is:

1. A phosphaguanidine compound comprising the structure of formula I:

wherein
R 2 , R 5 , R 7 , and R 9 are independently selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties, and a lone pair of electrons;
R 6 is an aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety;
R 1 and R 8 are independently selected from the same or different moieties selected from aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties and a lone pair of electrons;
R a1 , R a2 , R b1 , and R b2 are independently selected from aliphatic moieties, heteroaliphatic moieties, aromatic moieties, and heteroaromatic moieties.

2. The phosphaguanidine compound according to claim 1 , wherein one of R 2 and R 5 is a lone pair of electrons and the other of R 2 and R 5 is a hydride, aliphatic moiety, heteroaliphatic moiety, aromatic moiety, or heteroaromatic moiety; and one of R 9 and R 7 is a lone pair of electrons and the other of R 9 and R 7 is a hydride, aliphatic moiety, heteroaliphatic moiety, aromatic moiety, or heteroaromatic moiety.

3. The phosphaguanidine compound according to claim 1 , wherein R 6 is a (C 3 -C 6 )hydrocarbyl moiety.

4. The phosphaguanidine compound according to claim 1 , wherein R 6 is a heteroatom selected from a silicon atom, a germanium atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

5. The phosphaguanidine compound according to claim 1 , wherein R a1 , R a2 , R b1 , and R b2 comprise substituted and unsubstituted phenyl rings.

6. The phosphaguanidine compound according to claim 1 , wherein R a1 , R a2 , R b1 , and R b2 comprise (C 5 -C 6 )cyclohydrocarbyl groups.

7. The phosphaguanidine compound according to claim 1 , wherein R 1 or R 2 and R 7 or R 8 comprise adamantyl groups.

8. The phosphaguanidine compound according to claim 1 , wherein R 1 or R 2 and R 7 or R 8 are independently selected from methyl, ethyl, cyclohexyl, iso-propyl, iso-butyl, and tert-butyl moieties.

9. The phosphaguanidine compound according to claim 1 , wherein R 8 is a repeating unit, the phosphaguanidine compound of formula II comprising:

where
n is an integer from two to six; R 10 is selected from a hydrogen atom, an aliphatic moiety, heteroaliphatic moiety, aromatic moiety, or heteroaromatic moiety;
R y and R z include the same or different moieties selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties, or a lone pair of electrons;
R a and R b are independently selected from aliphatic moieties, heteroaliphatic moieties, and aromatic moieties, heteroaromatic moieties; and
wherein each R a , R b , R y , and R z is the same or different.

10. A metal-ligand complex comprising the phosphaguanidine compound of formula III:

where
R 1 and R 8 are independently selected from hydride, aliphatic, heteroaliphatic, aromatic, and heteroaromatic moieties;
R a1 , R a2 , R b1 , and R b2 are the same or different moieties selected from aliphatic moieties, aromatic moieties, and heteroaromatic moieties;
M is selected from titanium, zirconium, or hafnium; each X is independently selected from aliphatic moieties, aromatic moieties, NR N 2 moieties and halide moieties, wherein R N is selected from alkyl, aryl, or heteroaryl moieties;
R 6 is selected from an aliphatic moiety, heteroaliphatic moiety, aromatic moiety, and a heteroatom; and
each dotted line optionally defines a bridging connection.

11. A biphenyl- phosphaguanidine compound comprising the structure of Formula IV:

where
G 1 , G 2 , G 3 , G 4 , G 5 , G 7 , G 8 , G 9 , G 10 , and G 11 are independently selected from hydrides, alkyl groups, aryl groups, heteroaryl groups, and guanidine moiety;
each phenyl ring comprises at least one guanidine moiety, the guanidine moiety has a structure according to formula V:

where
R d and R e are independently selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties, and lone pair of electrons;
R c is selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties and lone pairs of electrons;
R a and R b are independently selected from aliphatic moieties, heteroaliphatic moieties, aromatic moieties, and heteroaromatic moieties; and
each curved dotted line optionally defines a bridging connection,
wherein, in cases where there are a plurality of guanidine moieties, R a , R b , R c , R d , and R e may be the same or different within the plurality of guanidine moieties.

12. The biphenyl- phosphaguanidine compound according to claim 11 , wherein G 1 , G 5 , G 7 , and G 11 include the guanidine moiety of formula V, and G 2 , G 3 , G 4 , G 8 , G 9 , and G 10 are hydrogen atoms.

13. The biphenyl- phosphaguanidine compound according to claim 11 , wherein G 2 , G 4 , G 8 , and G 10 include the guanidine moiety of formula V, and G 1 , G 3 , G 5 , G 7 , G 9 , and G 11 include hydrides, alkyl, aryl, or heteroaryl moieties.

14. The biphenyl- phosphaguanidine compound according to claim 11 , wherein one of R e and R d is a hydrogen atom, an aliphatic moiety, a heteroaliphatic moiety, an aromatic moiety, a heteroaromatic moiety and the other of R d and R e is a lone pair of electrons.

15. The biphenyl- phosphaguanidine compound according to claim 11 , wherein R d is selected from hydride, methyl, ethyl, iso-propyl, cyclohexyl, iso-butyl, benzyl, adamantyl, tert-butyl, phenyl, 2,6-dimethylphenyl, 2,6-diiso-propylphenyl, and a lone pair of electrons.

16. A polymerization catalyst comprising the biphenyl-phosphaguanidine compound according to claim 11 and a transition metal catalyst bonded to the biphenyl-phosphaguanidine compound, wherein the transition metal catalyst is hafnium, zirconium, or titanium.

17. A phosphaguanidine naphthalene compound comprising the structure of formula VI:

where
G 21 , G 22 , G 23 , G 24 , G 25 , G 27 , and G 28 are independently selected from hydrides, alkyl groups, aryl or heteroaryl groups, or alkylguanidine moieties; each phenyl ring comprises at least one guanidine moiety;
the guanidine moiety comprising the structure of formula V:

where
R d and R e are independently selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties, and may include lone pair of electrons;
R c is selected from hydrides, aliphatic moieties, heteroaliphatic moieties, aromatic moieties, heteroaromatic moieties and or lone pairs of electrons;
R a and R b are independently selected from aliphatic moieties, heteroaliphatic moieties, aromatic moieties, and heteroaromatic moieties; and
each curved dotted line optionally define

Assignees

• Dow Global Technologies Llc

Inventors

• Camelio Andrew M
• Krasovskiy Arkady L
• Christianson Matthew D
• Froese Robert D J

Classifications

• C08F2500/04

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

• C08F4/64013 Primary

  NN · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F210/16 Primary

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

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title