Bis(Metallocene) Compounds and Catalyst Compositions Employing Such Compounds

Patent metadata

Field	Value
Publication number	US-2021317238-A1
Application number	US-201716330612-A
Country	US
Kind code	A1
Filing date	Sep 7, 2017
Priority date	Sep 8, 2016
Publication date	Oct 14, 2021
Grant date	—

Abstract

The present invention relates to new bis(metallocene) compounds, new catalyst compositions, process for preparing the new bis(metallocene) compounds and use of said new catalyst compositions to polymerise olefins. The bis(metallocene) compounds of the invention are homo- or hetero bis(metallocene) molecules in which same or different metallocene moieties are connected by a phenylene bridge. The phenylene bridge is either para-substituted, meta-substituted or ortho-substituted by the two metallocene moieties.

First claim

1 .- 15 . (canceled)

16 . A bis(metallocene) compound (A) having one of the following formulas:

A1 and A3 are the same or different substituted or unsubstituted cyclopentadienyl rings, or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings, wherein if substituted, the substitutions may be independent and/or linked to form multicyclic structures;
A2 and A4 are the same or different and selected from substituted or unsubstituted cyclopentadienyl rings or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings;
X1, X2, X3 and X4 are independently hydrogen, halogen, hydride group, hydrocarbyl group, substituted hydrocarbyl group, alkoxide group, substituted alkoxide group, aryloxide group, substituted aryloxide group, halocarbyl group, substituted halocarbyl group, silylcarbyl group, substituted silylcarbyl group, germylcarbyl group, substituted germylcarbyl group, or both X1 and X2 and/or both X3 and X4 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms.
M1 is Zirconium.
M2 is selected from Zirconium, Hafnium and Titanium.
R1 and R2 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.
R3, R4, R5 and R6 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.

17 . The bis(metallocene) compound (A) according to claim 16 characterized in that both M1 and M2 are zirconium or M1 and M2 are different and preferably M2 is hafnium.

18 . The bis(metallocene) compound (A) according to claim 16 characterized in that A1 and A3 are the same and A2 and A4 are the same so that the bis(metallocene) compound (A) shows a symmetry.

19 . The bis(metallocene) compound (A) according to claim 16 characterised in that
R1 and R2 are independently hydrogen or a methyl group, and/or
R3, R4, R5 and R6 are hydrogen, and/or,
at least one of Al, A2, A3 or A4 is a fluorenyl ring.

20 . The bis(metallocene) compound (A) according to claim 16 characterized in that the compound is:

21 . A catalyst composition comprising a bis(metallocene) compound (A) according to claim 16 and a co-catalyst (B).

22 . The catalyst composition of claim 21 characterized in that the co-catalyst (B) is an alumoxane selected from methylalumoxane, modified methyl alumoxane, ethylalumoxane, isobutylalumoxane, or any combination thereof, preferably the co-catalyst (B) is methylalumoxane (MAO).

23 . The catalyst composition of claim 21 characterized in that the co-catalyst is an ionic activator selected from dimethylanilinium tetrakis(perfluorophenyl)borate, triphenylcarbonium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis(perfluorophenyl)aluminate, or any combination thereof, preferably the ionic activator is dimethylanilinium tetrakis(perfluorophenyl)borate.

24 . The catalyst composition of claim 21 characterized in that the co-catalyst (B) is an ionic activator used in combination with a co-activator being a trialkylaluminium selected from Tri-Ethyl Aluminum (TEAL), Tri-Iso-Butyl Aluminum (TIBAL), Tri-Methyl Aluminum (TMA), and Methyl-Methyl-Ethyl Aluminum (MMEAL), preferably the co-activator is Tri-Iso-Butyl Aluminum (TIBAL).

25 . The catalyst composition according to claim 21 characterized in that the bis(metallocene) compound (A) is or comprises a mixture of a homo bis(metallocenes) wherein both M1 and M2 are Zirconium and of a hetero bis(metallocene) wherein M1 and M2 are different metal centers and further wherein preferably M2 is Hafnium.

26 . The use of the catalyst composition of claim 21 in a process for polymerising olefins, the process comprising the step of contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerisation conditions to produce an olefin polymer.

27 . The use of claim 26 characterised in that the olefin monomer is ethylene or propylene.

28 . A process for preparing a bis(metallocene) compound comprising the steps of conducting a salt-metathesis reaction of a metal precursor and a tetra anion ligand wherein the proligand has one of the following formulas:

wherein
A1 and A3 are the same or different substituted or unsubstituted cyclopentadienyl rings, or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings, wherein if substituted, the substitutions may be independent and/or linked to form multicyclic structures.
A2 and A4 are the same or different and selected from substituted or unsubstituted cyclopentadienyl rings, or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings.
R1 and R2 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.
R3, R4, R5 and R6 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group, and
wherein the bis(metallocene) compound comprises a compound having one of the following formulas:

A1 and A3 are the same or different substituted or unsubstituted cyclopentadienyl rings, or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings, wherein if substituted, the substitutions may be independent and/or linked to form multicyclic structures;
A2 and A4 are the same or different and selected from substituted or unsubstituted cyclopentadienyl rings or substituted or unsubstituted fluorenyl rings, or substituted or unsubstituted indenyl rings;
X1, X2, X3 and X4 are independently hydrogen, halogen, hydride group, hydrocarbyl group, substituted hydrocarbyl group, alkoxide group, substituted alkoxide group, aryloxide group, substituted aryloxide group, halocarbyl group, substituted halocarbyl group, silylcarbyl group, substituted silylcarbyl group, germylcarbyl group, substituted germylcarbyl group, or both X1 and X2 and/or both X3 and X4 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms.
M1 is Zirconium.
M2 is selected from Zirconium, Hafnium and Titanium.
R1 and R2 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.
R3, R4, R5 and R6 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.

29 . The process of claim 29 wherein the proligand is a bis (Cp/Flu) proligand of the following formula

wherein R1 and R2 are independently hydrogen or a substituted or unsubstituted aliphatic, aromatic, or cyclic group.

30 . The process according to claim 29 characterized in that the metal precursor is a mixture of zirconium tetrachloride (ZrCl 4 ) with one selected from zirconium tetrachloride (ZrCl 4 ), hafnium tetrachloride (HfCl 4 ) and titanium tetrachloride (TiCl 4 ).

Assignees

• Total Res & Technology Feluy
• Centre Nat Rech Scient

Inventors

• Welle Alexandre
• Vantomme Aurélien
• Carpentier Jean-François
• Schnee Gilles
• Miserque Olivier
• Kirillov Evgueni

Classifications

• C08F2410/03

  Multinuclear procatalyst, i.e. containing two or more metals, being different or not · CPC title

• C08F4/6423

  Component of C08F4/64 containing at least two different metals · CPC title

• C08F4/6428

  with an aluminoxane, i.e. a compound containing an Al-O-Al- group · CPC title

• C08F110/02

  Ethene · CPC title

• C08F210/06

  Propene · CPC title