Indenyl compounds for the polymerization of olefins

Details Indenyl compounds for the polymerization of olefins Indenyl compounds for the polymerization of olefins

2000-06-12

2002-01-29

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S001000, C556S043000, C556S058000, C502S103000, C502S117000, C502S120000, C534S015000, C526S160000, C526S351000, C526S352000, C526S943000

Reexamination Certificate

active

06342622

ABSTRACT:

The invention relates to indenyl compounds that can be used as catalyst component for the polymerisation of olefins. The invention also relates to a process for the polymerisation of olefins, using indenyl compounds. Such indenyl compounds are for instance known from WO-A-94/11406.
In said patent publication indenyl compounds are described of formula
wherein:
M is a transition metal from the lanthanides or from group 3, 4, 5 or 6 of the Periodic System of Elements,
Q is an anionic ligand to M,
k is the number of Q-groups and equals the valence of M minus 2, and
R is a bridging group. It is now surprisingly discovered that indenyl compounds, wherein R contains at least one sp2-hybridised carbon atom that is bonded to the indenyl group at the 2-position, are more active and/or give polymers with a higher molecular weight (Mw) and/or yield a polypropylene with a low amount of misinsertions when used as a catalyst component during the polymerisation of olefins.
The indenyl compounds according to the invention are indenyl compounds according to (1)
wherein:
M is a transition metal from the lanthanides or from group 3, 4, 5 or 6 of the Periodic System of Elements,
Q is an anionic ligand to M,
k is the number of Q groups, and equals the valence of M minus 2,
R is a bridging group containing at least one sp2-hybridised carbon atom that is bonded to the indenyl group at the 2-position,
and Z and X are substituents, with the exclusion of Ti(deshydronorbiphenacene)dichloride. In ‘Synthesis, Structure, and Properties of Chiral Titanium and Zirconium Complexes Bearing Biaryl Strapped Substituted Cyclopentadienyl Ligands’, W. W. Ellis c.s., Organometallics 1993, 12, 4391-4401 Ti(deshydronorbiphenacene)dichloride is described, but not the polymerisation of olefins with this indenyl compound.
The various components of the indenyl compound of the present invention will hereafter be discussed in more detail.
a) The Transition Metal M
The transition metal M is selected from the lanthanides or from group 3, 4, 5 or 6 of the Periodic System of Elements. The Periodic System of Elements is understood to be the new IUPAC version as printed on the inside cover of the Handbook of Chemistry and Physics, 70th edition, CRC Press, 1989-1990. The transition metal M is preferably chosen from the group Ti, Zr, Hf, V and Sm. Most preferably the transition metal M is Ti, Zr or Hf.
b) The Anionic Ligand Q
The Q group in the indenyl compounds according to the invention comprises one or more uni- or polyvalent anionic ligands to the transition metal M. As examples of such ligands, which may be the same or different, the following can be mentioned:
a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a group with a heteroatom chosen from group 14, 15 or 16 of the Periodic System of Elements, such as:
an amine group or amide group,
a sulfur-containing compound, such as sulphide and sulphite,
a phosphorus-containing compound, such as phosphine and phosphite.
The ligand Q can also be a monoanionic ligand bonded to the transition metal M via a covalent metal-carbon bond and which is additionally capable to non-covalently interact with M via one or more functional groups. The functional group mentioned above can be one atom, but also a group of atoms connected together. The functional group is preferably an atom of group 17 of the Periodic Table of the Elements or a group containing one or more elements from groups 15, 16 or 17 of the Periodic Table of the Elements. Examples of functional groups are F, Cl, Br, dialkylamino and alkoxy groups. Q can for instance be a phenyl group in which at least one of the ortho-positions is substituted with a functional group capable of donating electron density to the transition metal M. Q can also be a methyl group in which one or more of the alpha-positions is substituted with a functional group capable of donating electron density to the transition metal M. Examples of methyl groups substituted in one or more of the alpha-positions are benzyl, diphenylmethyl, ethyl, propyl and butyl substituted with a functional group capable of donating electron density to the transition metal M. Preferably at least one of the ortho-positions of a benzyl-group is substituted with a functional group capable of donating electron density to the transition metal M.
Examples of these Q groups are: 2,6-difluorophenyl, 2,4,6-trifluorophenyl, pentafluorophenyl, 2-alkoxyphenyl, 2,6-dialkoxyphenyl, 2,4,6-tri(trifluoromethyl)phenyl, 2,6-di(trifluoromethyl)phenyl, 2-trifluoromethylphenyl, 2-(dialkylamino)benzyl and 2,6-(dialkylamino)phenyl. The man skilled in the art can determine the suitability of these and other ligands through simple experimenting.
The number of Q groups in the indenyl compound according to the invention (index k in formula (1)) is determined by the valence of the transition metal M and the valence of the Q groups itself. In the indenyl compounds according to the invention k is equal to the valence of M minus 2 divided by the valence of Q.
Preferably, Q is a mono-anionic ligand. Most preferably, Q is Cl or a methyl group.
c) The Bridging Group R
R is a bridging group containing at least one sp2-hybridised carbon atom that is bonded to the indenyl group at the 2-position. In general and in this description, the substituent locants of the indenyl ring are numbered in accordance with the IUPAC Nomenclature of Organic Chemistry, 1979, rule A 21.1. The numbering of the substituents for indene is given below. This numbering is analogous in the case of an indenyl ligand:
The R group connects the indenyl group with the cyclopentadienyl group in the indenyl compound according to the invention. Sp2-hybridised carbon atoms are also known as trigonal carbon atoms. The chemistry related to sp2-hybridised carbon atoms is for instance descibed by S.N. Ege, Organic Chemistry, D.C. Heath and Co., 1984, p. 51-54. Sp2-hybridised carbon atoms are carbon atoms that are connected to three other atoms. In the indenyl compounds according to the invention the sp2-hybridised carbon atom is in any case connected to the indenyl group at the 2-position.
The sp2-hybridised carbon atom may be a part of, for instance, an alkylene-containing bridging group R or of an aryl group forming part of the bridging group R.
Alkylene-containing bridging groups can be, for instance of the formulas
wherein R′ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a group with a heteroatom chosen from group 14, 15 or 16 of the Periodic System of Elements, such as
an amine group or amide group,
a sulfur-containing compound, such as sulphide and sulphite,
a phosphorus-containing compound, such as phosphine and phosphite, E can be carbon, silica or germanium atom and
s is 1-20.
Examples of alkylene-containing bridging groups are ethylene, propylene, which can also be subsituted.
Examples of aryl groups that can form part of a bridging group are phenylene, biphenylene, pyridyl, furyl, thiophyl and N-substituted pyrroles, such as N-phenylpyrrole or an inorganic compound containing an aromatic group, for instance a metallocene compound and a ferrocene compound.
The bridging group R preferably contains at least one aryl group; preferably the aryl group is a phenylene group. When R is a phenylene group the indenyl compounds are more active catalyst components. More preferably R is a bisaryl group; preferably a 2,2′-biphenylene. When R is a 2,2′-biphenylene group the indenyl compound, as a catalyst component, gives rise to better comonomer incorporation, polymers with a higher molecular weight and to a propylene homopolymer with a higher isotacticity when propylene is polymerised.
d) The Substituents X
1
-X
4
The cyclopentadienyl group may be substituted. The substituents X may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl). Examples of alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl. Examples of aryl groups are phenyl

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