Organometallic fluorenyl compounds, preparation, and use

Claim 2

The metallocene according to claim 1 wherein x is 1.

Claim 3

The metallocene according to claim 2 wherein (CpR m ) and (FlR n ) are different.

Claim 4

The metallocene according to claim 2 wherein R''is the divalent methylene radical --CH₂--.

Claim 5

The metallocene according to claim 2 wherein R'' has the formula II wherein each R' is hydrogen or at least one of R' is hydrocarbyl, having from 1 to 7 carbon atoms, preferably an aliphatic hydrocarbyl.

Claim 6

The metallocene according to claim 5 wherein said R' is an alkyl radical, preferably methyl.

Claim 7

The metallocene according to claim 1 wherein x is 0.

Claim 8

The metallocene according to claim 7 wherein (FlR n ) and (CpR m ) are the same.

Claim 9

The metallocene according to any of the preceding claims wherein n is a number in the range of 1 to 4 and/or m is a number in the range of 1 to 4.

Claim 10

The metallocene according to any of the preceding claims wherein Me is selected from Ti, Zr, and Hf, preferably Zr and Hf.

Claim 11

The metallocene according to any of the preceding claims wherein (CpR m ) is selected from fluorenyl, cyclopentadienyl, indenyl, and methyl cyclopentadienyl.

Claim 12

The metallocene according to any of the preceding claims wherein (FlR n ) is selected from fluorenyl (n=0), 1-tert-butyl fluorenyl, 2-ethyl fluorenyl, 2-tert-butyl fluorenyl, 4-tert-butyl fluorenyl, 4-methyl fluorenyl, 2,7-di-tert-butyl fluorenyl, and 2,7-di-tert-butyl-4-methyl fluorenyl.

Claim 13

The metallocene according to any of the preceding claims wherein Q is halogen, preferably chlorine.

Claim 14

The metallocene according to claim 2 being selected from (1,1-difluorenylmethane)zirconium dichloride, (1,2-difluorenyl ethane) zirconium dichloride, (1,2-difluorenyl ethane) hafnium dichloride, (1,3-difluorenylpropane) zirconium dichloride, (1,2-difluorenylethane) hafnium dichloride, (1,3-difluorenylpropane) hafnium dichloride, (1-fluorenyl-2-methyl-2-fluorenylethane)zirconium dichloride, dimethylsilyldifluorenyl zirconium dichloride, (1,2-di(1-methyl fluorenyl)ethane)zirconium dichloride, (1,2-di(1-methyl fluorenyl)ethane) hafnium dichloride, (1,2-di-(2-ethyl fluorenyl)ethane)zirconium dichloride, (1,2-di(2-tert-butyl fluorenyl)ethane)sirconium dichloride, (1,2-di(2-tert-butyl fluorenyl)ethane)hafnium dichloride, (1,2-di(1-tert-butyl fluorenyl) ethane) zirconium dichloride, (1,2-di(4-methyl fluorenyl) ethane) zirconium dichloride, (1,2-di(4-methyl fluorenyl)ethane) hafnium dichloride, (1,2-di(4-tert-butyl fluorenyl)ethane) zirconium dichloride, (1-(fluorenyl)-1-(cyclopentadienyl)methane) zirconium dichloride, (1-(fluorenyl)-1-(cyclopentadienyl)methane) hafnium dichloride, (1-(2,7-di-tert-butyl fluorenyl)-1-(cyclopentadienyl)methane)zirconium dichloride, (1-fluorenyl-2-cyclopentadienylethane)zirconium dichloride, (1-fluorenyl-2-(3-methyl cyclopentadienyl)ethane)zirconium dichloride, (1-fluorenyl-2-indenyl ethane)zirconium dichloride, (1-fluorenyl-2-indenyl ethane)hafnium dichloride, (1-fluorenyl-2-methyl-2-indenyl ethane) zirconium dichloride, (1-fluorenyl-2-methyl-2-indenyl ethane) hafnium dichloride, (bis-fluorenylmethane)vanadium dichloride, (1,2-difluorenyl ethane)vanadium dichloride, (1-fluorenyl-1-cyclopentadienyl methane) zirconium trichloride, (1-fluorenyl-2-methyl-2-(3-methyl cyclopentadienyl)ethane)zirconium dichloride, (1-(1-methyl fluorenyl)-2-(4-methyl fluorenyl)ethane)zirconium dichloride, (1-(2,7-di-tert-butyl fluorenyl)-2-(fluorenyl)ethane)zirconium dichloride, (1,2-di(2,7-di-tert-butyl-4-methyl fluorenyl)ethane zirconium dichloride, and (1,2-di-(1-methyl-4-methyl fluorenyl)ethane) zirconium dichloride.

Claim 15

The metallocene according to claim 2 being (fluorenyl)-1-(cyclopentadienyl) methane zirconium dichloride.

Claim 16

The metallocene according to claim 7 being selected from bis(1-methyl-fluorenyl)zirconium dichloride, bis(1-methyl fluorenyl)zirconium dimethyl, bis(1-methyl fluorenyl) hafnium dichloride, bis(1-tert-butyl fluorenyl)zirconium dichloride, bis(2-ethyl fluorenyl) zirconium dichloride, bis(4-methyl fluorenyl)zirconium dichloride, bis(4-methyl fluorenyl)hafnium dichloride, bis(2-tert-butyl fluorenyl)zirconium dichloride, bis(4-tert-butyl fluorenyl)zirconium dichloride, bis(2,7-di-tert-butyl fluorenyl)zirconium dichloride, bis(2,7-di-tert-butyl-4-methyl fluorenyl)zirconium dichloride, and bis (2-methyl fluorenyl)zirconium dichloride.

Claim 17

A process for preparing a fluorenyl-containing metallocene comprising reacting an alkali metal salt of at least one fluorenyl-containing compound with a transition metal compound of the formula MeQ k in the presence of a non-halogenated solvent for the fluorenyl salt which solvent is non-coordinating with the transition metal compound.

Claim 18

The process according to claim 17 wherein said solvent is selected from toluene, pentane, hexane, and diethylether.

Claim 19

The process according to claim 17 wherein said fluorenyl-containing compound is a bridged compound in which a fluorenyl radical is bonded to another cyclopentadienyl-type radical by a bridging group.

Claim 20

The process according to claim 17 wherein said alkali metal salt of said fluorenyl-containing compound has been formed by reacting an alkali metal alkyl with a fluorenyl-containing compound in the presence of a non-halogenated solvent for the fluorenyl salt which is non-coordinating with the transition metal compound.

Claim 21

The process according to claim 17 wherein said metallocene has the formula (I) as defined in any of claims 1 to 16.

Claim 22

A process comprising reacting fluorenyl methyl chloride with an alkali metal salt of cyclopentadiene to produce 1-fluorenyl-1-cyclopentadienyl methane; forming a divalent alkali metal salt of 1-fluorenyl-1-cyclopentadienyl methane; reacting the said divalent alkali metal salt with a transition metal halide of the formula MeQk wherein Me is selected from Zr, Hf, and Ti; each Q is individually selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogens; at least one Q is a halogen; and k is a number corresponding to the valence of Me; to produce the corresponding bridged metallocene; and using said metallocene to polymerize an α-olefin containing at least three carbons per molecule.

Claim 23

The use of the metallocene of the formula (I) as defined in any of the claims 1 to 16 in combination with an organometallic co-catalyst for the polymerization of olefins.

Claim 24

The use of claim 23 wherein said co-catalyst is an alkylaluminoxane.

Claim 25

An ethylene/1-hexene-copolymer having a density of less than 0.90 and a relative comonomer dispersity of at least 106 %.

Claim 26

The copolymer of claim 25 having a density of about 0.88.

Claim 27

A syndiotactic homopolymer of 4-methyl-1-pentene having a ¹³C NMR spectrum having a peak at 43.1 ppm which is greater than 0.5 of the total peak intensities present in the range of 42.0 and 43.5 ppm, wherein the next most intense peak above the peak at about 46.1 ppm is more intense than any peak between the major peaks at 46.1 ppm and 43.1 ppm, and the next most intensive peak between 43.1 ppm and 35 ppm is more intense than any peak between the major peaks at 46.1 and 43.1 ppm.

Claim 28

The polymer of claim 27 characterized by the ¹³C NMR spectrum of figure 1.