Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1995-04-05
2001-04-03
Wu, David W. (Department: 1715)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C526S160000, C526S127000, C526S943000, C556S011000, C556S028000, C556S053000
Reexamination Certificate
active
06211108
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a class of metallocene compounds, to a catalyst for the polimerization of olefins comprising said metallocenes and to processes for the polimerization of olefins carried out in the presence of said catalyst.
The invention also relates to processes for the preparation of the ligands of said metallocenes, as well as to a class of novel bridged ligands.
2. Description of the Prior Art
Metallocene compounds are known which are active as catalyst components in the olefin polymerization reactions.
European patent application EP-A-35 242, for instance, discloses a process for the polymerization of ethylene and propylene in the presence of a catalyst system comprising (a) a cyclopentadienyl compound of a transition metal and (b) an alumoxane.
European patent application EP-A-129 368 discloses a catalyst system for the polymerization of olefins comprising (a) a mono-, bi- or tri-cyclopentadienyl coordination complex with a transition metal and (b) an alumoxane. With this catalyst it is possible to prepare polyolefins of controlled molecular weight.
European patent application EP-A-351 392 discloses a catalyst, which can be used in the preparation of syndiotactic polyolefins, comprising a metallocene compound with two cyclopentadienyl based rings linked with a bridging group in which one of the two cyclopentadiene rings is substituted differently from the other. The preferred compound indicated is isopropylidene(fluorenyl)(cyclopentadienyl)hafnium dichloride.
EP-A-604 908 discloses a class of bis-fluorenyl compounds bridged with a one-atom-bridge. These metallocenes are useful as catalyst components for the polymerization of olefins and, especially, for the preparation of high molecular weight atactic polypropylene.
SUMMARY OF THE INVENTION
New metallocene compounds have now been found which can be advantageously used as catalyst components in the polymerization reactions of olefins.
An object of the present invention consists of a new metallocene compound of formula (I)
(YR
p
)
q
(CP)(CP′)MX
2
(I)
wherein Cp is a group selected from those of formula (II) and (III):
wherein m and n, same or different from each other, are integer comprised between 2 and 6 and, preferably, comprised between 3 and 5;
Cp′ is a group selected from those of formula (II), (III) e (IV):
wherein (YR
p
)
q
is a divalent group which bridges the two groups Cp and Cp′, Y being selected indifferently from C, Si, Ge, N and P; p is 1 when Y is N or P, and is 2 when Y is C, Si or Ge;
q can be 0, 1, 2 or 3;
M is a transition metal selected from Ti, Zr or Hf;
the substituents X, same or different from each other, are halogen atoms, —OH, —SH, R, —OR, —SR, —NR
2
or —PR
2
;
the substituents R, same or different from each other, are hydrogen atoms, C
1
-C
20
alkyl radicals, C
3
-C
20
cycloalkyl radicals, C
2
-C
20
alkenyl radicals, C
6
-C
20
aryl radicals, C
7
-C
20
alkylaryl radicals or C
7
-C
20
arylalkyl radicals, optionally containing Si or Ge atoms and, additionally, two adjacent R substituents on Cp or Cp′ may form a C
5
-C
8
cycle and, further, two R substituents of the same YR
2
group or of two adjacent YR
2
groups may form a ring comprising from 3 to 8 atoms; when q=0, the R′ substituents are difined as the R substituents while, when q=1, 2 or 3, the two R′ substituents of the groups Cp and Cp′ together form the divalent group (YR
p
)
q
.
Another object of the present invention is a process for the preparation of a cyclopentadienylic compound of formula (II), which comprises reacting a cycloalkene of formula (V) with a cycloalkene derivative of formula (VI) to obtain a cyclopentenone of formula (VII), wherein n, m and R have the meaning given, and X is OH, OR, O(CO)R, Cl or Br, in accordance with the reaction scheme below:
Still another object of the present invention is a process for the preparation of a cyclopentadienylic compound of formula (III), which comprises reacting a cycloalkene of formula (V′) with a benzene derivative of formula (VIII) to obtain a compound of formula (IX), wherein n, m, R and X have the meaning given, in accordance with the reaction scheme below:
Yet another object of the present invention is a cyclopentadiene ligand of formula (XI):
(YR
p
)
q
(CP)(CP′) (XI)
wherein Cp, Cp′, (YR
p
)
q
, Y, R, p and q have the meaning given.
A further object of the present invention is a catalyst for the polymerization of olefins comprising the product of the reaction between:
(A) a metallocene compound of formula (I), optionally as a reaction product with a organo-aluminium of formula AlR
4
3
or Al
2
R
4
6
, in which the substituents R
4
, same or different from each other are R
1
or halogen, and
(B) an aluminoxane, optionally in admixture with a organo-aluminium compound of formula AlR
4
3
or Al
2
R
4
6
, in which the substituents R
4
, same or different from each other, are defined as above or one or more compounds capable of forming a alkyl metallocene cation.
Still a further object of the invention consists of a process for the polymerization of olefins comprising the polymerization reaction of at least one olefinic monomer in the presence of the above described catalyst.
Yet a further object of the present invention is a process for the oligomerization of propylene carried out in the presence of the above described catalyst.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred R substituents are hydrogen, C
1
-C
10
alkyl radicals, more preferably C
1
-C
3
, C
3
-C
10
cycloalkyl radicals, more preferably C
3
-C
6
, C
2
-C
10
alkenyl radicals, more preferably C
2
-C
3
, C
6
-C
10
aryl radicals C
7
-C
10
alkaryl radicals or C
7
-C
10
aralkyl radicals. The alkyl radicals may be straight chain or branched in addition to cyclic.
The divalent group (YR
p
)
q
is preferably selected from CR
2
, SiR
2
, GeR
2
, NR, PR and (CR
2
)
2
. More preferably it is a group selected from Si(CH
3
)
2
, CH
2
, (CH
2
)
2
and C(CH
3
)
2
.
The preferred transition metal M is Zr.
The X substituents are preferably halogen atoms or R groups. More preferably they are chlorine or a methyl radical.
Non limitative examples of ligands of formula (II) according to the invention are: octahydrofluorene, 9-methyl-octahydrofluorene, bis(cyclotrimethylene)cyclopentadiene.
Non limitative examples of ligands of formula (III) according to the invention are: tetrahydrofluorene, 1,2-cyclo-hexamethylene-indene.
Non limitative examples of ligands of formula (IV) according to the invention are: cyclopentadienyl, indenyl, tetrahydroindenyl.
A particular class of metallocene according to the invention is those compounds of formula (I) in which q=0, and that is those in which the Cp and Cp′ groups are not linked to each other by a bridge.
Non limitative examples of the above mentioned class of metallocenes are:
bis(1,2-cyclotetramethyleneinden-1-yl)titanium dichloride,
bis(1,2-cyclotetramethyleneinden-1-yl)zirconium dichloride,
bis(1,2-cyclotetramethyleneinden-1-yl)hafnium dichloride,
bis(1,2-cyclotetramethyleneinden-1-yl)titanium dimethyl,
bis(1,2-cyclotetramethyleneinden-1-yl)zirconium dimethyl,
bis(1,2-cyclotetramethyleneinden-1-yl)hafnium dimethyl,
bis(octahydrofluorenyl)titanium dichloride,
bis(octahydrofluorenyl)zirconium dichloride,
bis(octahydrofluorenyl)hafnium dichloride,
bis(octahydrofluorenyl)titanium dimethyl,
bis(octahydrofluorenyl)zirconium dimethyl,
bis(octahydrofluorenyl)hafnium dimethyl,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)titanium dichloride,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)zirconium dichloride,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)hafnium dichloride,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)titanium dimethyl,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)zirconium dimethyl,
(cyclopentadienyl)(1,2-cyclotetramethyleneinden-1-yl)hafnium dimethyl,
(cyclopentadienyl)(octahydrofluorenyl)titanium dichloride,
(cyclopentadienyl)(octahydrofluoreny
Bishop Clyde E.
Dall'Occo Tiziano
Dang Vu Anh
Galimberti Maurizio
Jones, Jr. Robert L.
Bryan Cave LLP
Choi Ling-Siu
Montell Technology Company BV
Wu David W.
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