Transition metal compound containing cationic groups which...

Details Transition metal compound containing cationic groups which... Transition metal compound containing cationic groups which...

2000-09-07

2003-04-22

Shaver, Paul F. (Department: 1621)

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

Organic compounds

Heavy metal containing

C526S127000, C526S128000, C526S129000, C526S351000

Reexamination Certificate

active

06552210

ABSTRACT:

The present invention relates to specifically substituted metallocenes, a process for preparing them and their use in the polymerization of olefins.
Processes for preparing polyolefins with the aid of soluble, homogeneous catalyst systems comprising a transition metal component of the metallocene type and a cocatalyst component such as an aluminoxane, a Lewis acid or an ionic compound are known. These catalysts have a high activity and give polymers and copolymers having a narrow molar mass distribution.
In polymerization processes using soluble, homogeneous catalyst systems, thick deposits are formed on reactor walls and stirrer when the polymer is formed as a solid. These deposits are formed by agglomeration of the polymer particles whenever metallocene and/or cocatalyst are present in dissolved form in the suspension. Such deposits in the reactor systems have to be removed regularly, since they quickly attain considerable thicknesses, have a high strength and prevent heat exchange to the cooling medium. Such homogeneous catalyst systems cannot be used industrially in modern polymerization processes in the liquid monomer or in the gas phase.
To avoid deposit formation in the reactor, supported catalyst systems in which the metallocene and/or the aluminum compound serving as cocatalyst are/is fixed to an inorganic support material have been proposed.
EP-A-0,576,970 A1 discloses metallocenes and corresponding supported catalyst systems.
However, a frequent problem in the industrial use of supported catalyst systems is leaching of the metallocene component from the support material, resulting, for example, in undesirable deposit formation in the reactor.
It is an object of the present invention to find novel metallocenes which can be firmly fixed to a support and are not leached from the support material under industrially relevant polymerization conditions.
We have found that this object is achieved by specifically substituted metallocenes containing a cationic-group as substituent.
The present invention accordingly provides metallocenes of the formula (I),
where
M
1
is a transition metal of group 4 of the Periodic Table of the Elements, for example titanium, zirconium or hafnium, preferably zirconium,
R
1
and R
2
are identical or different and are each a hydrogen atom, a C
1
-C
20
group, preferably a C
1
-C
20
-alkyl group, a C
6
-C
14
-aryl group, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group, a C
7
-C
20
-alkylaryl group, each of which may bear one or more identical or different halogen atoms as substituents, a halogen atom, an —SiMe
3
group or an OSiMe
3
group; R
1
and/or R
2
are particularly preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, branched pentyl, n-hexyl, branched hexyl, cyclohexyl or benzyl,
R
3
are identical or different and are each a hydrogen atom or a C
1
-C
40
group, preferably a C
1
-C
20
-alkyl group which may be substituted, in particular methyl, ethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, cyclopropyl, cyclopentyl or cyclohexyl, a C
6
-C
14
-aryl group which may be substituted, in particular phenyl, tolyl, xylyl, tert-butylphenyl, ethylphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, methoxyphenyl, fluorophenyl, dimethylaminophenyl, trimethylammoniumphenyl iodide, dimethylsulfoniumphenyl bromide, triethylphosphoniumphenyl triflate, naphthyl, acenaphthyl, phenanthrenyl or anthracenyl, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group, a C
7
-C
20
-alkylaryl group, a halogen atom, an SiMe
3
group, an OSiMe
3
group, a C
1
-C
20
-heterocyclic group which may be substituted, where the term heteroatom encompasses all elements with the exception of carbon and hydrogen, preferably atoms of groups 14, 15 or 16 of the Periodic Table of the Elements, and two radicals R
3
may form a monocyclic or polycyclic ring system which may in turn be substituted, where at least one of the radicals R
1
, R
2
, R
3
comprises a cationic group (—DE
L
)
+
Y
−
, where
D is an atom of group 15 or 16 of the Periodic Table of the Elements, preferably nitrogen, phosphorus, oxygen or sulfur,
E are identical or different and are each a hydrogen atom, a C
1
-C
20
group, preferably a C
1
-C
20
-alkyl group, a C
6
-C
14
-aryl group, a C
2
-C
20
-alkenyl group, a C
2
-C
20
-alkynyl group or a C
7
-C
20
-alkylaryl group, a trialkylsilyl group, a triarylsilyl group, an alkylarylsilyl group which may be substituted, and two radicals E may form a monocyclic or polycyclic ring system which may in turn be substituted;
E is particularly preferably a hydrogen atom, methyl, ethyl, propyl, butyl, allyl, benzyl, methoxymethyl, benzyloxymethyl, 2-methoxyethoxymethyl, 2-trimethylsilylethoxymethyl, trimethylsilyl;
L is 3 when D is an atom of group 15 of the Periodic Table of the Elements and is 2 when D is an atom of group 16 of the Periodic Table of the Elements,
Y is halide, C
1
-C
10
-alkylsulfonate, C
1
-C
10
-haloalkylsulfonate, C
6
-C
20
-arylsulfonate, C
6
-C
20
-haloarylsulfonate, C
7
-C
20
-alkylarylsulfonate, C
1
-C
20
-haloalkylcarboxylate, C
1
-C
10
-alkyl sulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate; Y is preferably chloride, bromide, iodide, triflate, mesylate, tosylate, benzenesulfonate, trifluoroacetate, methyl sulfate, tetrafluoroborate or hexafluorophosphate;
m is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
m′ is an integer less than or equal to 4 and greater than or equal to 1, preferably 1 or 2, particularly preferably 1,
k is zero or 1, where the metallocene is unbridged when k=0 and is bridged when k=1,
A is a bridge of the following type
 or ═BR
4
, AIR
4
, —S—, —SO—, —SO
2
—, ═NR
4
, ═PR
4
, ═P(O)R
4
, o-phenylene, 2,2′-biphenylene, where
M
2
is carbon, silicon, germanium, tin, nitrogen or phosphorus, preferably carbon, silicon or germanium, in particular carbon or silicon,
o is 1, 2, 3 or 4, preferably 1 or 2,
R
4
and R
5
are identical or different and are each a hydrogen atom, halogen, a C
1
-C
20
group, preferably C
1
-C
20
-alkyl, in particular a methyl group, C
6
-C
14
-aryl, in particular a phenyl or naphthyl group, C
1
-C
10
-alkoxy, C
2
-C
10
-alkenyl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, C
6
-C
10
-aryloxy, C
1
-C
10
-fluoroalkyl, C
6
-C
10
-haloaryl, C
2
-C
10
-alkynyl, C
3
-C
20
-alkylsilyl, in particular trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, C
3
-C
20
-arylsilyl, in particular triphenylsilyl, or C
3
-C
20
-alkylarylsilyl, in particular dimethylphenylsilyl, diphenylsilyl or diphenyl-tert-butylsilyl, and R
4
and R
5
may form a monocyclic or polycyclic ring system;
A is preferably dimethylsilanediyl, dimethylgermanediyl, ethylidene, methylethylidene, 1,1-dimethylethylidene, 1,2-dimethylethylidene, tetramethylethylidene, isopropylidene, phenylmethylmethylidene, diphenylmethylidene, particularly preferably dimethylsilanediyl or ethylidene;
The radicals X are identical or different and are each a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a C
1
-C
10
-alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, cyclohexyl, a C
6
-C
15
-aryl group such as phenyl, naphthyl, a C
1
-C
10
-alkoxy group such as methoxy, ethoxy, tert-butoxy, a C
6
-C
15
-aryloxy group, a benzyl group, preferably a chlorine atom, a fluorine atom, a methyl group, a benzyl group, particularly preferably a chlorine atom or a methyl group.
Particularly preferred novel metallocenes of the formula (I) have the formula (I*),
where
M
1
, A, R
1
, k and X are as defined in formula (I) and
R
6
are identical or different and are each a hydrogen atom or a C
1
-C
40
group, preferably a C
1
-C
20
-alkyl group which may be substituted, in particular methyl, ethyl, trifluoromethyl, trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-bu

Affiliated with

Also associated with

Rating

Transition metal compound containing cationic groups which... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Transition metal compound containing cationic groups which..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Transition metal compound containing cationic groups which... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3040880