U.S. patent application number 09/871735 was filed with the patent office on 2002-02-28 for catalyst composition.
Invention is credited to Mecking, Stefan.
Application Number | 20020026012 09/871735 |
Document ID | / |
Family ID | 7821249 |
Filed Date | 2002-02-28 |
United States Patent
Application |
20020026012 |
Kind Code |
A1 |
Mecking, Stefan |
February 28, 2002 |
CATALYST COMPOSITION
Abstract
A catalyst composition comprises at least two different
polymerization catalysts of which a) at least one is a
polymerization catalyst based on an early transition metal
component and b) at least one is a polymerization catalyst based on
a late transition metal component.
Inventors: |
Mecking, Stefan; (Offenbach,
DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Ave., N.W.
Washington
DC
20036
US
|
Family ID: |
7821249 |
Appl. No.: |
09/871735 |
Filed: |
June 4, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09871735 |
Jun 4, 2001 |
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09367945 |
Aug 24, 1999 |
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6262196 |
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09367945 |
Aug 24, 1999 |
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PCT/EP98/00857 |
Feb 23, 1998 |
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Current U.S.
Class: |
525/240 ;
525/191 |
Current CPC
Class: |
C08F 10/00 20130101;
C08F 4/65912 20130101; C08F 2410/04 20130101; C08F 4/65925
20130101; C08F 10/00 20130101; C08F 4/61904 20130101; C08F 10/00
20130101; C08F 4/7006 20130101 |
Class at
Publication: |
525/240 ;
525/191 |
International
Class: |
C08L 023/04; C08L
023/06; C08L 023/08 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 24, 1997 |
DE |
19707236.4 |
Claims
We claim:
1. A catalyst composition comprising at least two different
polymerization catalysts of which a) at least one is a
polymerization catalyst based on an early transition metal
component and b) at least one is a polymerization catalyst based on
a late transition metal component.
2. A catalyst composition as claimed in claim 1, wherein the early
transition metal component is a Ziegler catalyst component and/or a
metallocene catalyst component.
3. A catalyst composition as claimed in claim 1 or 2, wherein each
of the transition metal components has a productivity which is
greater than 2800 kg of polymer/(mole of transition
metal.times.h).
4. A catalyst composition as claimed in one or more of claims 1 to
3 further comprising one or more activators.
5. A catalyst composition as claimed in one or more of claims 1 to
4 further comprising one or more supports.
6. A process for the polymerization of olefins in the presence of a
catalyst composition as claimed in one or more of claims 1 to
5.
7. A process as claimed in claim 6 in which ethylene is
polymerized.
8. A polyolefin which is able to be prepared by a process as
claimed in claim 6 or 7.
9. The use of a catalyst composition as claimed in one or more of
claims 1 to 5 for olefin polymerization.
Description
[0001] The present invention relates to a catalyst composition
comprising a polymerization catalyst based on an early transition
metal component and a polymerization catalyst based on a late
transition metal component.
[0002] The use of catalysts of the Ziegler type or the metallocene
type for the polymerization of nonpolar olefins such as ethylene
and propylene is known. Such catalysts usually comprise an early
transition metal component, for example a halide-containing
titanium or zirconium compound, in combination with an excess of a
cocatalyst, for example an aluminum compound. Recently, the
activation of suitable transition metal compounds using
stoichiometric amounts of a cocatalyst such as a [Ph.sub.3C].sup.+
or [Me.sub.2NPh].sup.+ salt of a non-coordinated anion has been
described.
[0003] The use of catalyst compositions comprising two or more
different olefin polymerization catalysts of the Ziegler type or
the metallocene type is known. For example, a combination of two
catalysts of which one produces a polyethylene having a different
mean molar mass than the other can be used for producing reactor
blends having broad molecular weight distributions (WO 95/11264).
The polymer blends obtained can have improved processing and use
properties.
[0004] The addition of metal components, including later transition
metals, to olefin polymerization catalysts based on early
transition metals for increasing the activity or stability of the
latter catalysts has been described many times (Herrmann, C.;
Streck, R.; Angew. Makromol. Chem. 94 (1981) 91-104).
[0005] The synthesis of branched polymers from ethylene without use
of a comonomer by means of bimetallic catalysts in which one
catalyst oligomerizes part of the ethylene and the other
copolymerizes the resulting oligomers with ethylene has been
described (Beach, David L.; Kissin, Yury V.; J. Polym. Sci., Polym.
Chem. Ed. (1984), 22, 3027-42. Ostoja-Starzewski, K. A.; Witte, J.;
Reichert, K. H., Vasiliou, G. in Transition Metals and
Organometallics as Catalysts for Olefin Polymerization. Kaminsky,
W.; Sinn, H. (editors); Springer-Verlag; Heidelberg; 1988; S.
349-360). The last literature reference describes, for example, the
use of a nickel-containing oligomerization catalyst in combination
with a chromium-containing polymerization catalyst.
[0006] It is an object of the present invention to provide a
catalyst composition which is suitable for preparing polyolefin
blends comprising at least two different polyolefins.
[0007] We have found that this object is achieved by means of a
specific catalyst composition.
[0008] The present invention accordingly provides a catalyst
composition comprising at least two different polymerization
catalysts of which a) at least one is a polymerization catalyst
based on an early transition metal component and b) at least one is
a polymerization catalyst based on a late transition metal
component.
[0009] The invention further provides a process for the
polymerization of olefins in the presence of the catalyst
composition of the present invention. A preferred embodiment of the
process of the present invention is a process for the
homopolymerization of ethylene by means of the catalyst composition
of the present invention, where particular preference is given to
obtaining a blend of polyethylenes having different branching
structures.
[0010] For the purposes of the present invention, an "early
transition metal" is a metal of groups IIIa to VIIa of the Periodic
Table of the Elements or a metal of the lanthanide group, and a
"late transition metal" is a metal of groups VIIIa and IB of the
Periodic Table of the Elements. The expressions "oligomerization"
and "oligomer" refer to products or product mixtures which, based
on the number average (Mn), consist of less than 400 monomer units.
The expressions "polymerization" and "polymer" or "polyolefin"
refer to products or product mixtures which, based on the number
average (Mn), consist of more than 400, preferably more than 1000,
monomer units. The term "polymerization catalyst" refers to
catalysts which are suitable for preparing polymers or polyols, ie.
for preparing products or product mixtures which, based on the
number average, consist of more than 400 monomer units, preferably
more than 1000 monomer units. The catalyst composition of the
present invention comprises a) at least one polymerization catalyst
based on an early transition metal component and b) at least one
polymeerization catalyst based on a late transition metal
component, of which each leads to the formation of a different
polymer or polyolefin. Each transition metal component comprises
exactly one transition metal.
[0011] As catalyst component based on an early transition metal,
the catalyst composition of the present invention preferably
comprises Ziegler catalyst components (as described, for example,
in Falbe, J.; Regitz, M. (editors); Rompp Chemie Lexikon; 9th
edition; Thieme; 1992; New York; volume 6, pp. 5128-5129) and/or
metallocene catalyst components. Particular preference is given to
metallocene catalyst components.
[0012] The Ziegler catalyst component is preferably a compound of a
metal of group IVa (ie. titanium, zirconium or hafnium), Va (eg.
vanadium or niobium) or VIa (eg. chromium or molybdenum) of the
Periodic Table of the Elements. Preference is given to halides,
oxides, oxyhalides, hydroxides or alkoxides. Examples of Ziegler
catalyst components are, without constituting a limitation:
titanium tetrachloride, zirconium tetrachloride, hafnium
tetrachloride, titanium trichloride, vanadium trichloride, vanadium
oxychloride, chromium trichloride or chromium oxide.
[0013] For the purposes of the present invention, metallocene
catalyst components are, for example, cyclopentadienyl complexes.
Preference is given to cyclopentadienyl complexes of metals of
group IIIa and the lanthanide group (eg. lanthanum or yttrium), and
also metals of group IVa (ie. titanium, zirconium or hafnium), Va
(eg. vanadium or niobium) or VIa (eg. chromium or molybdenum) of
the Periodic Table of the Elements; particular preference is given
to cyclopentadienyl complexes of titanium, zirconium or hafnium.
The cyclopentadienyl complexes can be, for example, bridged or
unbridged biscyclopentadienyl complexes as are described, for
example, in EP 129 368, EP 561 479, EP 545 304 and EP 576 970,
monocyclopentadienyl complexes such as bridged
amidocyclopentadienyl complexes as are described, for example, in
EP 416 815, multinuclear cyclopentadienyl complexes as described in
EP 632 063, tetrahydropentalenes substituted by pi ligands as
described in EP 659 758 or tetrahydroindenes substituted by pi
ligands as described in EP 661 300.
[0014] Preferred metallocene catalyst components are unbridged or
bridged metallocene compounds of the formula I, 1
[0015] where
[0016] M.sup.1 is a metal of group IIIa, IVa, Va or VIa of the
Periodic Table of the Elements, in particular Ti, Zr or Hf,
[0017] R.sup.1 are identical or different and are hydrogen or
SiR.sub.3.sup.3, where R.sup.3 are identical or different and are
each hydrogen or a C.sub.1-C.sub.40-group such as
C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.10-fluoroalkyl,
C.sub.1-C.sub.10-alkoxy, C.sub.6-C.sub.20-aryl,
C.sub.6-C.sub.10-fluoroaryl, C.sub.6-C.sub.10-aryloxy,
C.sub.2-C.sub.10-alkenyl, C.sub.7-C.sub.40-arylalkyl,
C.sub.7-C.sub.40-alkylaryl or C.sub.8-C.sub.40-arylalkenyl, or
R.sup.1 is a C.sub.1-C.sub.30-group such as C.sub.1-C.sub.25-alkyl,
eg. methyl, ethyl, tert-butyl, cyclohexyl or octyl,
C.sub.2-C.sub.25-alkenyl, C.sub.3-C.sub.15-alkylalkenyl,
C.sub.6-C.sub.24-aryl, C.sub.5-C.sub.24-heteroaryl such as pyridyl,
furyl or quinolyl, C.sub.7-C.sub.30-arylalkyl,
C.sub.7-C.sub.30-alkylaryl, fluorine-containing
C.sub.1-C.sub.25-alkyl, fluorine-containing C.sub.6-C.sub.24-aryl,
fluorine-containing C.sub.7-C.sub.30-arylalkyl, fluorine-containing
C.sub.7-C.sub.30-alkylaryl or C.sub.1-C.sub.12-alkoxy- , or two or
more radicals R.sup.1 can be joined to one another in such a way
that the radicals R.sup.1 and the atoms of the cyclopentadienyl
ring which connect them form a C.sub.4-C.sub.24 ring system which
may in turn be substituted,
[0018] l is 5 when v=0, and 1 is 4 when v=1,
[0019] Y is either
[0020] a) an element of main group V (eg. nitrogen or phosphorus)
or VI (eg. oxygen or sulfur) of the Periodic Table of the
Elelements which bears one or two C.sub.1-C.sub.20-hydrocarbon
substitutents such as C.sub.1-C.sub.10-alkyl or
C.sub.6-C.sub.20-aryl, or
[0021] b) 2
[0022] , where
[0023] R.sup.2 are identical or different and are hydrogen or
SiR.sub.3.sup.3, where R.sup.3 are identical or different and are
each hydrogen or a C.sub.1-C.sub.40-group such as
C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.10-fluoroalkyl,
C.sub.1-C.sub.10-alkoxy, C.sub.6-C.sub.14-aryl,
C.sub.6-C.sub.10-fluoroaryl, C.sub.6-C.sub.10-aryloxy,
C.sub.2-C.sub.10-alkenyl, C.sub.7-C.sub.40-arylalkyl,
C.sub.7-C.sub.40-alkylaryl or C.sub.8-C.sub.40-arylalkenyl, or
R.sup.2 is a C.sub.1-C.sub.30-group such as C.sub.1-C.sub.25-alkyl,
eg. methyl, ethyl, tert-butyl, cyclohexyl or octyl,
C.sub.2-C.sub.25-alkenyl, C.sub.3-C.sub.15-alkylalkenyl,
C.sub.6-C.sub.24-aryl, C.sub.5-C.sub.24-heteroaryl, eg. pyridyl,
furyl or quinolyl, C.sub.7-C.sub.30-arylalkyl,
C.sub.7-C.sub.30-alkylaryl, fluorine-containing
C.sub.1-C.sub.25-alkyl, fluorine-containing C.sub.6-C.sub.24-aryl,
fluorine-containing C.sub.7-C.sub.30-arylalkyl, fluorine-containing
C.sub.7-C.sub.30-alkylaryl or C.sub.1-C.sub.12-alkoxy- , or two or
more radicals R.sup.2 can be joined to one another in such a way
that the radicals R.sup.2 and the atoms of the cyclopentadienyl
ring which connect them form a C.sub.4-C.sub.24 ring system which
may in turn be substituted, and
[0024] m is 5 when v=0, and m is 4 when v=1,
[0025] L.sup.1 can be identical or different and are each a
hydrogen atom, a C.sub.1-C.sub.20-hydrocarbon radical such as
C.sub.1-C.sub.10-alkyl or C.sub.6-C.sub.20-aryl, a halogen atom or
OR.sup.6, SR.sup.6, OSiR.sub.3.sup.6, SiR.sub.3.sup.6,
PR.sub.2.sup.6 or NR.sub.2.sup.6, where R.sup.6 is a halogen atom,
C.sub.1-C.sub.10-alkyl group, a halogenated C.sub.1-C.sub.10-alkyl
group, a C.sub.6-C.sub.20-aryl group or a halogenated
C.sub.6-C.sub.20-aryl group, or L.sup.1 is a toluenesulfonyl,
trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl,
nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl
group,
[0026] o is an integer from 1 to 4, preferably 2,
[0027] Z is a a bridging structural element between the two
cyclopentadienyl rings and v is 0 or 1.
[0028] Examples of Z are groups (M.sup.2R.sup.4R.sup.5).sub.x,
where M.sup.2 is carbon, silicon, germanium or tin, x is 1, 2 or 3
and R.sup.4 and R.sup.5 are identical or different and are each
hydrogen or a C.sub.1-C.sub.20-hydrocarbon-containing group such as
C.sub.1-C.sub.10-alkyl, C.sub.6-C.sub.14-aryl or trimethylsilyl. Z
are preferably identical and are CH.sub.2, CH.sub.2CH.sub.2,
CH(CH.sub.3)CH.sub.2, CH(C.sub.4H.sub.9)C(CH.sub.3).sub.2,
C(CH.sub.3).sub.2, (CH.sub.3).sub.2Si, (CH.sub.3).sub.2Ge,
(CH.sub.3).sub.2Sn, (C.sub.6H.sub.5).sub.2Si,
(C.sub.6Hs)(CH.sub.3)Si, (C.sub.6H.sub.5).sub.2Ge,
(C.sub.6H.sub.5).sub.2Sn, (CH.sub.2).sub.4Si,
CH.sub.2Si(CH.sub.3).sub.2, o-C.sub.6H.sub.4 or
2,2'-(C.sub.6H.sub.4).sub- .2. Z together with one or more radicals
R.sup.1 and/or R.sup.2 can also form a monocyclic or polycyclic
ring system.
[0029] Examples of metallocene catalyst components are, without
constituting a limitation:
[0030] bis(cyclopentadienyl)titanium dichloride
[0031] bis(indenyl)titanium dichloride
[0032] bis(fluorenyl)titanium dichloride
[0033] bis(tetrahydroindenyl)titanium dichloride
[0034] bis(pentamethylcyclopentadienyl)titanium dichloride
[0035] bis(trimethylsilylcyclopentadienyl)titanium dichloride
[0036] bis(trimethoxysilylcyclopentadienyl)titanium dichloride
[0037] bis(isobutylcyclopentadienyl)titanium dichloride
[0038] bis(3-butenylcyclopentadienyl)titanium dichloride
[0039] bis(methylcyclopentadienyl)titanium dichloride
[0040] bis(1,3-di-tert-butylcyclopentadienyl)titanium
dichloride
[0041] bis(trifluoromethylcyclopentadienyl)titanium dichloride
[0042] bis(tert-butylcyclopentadienyl)titanium dichloride
[0043] bis(n-butylcyclopentadienyl)titanium dichloride
[0044] bis(phenylcyclopentadienyl)titanium dichloride
[0045] bis(N,N-dimethylaminomethylcyclopentadienyl)titanium
dichloride
[0046] bis(1,3-dimethylcyclopentadienyl)titanium dichloride
[0047] bis(-methyl-3-n-butylcyclopentadienyl)titanium
dichloride
[0048] (cyclopentadienyl)(methylcyclopentadienyl)titanium
dichloride
[0049] (cyclopentadienyl)(n-butylcyclopentadienyl)titanium
dichloride
[0050] (methylcyclopentadienyl)(n-butylcyclopentadienyl)titanium
dichloride
[0051]
(cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)titanium
dichloride
[0052] methylenebis(cyclopentadienyl)titanium dichloride
[0053] methylenebis(3-methylcyclopentadienyl)titanium
dichloride
[0054] methylenebis(3-n-butylcyclopentadienyl)titanium
dichloride
[0055] methylenebis(indenyl)titanium dichloride
[0056] methylenebis(tetrahydroindenyl)titanium dichloride
[0057] dimethylsilanediylbis(cyclopentadienyl)titanium
dichloride
[0058] dimethylsilanediylbis(tetramethylcyclopentadienyl)titanium
dichloride
[0059]
dimethylsilanediylbis(3-trimethylsilylcyclopentadienyl)titanium
dichloride
[0060] dimethylsilanediylbis(3-methylcyclopentadienyl)titanium
dichloride
[0061] dimethylsilanediylbis(3-n-butylcyclopentadienyl)titanium
dichloride
[0062] dimethylsilanediylbis(indenyl)titanium dichloride
[0063] dimethylsilanediylbis(tetrahydroindenyl)titanium
dichloride
[0064] isopropylidenebis(cyclopentadienyl)titanium dichloride
[0065] isopropylidenebis(3-trimethylsilylcyclopentadienyl)titanium
dichloride
[0066] isopropylidenebis(3-methylcyclopentadienyl)titanium
dichloride
[0067] isopropylidenebis(3-n-butylcyclopentadienyl)titanium
dichloride
[0068] isopropylidenebis(3-phenylcyclopentadienyl)titanium
dichloride
[0069] isopropylidenebis(indenyl)titanium dichloride
[0070] isopropylidenebis(tetrahydroindenyl)titanium dichloride
[0071] 1,2-ethanediylbis(cyclopentadienyl)titanium dichloride
[0072] 1,2-ethanediylbis(3-methylcyclopentadienyl)titanium
dichloride
[0073] 1,2-ethanediylbis(3-n-butylcyclopentadienyl)titanium
dichloride
[0074] 1,2-ethanediylbis(3-phenylcyclopentadienyl)titanium
dichloride
[0075] 1,2-ethanediylbis(indenyl)titanium dichloride
[0076] 1,2-ethanediylbis(tetrahydroindenyl)titanium dichloride
[0077] [(cyclopentadienyldimethylsilyl)(phenyl)amido]titanium
dichloride
[0078] [(cyclopentadienyldimethylsilyl)(methyl)amido]titanium
dichloride
[0079] [(cyclopentadienyldimethylsilyl)(tert-butyl)amido]titanium
dichloride
[0080] [(cyclopentadienyldimethylsilyl)(cyclohexyl)amido]titanium
dichloride
[0081] bis(cyclopentadienyl)zirconium dichloride
[0082] bis(indenyl)zirconium dichloride
[0083] bis(fluorenyl)zirconium dichloride
[0084] bis(tetrahydroindenyl)zirconium dichloride
[0085] bis(1,3-di-tert-butylcyclopentadienyl)zirconium
dichloride
[0086] bis(tetramethylcyclopentadienyl)zirconium dichloride
[0087] bis(trimethylsilylcyclopentadienyl)zirconium dichloride
[0088] bis(trimethoxysilylcyclopentadienyl)zirconium dichloride
[0089] bis(isobutylcyclopentadienyl)zirconium dichloride
[0090] bis(3-butenylcyclopentadienyl)zirconium dichloride
[0091] bis(methylcyclopentadienyl)zirconium dichloride
[0092] bis(trifluoromethylcyclopentadienyl)zirconium dichloride
[0093] bis(tert-butylcyclopentadienyl)zirconium dichloride
[0094] bis(n-butylcyclopentadienyl)zirconium dichloride
[0095] bis(phenylcyclopentadienyl)zirconium dichloride
[0096] bis(1,3-dimethylcyclopentadienyl)zirconium dichloride
[0097] bis(1-methyl-3-n-butylcyclopentadienyl)zirconium
dichloride
[0098] (cyclopentadienyl)(methylcyclopentadienyl)zirconium
dichloride
[0099] (cyclopentadienyl)(n-butylcyclopentadienyl)zirconium
dichloride
[0100] (methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium
dichloride
[0101]
(cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)zirconium
dichloride
[0102] methylenebis(cyclopentadienyl)zirconium dichloride
[0103] methylenebis(3-methylcyclopentadienyl)zirconium
dichloride
[0104] methylenebis(3-n-butylcyclopentadienyl)zirconium
dichloride
[0105] methylenebis(indenyl)zirconium dichloride
[0106] methylenebis(tetrahydroindenyl)zirconium dichloride
[0107] dimethylsilanediylbis(cyclopentadienyl)zirconium
dichloride
[0108] dimethylsilanediylbis(tetramethylcyclopentadienyl)zirconium
dichloride
[0109]
dimethylsilanediylbis(3-trimethylsilylcyclopentadienyl)zirconium
dichloride
[0110] dimethylsilanediylbis(3-methylcyclopentadienyl)zirconium
dichloride
[0111] dimethylsilanediylbis(3-n-butylcyclopentadienyl)zirconium
dichloride
[0112] dimethylsilanediylbis(indenyl)zirconium dichloride
[0113] dimethylsilanediylbis(tetrahydroindenyl)zirconium
dichloride
[0114] isopropylidenebis(cyclopentadienyl)zirconium dichloride
[0115] isopropylidenebis(3-trimethylsilylcyclopentadienyl)zirconium
dichloride
[0116] isopropylidenebis(3-methylcyclopentadienyl)zirconium
dichloride
[0117] isopropylidenebis(3-n-butylcyclopentadienyl)zirconium
dichloride
[0118] isopropylidenebis(3-phenylcyclopentadienyl)zirconium
dichloride
[0119] isopropylidenebis(3indenyl)zirconium dichloride
[0120] isopropylidenebis(tetrahydroindenyl)zirconium dichloride
[0121] 1,2-ethanediylbis(cyclopentadienyl)zirconiumdichloride
[0122] 1,2-ethanediylbis(3-methylcyclopentadienyl)zirconium
dichloride
[0123] 1,2-ethanediylbis(3-n-butylcyclopentadienyl)zirconium
dichloride
[0124] 1,2-ethanediylbis(3-phenylcyclopentadienyl)zirconium
dichloride
[0125] 1,2-ethanediylbis(indenyl)zirconium dichloride
[0126] 1,2-ethanediylbis(tetrahydroindenyl)zirconium dichloride
[0127] bis(cyclopentadienyl)hafnium dichloride
[0128] bis(trimethylsilylcyclopentadienyl)hafnium dichloride
[0129] bis(methylcyclopentadienyl)hafnium dichloride
[0130] bis(n-butylcyclopentadienyl)hafnium dichloride
[0131] bis(1,3-dimethylcyclopentadienyl)hafnium dichloride
[0132] methylenebis(cyclopentadienyl)hafnium dichloride
[0133] methylenebis(3-n-butylcyclopentadienyl)hafnium
dichloride
[0134] dimethylsilanediylbis(cyclopentadienyl)hafnium
dichloride
[0135] dimethylsilanediylbis(3-methylcyclopentadienyl)hafnium
dichloride
[0136] dimethylsilanediylbis(3-n-butylcyclopentadienyl)hafnium
dichloride
[0137] isopropylidenebis(cyclopentadienyl)hafnium dichloride
[0138] 1,2-ethanediylbis(cyclopentadienyl)hafnium dichloride
[0139] 1,2-ethanediylbis(3-methylcyclopentadienyl)hafnium
dichloride
[0140] 1,2-ethanediylbis(3-n-butylcyclopentadienyl)hafnium
dichloride
[0141] [(cyclopentadienyldimethylsilyl)(phenyl)amido]zirconium
dichloride
[0142] [(cyclopentadienyldimethylsilyl)(methyl)amido]zirconium
dichloride
[0143] [(cyclopentadienyldimethylsilyl)(tert-butyl)amido]zirconium
dichloride
[0144] [(cyclopentadienyldimethylsilyl)(cyclohexyl)amido]zirconium
dichloride
[0145] 1-silacyclopentane-1,1-bis(indenyl)zirconium dichloride
[0146] 1,6-bis[methylsilylbis(indenyl)zirconium
dichloride]hexane
[0147] 1,4-disila-1,4-bis[cyclopentadienylzirconium
dichloride]-cyclohexane
[0148]
1,4-disila-1,4-bis[cyclopentadienyltitandichlorid]cyclohexane.
[0149] Further examples are the corresponding metallocene compounds
in which one or both of the chloride ligands are replaced by
bromide, iodide or methyl.
[0150] As catalyst component based on a late transition metal, the
catalyst composition of the present invention preferably comprises
a nickel, rhodium, platinum, iron, ruthenium, cobalt or palladium
compound, particularly preferably a nickel, iron or palladium
compound. The late transition metal compound preferably contains,
exclusively or in combination with other ligands, ligands which
coordinate to the metal in a chelating fashion via two or more
atoms. The two coordinating atoms are preferably nitrogen atoms.
Particular preference is given to ligands of the formulae II and
III below. 3
[0151] In these formulae, R.sup.7 and R.sup.8 are, independently of
one another, identical or different C.sub.1-C.sub.40-hydrocarbon
radicals in which the carbon atom joined to the nitrogen atom is
preferably joined to at least two further carbon atoms. R.sup.7 and
R.sup.8 are preferably C.sub.6-C.sub.20-aryl radicals which are
preferably substituted in both ortho positions, eg. by
C.sub.1-C.sub.10-alkyl radicals such as methyl or isopropyl.
R.sup.9 and R.sup.10 are, independently of one another, identical
or different and are each hydrogen or a C.sub.1-C.sub.40-hydroc-
arbon radical such as C.sub.1-C.sub.20-alkyl or
C.sub.6-C.sub.20-aryl, or R.sup.9 and R.sup.10 together form a ring
system which is preferably derived from acenaphthenequinone.
[0152] Particular preference is given to nickel or palladium
compounds, in particular those in the oxidation states zero or two
and containing the ligands of the formula III.
[0153] Also preferred are iron, ruthenium, cobalt or rhodium
catalysts containing ligands of the formula II.
[0154] As catalyst component based on a late transition metal, the
catalyst composition of the present invention preferably comprises
the nickel or palladium compounds described in WO 96/23010 (which
is hereby expressly incorporated by reference) which have a ligand
coordinated in a bidentate fashion via nitrogen atoms.
[0155] The late transition metal component can already contain the
ligand coordinating to the metal or it can be prepared in situ (ie.
in the polymerization reactor) by combining a suitable transition
metal component with the free ligand or a ligand derivative.
[0156] Examples of particularly useful late transition metal
components are listed below. In these examples, An is a ligand of
the formula III in which the radicals R.sup.9 and R.sup.10 form a
ring system derived from acenaphthenequinone as shown in the
following formula: 4
[0157] Me=methyl, Et=ethyl and .sup.iPr=isopropyl.
[0158] The examples of late transition metal compounds are:
[0159]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}NiBr.sub.2]
[0160]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiBr.sub.2]
[0161]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiBr.sub.2]
[0162]
[{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-Me.sub.2-
C.sub.6H.sub.3)}NiBr.sub.2]
[0163]
[{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6-Me.sub-
.2C.sub.6H.sub.3)}NiBr.sub.2]
[0164]
[{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6-Me.sub-
.2C.sub.6H.sub.3)}NiBr.sub.2]
[0165]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0166]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0167]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0168]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+BF.sub.4.sup.-
[0169]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+BF.sub.4.sup.-
[0170]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}PdMe(NC--Me)].sup.+BF.sub.4.sup.-
[0171]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(SbF.sub.6.sup.-)
[0172]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(SbF.sub.6-)
[0173]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(SbF.sub.6-)
[0174]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(BF.sub.4-).sub.2
[0175]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(BF.sub.4-)
[0176]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}Pd(NC--Me).sub.2].sup.2+(BF.sub.4-).sub.2
[0177]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}NiMe(OEt.sub.2)].sup.+
[0178] [B{3,5-(F.sub.3C).sub.2C.sub.6H.sub.3}.sub.4].sup.-
[0179]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiMe(OEt.sub.2)].sup.+
[0180] [B{3,5-(F.sub.3C).sub.2C.sub.6H.sub.3}.sub.4].sup.-
[0181]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiMe(OEt.sub.2)].sup.+
[0182] [B{3,5-(F.sub.3C).sub.2C.sub.6H.sub.3}.sub.4].sup.-
[0183]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(H)--C(H).dbd.N-(2,6-.s-
up.iPr.sub.2C.sub.6H.sub.3)}NiMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0184]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(An)--C(An).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0185]
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)--C(Me).dbd.N-(2,6--
.sup.iPr.sub.2C.sub.6H.sub.3)}NiMe(NC--Me)].sup.+SbF.sub.6.sup.-
[0186]
[2,6-{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]FeBr.s-
ub.2
[0187]
[2,6-{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]FeBr.sub.2
[0188]
[2,6-{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]CoBr.s-
ub.2
[0189]
[2,6-{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]CoBr.sub.2
[0190]
[2,6-{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]FeBr.s-
ub.3
[0191]
[2,6-{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]FeBr.sub.3
[0192]
[2,6-{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]CoBr.s-
ub.3
[0193]
[2,6-{(2,6-Me.sub.2C.sub.6H.sub.3)-N.dbd.C(Me)}pyridyl]CoBr.sub.3
[0194] In place of the dibromides listed, it is also possible to
use the corresponding compounds in which one or both of the bromide
ligands are replaced by chloride, iodide or methyl.
[0195] Further examples of suitable polymerization catalyst
components based on a late transition metal are reaction products
of nickel compounds with
(Me.sub.3Si)N.dbd.P{N(SiMe.sub.3).sub.2}.dbd.N(SiMe.sub.3) or
(2,4,6-Me.sub.3C.sub.6H.sub.2)P.dbd.C(OSiMe.sub.3)-PH(2,4,6-Me.sub.3C.-
sub.6H.sub.2).
[0196] The catalyst composition of the present invention preferably
comprises one or more activators such as Lewis acids.
[0197] Lewis acid activators, preference is given to using boron
compounds such as boranes or aluminum compounds such as aluminum
alkyls or aluminoxanes. Examples of suitable activators are boranes
such as trifluoroborane, triphenylborane,
tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,
tris(4-fluoropethylphenyl)borane, tris(pentafluorophenyl)borane,
tris(tolyl)borane, tris(3,5-dimethylphenyl- )borane,
tris(3,5-difluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane
or dimethylanilinium [tetrakis(pentafluorophenyl)borate],
[H(OEt.sub.2)][B{3,5-(CF.sub.3).sub.2C.sub.6F.sub.3}.sub.4],
aluminum alkyls such as Al(C.sub.2H.sub.5).sub.3,
Al(CH.sub.2CH(CH.sub.3).sub.2).s- ub.3, Al(C.sub.3H.sub.7).sub.3,
Al((CH.sub.2).sub.3CH.sub.3).sub.3,
Al((CH.sub.2).sub.5CH.sub.3).sub.3, Al(C.sub.6F.sub.5).sub.3,
Al(C.sub.2H.sub.5).sub.2Cl, Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.2
or AlCl.sub.3, or aluminoxanes such as methylaluminoxane,
isobutylaluminoxane, butylaluminoxane, heptylaluminoxane and
ethylbutylaluminoxane. Particular preference is given to using
aluminoxanes.
[0198] The activator can be used in any amounts based on the
transition metal components of the catalyst composition of the
present invention; it is preferably used in excess or in a
stoichiometric amount. It is possible to activate the early
transition metal component and the late transition metal component
of the catalyst composition using the same activator or different
activators. Preferably, the same activator is used for all
transition metal components. The activation of the various
transition metal components can be carried out at the same place,
eg. in the reactor, or at different places. In a preferred
embodiment, an excess of the activator is mixed with the early
transition metal component and this mixture is added to the late
transition metal component which has already been contacted with
the monomer.
[0199] As activator for the catalyst component based on a late
transition metal, preference is given to using an aluminoxane.
[0200] As activator for the catalyst component based on an early
transition metal, preference is given to using an aluminum alkyl in
the case of a Ziegler catalyst component and to using an
aluminoxane and/or a borane in the case of a metallocene catalyst
component.
[0201] It is possible but not necessary for the catalyst
composition of the present invention to comprise one or more
support components. In this case, both the early and the late
transition metal components can be supported, or only one of the
two components an be supported. In a preferred embodiment, both
components are supported in order to ensure that the various
catalyst centers are relatively close together and thus to ensure
good mixing of the different polymers formed.
[0202] The support component is preferably a porous inorganic or
organic solid. The support material preferably comprises at least
one inorganic halide such as MgCl.sub.2 or an inorganic oxide such
as SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO.sub.2, TiO.sub.2,
B.sub.2O.sub.3, CaO, ZnO, ThO.sub.2, carbonates such as
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, CaCO.sub.3, MgCO.sub.3, sulfates
such as Na.sub.2SO.sub.4, Al.sub.2(SO.sub.4).sub.3, BaSO.sub.4,
nitrates such as KNO.sub.3, Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3
or oxides such as Na.sub.2O, K.sub.2O, Li.sub.2O, in particular
silicon oxide and/or aluminum oxide or it preferably comprises at
least one homopolymer or copolymer which may be crosslinked, eg.
polyethylene, polypropylene, polybutene, polystyrene,
divinylbenzene-crosslinked polystyrene, polyvinyl chloride,
acryl-butadiene-styrene copolymers, polyamide, polymethacrylate,
polycarbonate, polyester, polyacetal or polyvinyl alcohol. Polymer
blends can also be used.
[0203] The support material may be pretreated, eg. by heating at
from 50.degree. C. to 1000.degree. C., eg. in a stream of inert gas
or under reduced pressure at from 0.01 bar to 0.001 bar, or by
mixing or reacting with a chemical compound. The chemical compound
can react with catalyst poisons, eg. aluminum alkyls, magnesium
alkyls, boron alkyl or lithium alkyls, or lead to a
functionalization of the surface of the support. It is immaterial
whether the support material bears functional groups at the outset
or these are introduced only after the pretreatment by means of
appropriate reactions on the surface.
[0204] The application to the support can be carried out by mixing
the individual catalyst components in any order. Thus, for example,
the early transition metal compound and the late transition metal
compound can be applied to the optimally pretreated support (eg.
comprising SiO.sub.2) and subsequently admixed with the activator,
preferably in the presence of monomer.
[0205] The present invention further relates to a process for the
polymerization of olefins in the presence of the catalyst
composition of the present invention. The term polymerization
includes both homopolymerization and copolymerization.
[0206] The catalyst system of the present invention can be used for
reacting one or more olefinic comonomers such as ethylene or
C.sub.3-C.sub.20-.alpha.-olefins. If two or more comonomers are
used, the early and the late transition metal components can be
active for all monomers used, although it is also possible for one
transition metal component to specifically react only one or more
of the monomers used. For example, ethylene and an .alpha.-olefin,
which preferably has from 3 to 20 carbon atoms, can be used. This
gives a mixture of two copolymers or a mixture of one copolymer
with an ethylene homopolymer. The copolymer having the lower
proportion of .alpha.-olefin is preferably formed by the late
transition metal component. In the process of the present
invention, particular preference is given to homopolymerizing
ethylene, giving a blend of at least two different polyethylenes
which have a different branching structure.
[0207] The polymerization process can be carried out in the liquid
phase or in the gas phase. The process is preferably carried out in
the liquid phase. As solvents or suspension media, preference is
given to using inert organic compounds. Particular preference is
given to using aromatic or aliphatic hydrocarbons or their
mixtures. Particularly suitable solvents or suspension media are
toluene, xylenes and saturated aliphatic
C.sub.10-C.sub.30-hydrocarbons. The process can also be carried out
in supercritical media.
[0208] The polymerization process is preferably carried out at from
-100 to 300.degree. C., preferably from 0 to 200.degree. C.,
particularly preferably from 25 to 150.degree. C. The process is
carried out in the pressure range from 1 to 300 atm, preferably
from 1 to 100 atm, particularly preferably from 3 to 30 atm. The
process can be carried out in one or more stages.
[0209] The selection of appropriate reaction conditions, eg.
temperature, addition of chain transfer agents such as hydrogen,
monomer concentrations and the catalyst concentrations makes it
possible to control the molecular weight distributions, degree of
branching and other properties of the polymers formed. The degree
of branching of the polymers can be controlled via the
concentration of the monomers. The reaction can also be carried out
in two or more reactors connected in series. Feeding the catalyst
components into the individual reactors makes it possible to change
the ratio of the two catalysts.
[0210] The productivity of each individual transition metal
component is preferably above 2800 kg of polymer/(mole of
transition metal.times.h), particularly preferably above 15,000 kg
of polymer/(mole of transition metal.times.h).
[0211] The catalyst composition of the present invention is
suitable for preparing reactor blends of two or more polymers which
have advantageous use and processing properties. The number average
molar masses of the individual polymer fractions are preferably in
the range from 11 to 10,000 kg/mole, particularly preferably from
20 to 1000 mole. The molar ratio of the early transition metal
components to the late transition metal component(s) can be in the
range from 0.1:99.9 to 99.9:0.1, preferably from 1:30 to 1:1. The
ratio of the proportions of polymers formed by the early transition
metal catalyst and by the late transition metal catalyst can be in
the range from 0.1:99.9 to 99.9:0.1, preferably from 10:90 to
90:10, particularly preferably from 1:1 to 50:1.
[0212] The polymerization process of the present invention is
particularly suitable for the homopolymerization of ethylene to
give a blend of two or more polymers of which at least one has the
following branching structure: it contains at least 10 branches per
1000 carbon atoms and at least two ethyl branches, at least one
butyl branch and from one to fifty amyl or higher branches are
present per 100 methyl branches.
[0213] The polymerization process of the present invention is
particularly preferably used for the polymerization of ethylene to
give a blend of two or more polymers of which at least one has the
following branching structure: it contains at least 30 branches per
1000 carbon atoms and at least four ethyl branches, at least two
butyl branches and from two to thirty amyl or higher branches are
present per 100 methyl branches.
[0214] In particular, it is possible to obtain a reactor blend of
two polyethylenes of which preferably one contains >10
branches/1000 carbon atoms, preferably >20 branches/1000 carbon
atoms, particularly preferably >40 branches/1000 carbon
atoms.
[0215] The preparation of the polymer blend in the reactor reduces
the energy consumption, requires no subsequent blending processes
and makes it possible to control the molecular weight distributions
and the molecular weight fractions of the various polymers in a
simple manner. In addition, good mixing of the polymers can be
achieved. The preparation of a blend of two or more polymers having
different degrees of branching from ethylene without addition of a
comonomer reduces the costs for the olefins used, and also the
plant and other costs for providing the comonomer.
[0216] The following examples illustrate the invention:
EXAMPLE 1
[0217] A solution of 2.2 mg of
[{(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)-N.dbd.-
C(An)--C(An).dbd.N-(2,6-.sup.iPr.sub.2C.sub.6H.sub.3)}NiBr.sub.2]
in 600 ml of toluene was placed in a 1 l steel autoclave fitted
with a heating/cooling jacket and a mechanical stirrer. The
solution was saturated with ethylene by stirring briefly under 10
atm of ethylene. The reactor was then depressurized and a solution
of 0.05 mg of bis(cyclopentadienyl)zirconium dichloride in 10 ml of
a 10% strength methylaluminoxane solution in toluene was added. The
autoclave was closed and a constant pressure of 10 atm of ethylene
was applied. The autoclave was heated to 50.degree. C. After 15
minutes, the reaction was interrupted by venting the ethylene and
destroying the catalyst by means of isopropanol.
[0218] The reaction mixture obtained was poured into 1 l of
methanol acidified with HCl. The polymer product obtained was dried
under reduced pressure, giving 33.4 g of polymer.
[0219] 1H-NMR (1,2-C.sub.6D.sub.4Cl.sub.2: 120.degree. C.): 21
branches/1000 carbon atoms
EXAMPLE 2
[0220] Example 1 was repeated using 0.28 mg of the nickel compound
and 0.175 mg of Cp.sub.2ZrCl.sub.2. The polymerization was carried
out at 40.degree. C. and was stopped after half an hour. 5.8 g of
polymer were obtained.
[0221] 1H-NMR (1,2-C.sub.6D.sub.4Cl.sub.2: 120.degree. C.): 12
branches/1000 carbon atoms.
* * * * *