Catalysts systems for the polymerization and...

Details Catalysts systems for the polymerization and... Catalysts systems for the polymerization and...

1997-10-30

2003-10-21

Kopec, Mark (Department: 1751)

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

Organic compounds

Heavy metal containing

C502S102000, C502S114000, C502S160000, C502S300000, C585S311000, C585S312000, C585S702000

Reexamination Certificate

active

06635778

ABSTRACT:

Incorporated herein by this reference is Spanish Application No. 9602302, filed on Oct. 30, 1996. This U.S. application claims priority under 35 U.S.C. 119 to Spanish Application No. 9602302, filed on Oct. 30, 1996.
BACKGROUND
The present invention relates to new organometallic catalysts to the process for preparation thereof and their use for the polymerization and copolymerization of ethylene and alpha-olefins in industrial production plants.
There is a great variety of processes and catalysts useful for the homo- and copolymerization of olefins. Catalytic systems such as Ziegler-Natta are typically able to produce polyolefins with high molecular weight and broad distribution of molecular weight. However, for many industrial applications it is of the greatest importance to obtain polyolefins characterized by a high molecular weight, and narrow molecular weight distribution. Besides, with these Ziegler-Natta type of catalysts, to obtain copolymers with fit comonomer contents it is necessary to use high comonomer/monomer molar ratios in the feed and as a consequence the industrial process becomes enormously more expensive.
In the last years there has been the development of organometallic catalytic metallocene systems, that, combined with non-coordinative anions, alkylaluminoxanes or boron perfluorinated compounds (U.S. Pat. No. 4,542,199 and EP 426637) allow to obtain polyolefins with narrow distributions of molecular weight and high molar comonomer contents. However, the molecular weights are not as high as it would be useful to give the polymer the desired properties. Besides, these molecular weights suddenly lower when the comonomer content increases, or when the polyme zation temperature rises.
In EP 416815 and EP 420436 there is the description of a new type of organometallic catalysts in which a transition metal is coordinated to a cyclopentadienyl ring and to a heteroatom. These organometallic compounds, when they are activated with alkylaluminoxanes, are able to produce ethylene polymers with high molecular weight and narrow distribution of molecular weight. They moreover own a great effectiveness in comonomer incorporation. However, when the comonomer content of the polymeric chain is increasing, the molecular weight sensibly decreases.
Therefore it is an object of the present invention to provide new compounds, useful in the (co)polymerization of alpha-olefins, in particular in the (co)polymerization of ethylene, which can produce polymers with high molecular weights. Besides, these catalysts are especially efficient in the comonomer incorporation, and produce copolymers with totally random distributions of the comonomer.
The organo metallic complexes (catalysts) disclosed in the present invention are characterized by the following general formula I:
wherein:
M is a transition metal of groups 3, 4-10 of the periodic table of the elements, lanthanide or actinide, preferably titanium, zirconium or hafnium.
Each X group, equal to or different from each other, is hydrogen, halogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl with 1 to 20 carbon atoms, linear or branched, the hydrogens of these groups optionally are substituted by SiR
3
, GeR
3
, OR, NR
2
, OSiR
3
groups or any combination thereof wherein R is selected from the group comprising: hydrogen, C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkenyl, C
7
-C
20
arylalkyl, C
7
-C
20
arylalkenyl or alkylaryl, branched or linear.
n is a number whose value is: 0, 1, 2 or 3, in order to fill the remaining free valences of the metal M;
L is a neutral Lewis base such as dietylether, tetrahydrofurane, dimethylaniline, aniline, triphenilphosphine, n-butylamine, etc.
z is a number whose value is: 0, 1, 2 or 3.
A is a ring with delocalized &pgr; electrons, that directly coordinates to the transition metal M. Preferably A is a cyclopentadienyl type of ring of formula C
5
R
1
4
, wherein each RW group, equal to or different from each other is hydrogen, C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkenyl, C
7
-C
20
arylalkyl, C
7
-C
20
arylalkenyl or alkylaryl, branched or linear, the hydrogens of these groups optionally are substituted by SiR
3
, GeR
3
, OR, NR
2
, OSiR
3
groups or any combination thereof wherein R is above defined; R
1
is also selected from the group comprising SiR
3
, GeR
3
, OR, R
2
N, OSiR
3
groups or any combination thereof. Two adjacent R
1
optionally unite in order to form a saturated or unsaturated polycyclic cyclopentadienyl ring such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl, optionally substituted with R
1
groups.
R
II
is hydrogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl from 1 to 20 carbon atoms, linear or branched, whose hydrogens are optionally substituted by SiR
3
, GeR
3
, OR, NR
2
, OSiR
3
groups or any combination thereof wherein R is above defined; it optionally forms a condensed ring through another bond with E. Preferably R
II
is tertbutyl.
Each E group, equal to or different from each other, is BR
III
, CR
IV
2
, SiR
III
2
, GeR
III
2
; at least one E is SiR
III
2
. Preferably the bridge E—E is CR
IV
2
—SiR
III
2
. Each R
III
, equal to or different from each other, is hydrogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl with 1 to 20 carbon atoms, linear or branched, whose hydrogens optionally are substituted by SiR
3
, GeR
3
, OR, NR
2
, OSiR
3
groups or any combination thereof wherein R is above defined; R
IV
has the same meaning of R
III
or it is halogen; besides two groups selected from R
IV
and R
III
belonging to different E optionally form a cyclic structure.
The catalysts component of general formula I, can be suitably prepared through reaction of a compound of general formula M′—A—E—E—NR
II
—M′, wherein M′ is Li, Na or K, with a metal M compound, preferably of formula MX
4
or with an adduct of formula MX
4
2L or MX
3
3L, where X is above defined and L preferably is a linear or cyclic ether as for example: ethylic ether, tetrahydrofurane, dimetoxyethane, etc.
The compound of general formula M′—A—E—E—NR
II
—M′ can be suitably prepared through reaction of HA—E—E—NR
II
H with two equivalents of an alkyl or aryl alkali metal salt, or with an alkali metal hydride or an alkaline metal:
Wherein R
c
is C
1
-C
20
alkyl or C
6
-C
20
aryl.
Alternatively, alkyl magnesium salts, which are obtained in the same way, can be used, but using an alkyl magnesium halide instead of alkyl lithium.
When the bridge E—E is SiR
III
2
—CR
IV
2
, the compound HA—SiR
III
2
—CR
IV
2
—NR
II
H can be suitably prepared starting from a compound of general formula HA—SiR
III
2
—CR
IV
2
—OH or its lithium salts. The process comprises the following steps:
a) reacting a compound of formula HA—SiR
III
2
—CR
IV
2
—OJ wherein J is lithium or hydrogen with an alkyl- or aryl-sulphonates according to the scheme:
HA—SiR
III
2
—CR
IV
2
—OJ+ClSO
2
R
a
→HA—SiR
III
2
—CR
IV
2
—OSO
2
R
a
b) contacting the recovered product of step a) with an excess of an amine of formula NR
II
H
2
HA—SiR
III
2
—CR
IV
2
—OSO
2
R
a
+H
2
NR
II
→HA—SiR
III
2
—CR
IV
2
—NHR
II
+HNR
II
—OSO
2
R
a
wherein R
a
is C
1
-C
20
alkyl, perfluoroalkyl or C
6
-C
20
aryl radical.
During the process for obtaining the intermediate compound of formula HA—E—E—NR
II
H and their alkali metal or magnesium halide salts, as well as the organometallic complexes obtained therefrom with the transition metal salts, the reaction temperature is kept between −100° C. and 95° C., preferably between −80° C. and 80° C., operating preferably under nitrogen inert atmosphere.
As non polar solvents pentane, hexane and toluene can be used; as polar aprotic solvents ethers such as diethyl ether, tetrahydrofurane or dimetoxyethane can be used.
During the whole process, both the chemical species and the solvents were protected from oxygen and humidity. The organometallic catalysts, when stored under inert atmosphere, are active in polymerization fo

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