Catalysts for the polymerization of olefins and process for...

Details Catalysts for the polymerization of olefins and process for... Catalysts for the polymerization of olefins and process for...

1999-06-29

2002-11-05

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S092000, C526S153000, C526S160000, C526S943000, C502S103000, C502S111000, C502S117000, C502S132000

Reexamination Certificate

active

06476163

ABSTRACT:

The present invention relates to catalysts for the polymerisation of olefins. In particular, it relates to high activity catalysts for the polymerisation of olefins obtained from cyclopentadienyl compounds of a transition metal, organometallic aluminium compounds and water.
The invention also relates to processes for the polymerisation of olefins carried out in the presence of the catalysts of the invention.
Homogeneous catalytic systems based on metallocene compounds, aluminium alkyl compounds and water are known to be active in the polymerisation of olefins.
In European Patent Application EP 384,171, catalysts for the polymerisation of olefins are described which comprise the reaction product of:
(a) a metallocene compound of formula:
(C
5
R′
n
)
m
R″
p
(C
5
R′
n
)MX
3−m
wherein (C
5
R′
n
) is an optionally substituted cyclopentadienyl group and two or four R′ substituents of one and the same cyclopentadienyl group can form one or two rings having 4 to 6 carbon atoms; R″ is a divalent radical bridging the two cyclopentadienyl groups; X can be for instance an halogen atom; M is a transition metal selected from Ti, Zr and Hf; p is 0 or 1; m is 0, 1 or 2, and when m=0 then p=0, and when p=0 at least one R′ substituent is different from hydrogen; n=4 when p=1, and n=5 when p=0; and
(b) an alumoxane of the formula:
wherein the substituents R can generically be alkyl, alkenyl or alkylaryl radicals, having 2-20 carbon atoms.
The alumoxanes (b) are prepared by reacting the corresponding trialkylaluminium compounds with water in a molar ratio of 2:1. In the alumoxanes used in the embodiment examples, the R substituents are isobutyl or 2-methylpentyl groups.
European Patent Application EP 575,875 describes homogeneous catalytic systems for the polymerisation of olefins comprising:
(A) a cyclopentadienyl compound of formula:
(C
5
R
1
x−m
H
5−x
)R
2
m
(C
5
R
1
y−m
H
5−y
)
n
MQ
3−n
in which M is Ti, Zr or Hf; C
5
R
1
x−m
H
5−x
and C
5
R
1
y−m
H
5−y
are equally or differently substituted cyclopentadienyl rings and two or four substituents R
1
of the same cyclopentadienyl group can form one or two rings, having from 4 to 6 carbon atoms; R
2
is a bridging group which links the two cyclopentadienyl rings; the substituents Q are preferably chlorine atoms; m can be 0 or 1; n can be 0 or 1, being 1 when m=1; x is an integer comprised between m+1 and 5; y is an integer comprised between m and 5;
(B) an organometallic aluminium compound of formula:
AlR
4
3−z
H
z
wherein the substituents R
4
are alkyl, alkenyl or alkylaryl radicals, containing from 1 to 10 carbon atoms, which may also contain Si or Ge atoms, at least one of the substituents R
4
being different from a straight alkyl group; z is 0 or 1; and
(C) water.
The molar ratio between the organometallic aluminium compound and the water is comprised between 1:1 and 100:1. In the embodiment examples, only triisobutylaluminium and triisohexylaluminium are used as the organometallic aluminium compounds.
International Patent Application WO 96/02580 describes improved catalytic systems comprising:
(A) a cyclopentadienyl compound of formula:
(C
5
R
1
x−m
H
5−x
)R
2
m
(C
5
R
1
y−m
H
5−y
)
n
MQ
3−n
in which M is Ti, Zr or Hf; C
5
R
1
x−m
H
5−x
and C
5
R
1
y−m
H
5−y
are equally or differently substituted cyclopentadienyl rings; the substituents R
1
, the same or different from each other, are alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals, which have 1 to 20 carbon atoms, optionally containing Si or Ge atoms or groups Si(CH
3
)
3
, or two or four substituents R
1
of one and the same cyclopentadienyl group can also form one or two rings, having 4 to 6 carbon atoms; R
2
is a bridging group linking the two cyclopentadienyl rings and is selected from CR
3
2
, C
2
R
3
4
, SiR
3
2
, Si
2
R
3
4
, GeR
3
2
, Ge
2
R
3
4
, R
3
2
SiCR
3
2
, NR
1
and PR
1
, wherein the substituents R
3
, the same or different from each other, are R
1
or hydrogen, or two or four substituents R
3
can also form one or two rings, having 3 to 6 carbon atoms; the substituents Q, the same or different from each other, are halogen, hydrogen, R
1
, OR
1
, SR
1
, NR
1
2
or PR
1
2
; m can be 0 or 1; n can be 0 or 1, being 1, if m=1; x is an integer comprised between (m+1) and 5; and y is an integer comprised between m and 5;
(B) an organometallic aluminium compound of formula:
Al(CH
2
—CR
4
R
5
R
6
)
w
R
7
y
H
z
wherein in the (CH
2
—CR
4
R
5
R
6
) groups, the same or different from each other, R
4
is an alkyl, alkenyl or arylalkyl group, having from 1 to 10 carbon atoms; R
5
is an alkyl, alkenyl, aryl, arylalkyl or alkylaryl group, having from 3 to 50 carbon atoms which is different from a straight alkyl or alkenyl group and, optionally, R
4
and R
5
fused together can form a ring, having from 4 to 6 carbon atoms; R
6
is hydrogen or an alkyl, alkenyl or arylalkyl group, having from 1 to 10 carbon atoms; the R
7
substituents, the same or different from each other, are alkyl, alkenyl, aryl, arylalkyl or alkylarl radicals. containing from 1 to 10 carbon atoms, optionally containing Si or Ge atoms; w is 1, 2 or 3; z is 0 or 1; y=3−w−z; and
(C) water.
The molar ratio between the organometallic aluminium compound and water is comprised between 1:1 and 100:1. The only organometallic aluminium compounds disclosed are those wherein the (CH
2
—CR
4
R
5
R
6
) groups are 2,4,4-trimethyl-pentyl, 2-phenyl-propyl or 1-butene oligomers. According to the cited application, the compound (B) can be contacted with (A) and successively with (C), or can be reacted with (C) and successively with (A); moreover, in the examples, the three components are mixed together at the same time.
It has now surprisingly been found that, by contacting components (A), (B) and (C) described in the above-mentioned European patent application EP 575,875 according to a novel procedure, catalysts can be obtained with higher activity than those obtained according to the prior art.
It is therefore an object of the present invention a catalyst for the polymerisation of olefins, comprising the product obtainable by contacting the following components:
(A) a cyclopentadienyl compound of formula (I):
(C
5
R
1
x−m
H
5−x
)R
2
m
(C
5
R
1
y−m
H
5−y
)
n
MQ
3−n
  (I)
wherein M is a metal selected from the group consisting of Ti, Zr and Hf; C
5
R
1
x−m
H
5−x
and C
5
R
1
y−m
H
5−y
are equally or differently substituted cycopentadienyl rings; the substituents R
1
, the same or different from each other, are selected from the group consisting of a linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl or C
7
-C
20
arylalkyl groups radicals, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements (new IUPAC notation), such as B, P, Al, Si, Ge, O and S atoms, or two or four substituents R
1
of the same cyclopentadienyl group form one or two rings, having 4 to 6 carbon atoms; R
2
is a bridging group between the two cyclopentadienyl rings and is selected from the group consisting of CR
3
2
, C
2
R
3
4
, SiR
3
2
, Si
2
R
3
4
, GeR
3
2
, Ge
2
R
3
4
, R
3
2
SiCR
3
2
, NR
1
and PR
1
, wherein the substituents R
3
, the same or different from each other, are hydrogen or have the same meaning of R
1
, or two or four substituents R
3
form one or two rings, having 3 to 6 carbon atoms, the substituents Q, the same or different from each other, are selected from the group consisting of hydrogen, halogen, OH, SH, R
1
, OR
1
, SR
1
, NR
1
2
and PR
1
2
; m is 0 or 1; n is 0 or 1, being 1 when m=1; x ranges from (m+1) to 5, and preferably between (m+2) and 5; and y ranges from m to 5;
(B) one or more organometallic aluminium compounds of formula (II):
AlR
4
3−z
H
z
  (II)
wherein the substituent

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