Catalysts and processes for the polymerization of olefins

Details Catalysts and processes for the polymerization of olefins Catalysts and processes for the polymerization of olefins

1999-06-29

2003-05-06

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, C502S111000, C502S117000, C502S132000

Reexamination Certificate

active

06559252

ABSTRACT:

The present invention relates to catalysts for the polymerization of olefins. In particular, it relates to high activity catalysts for the polymerization of olefins obtained from cyclopentadienyl compounds of a transition metal, organometallic aluminium compounds and water.
The invention also relates to processes for the polymerization 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 polymerization of olefins.
In European Patent Application EP 384,171, catalysts for the polymerization 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; when m=O, 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 embodiment examples, alumoxanes are used in which the R substituents are ethyl, isobutyl or 2-methylpentyl groups.
European Patent Application EP 575,875 describes homogeneous catalytic systems for the polymerization of olefins comprising:
(A) a cyclopentadienyl compound of the 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
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−
H
z
wherein the substituents R
4
are alkyl, alkenyl or alkylaryl radicals containing from 1 to 10 carbon atoms, optionally containing 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 (B) and water (C) 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 WO96/02580 describes improved catalytic systems comprising:
(A) a cyclopentadienyl compound of formula:
(C
5
R
1
x−m
H
5−x
)R
3
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 cyclopentadienyl rings substituted in the same way or different ways; 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 and optionally contain Si or Ge atoms or Si(CH
3
)
3
groups, 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=l; x is an integer ranging from (m+1) to 5; and y is an integer of ranging from m to 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 alkylaryl 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 (B) and water (C) 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.
However, the catalysts described in the above-cited patent applications exert activities in the polymerization of olefins which are not completely satisfactory. Therefore, the problem addressed by the present invention is to improve the activities of the above-discussed known catalysts.
To solve this problem, novel catalysts have unexpectedly been found which are suitable for the polymerization of olefins and possess a considerably improved activity compared with the known catalysts.
Thus, according to a first object, the present invention provides a catalyst for the polymerization of olefins comprising the product obtained 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 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 selected from the group consisting of a linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl or C
7
-C
20
arylalkyl groups radicals, optionally containing Si or Ge atoms or Si(CH
3
)
3
groups, 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 halogen, hydrogen, 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 y ranges from m to 5;
(B) an organometallic aluminium compound of formula (II):
Al(CH
2
—CR
4
R
5
—CR
6
R
7
R
8
)
w
R
9
q
H
z
  (II)
wherein R
4
is a linear or branched, saturated or unsaturated C
1
-C
10
alkyl or C
7
-C
20
arylalkyl group; R
5
is hydrogen or a linear or branched, saturated or unsaturated C
1
-C
10
a

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