U.S. patent application number 08/961956 was filed with the patent office on 2003-10-16 for catalytic systems for the polimerisation and copolimerisation of alpha-olefins.
Invention is credited to CANAS, PILAR LAFUENTE, GARCIA, BEGONA PENA, LAFUENTE, ANTONIO MUNOZ-ESCALONA, LLINAS, GERARDO HIDALGO, MARCOS, CARLOS MARTIN, NUNEZ, M. FRANCISCA MARTINEZ, ROYO, JOSE SANCHO.
Application Number | 20030195109 08/961956 |
Document ID | / |
Family ID | 8296555 |
Filed Date | 2003-10-16 |
United States Patent
Application |
20030195109 |
Kind Code |
A1 |
ROYO, JOSE SANCHO ; et
al. |
October 16, 2003 |
CATALYTIC SYSTEMS FOR THE POLIMERISATION AND COPOLIMERISATION OF
ALPHA-OLEFINS
Abstract
Catalyst component for the polymerization of alpha-olefins in
solution, in suspension, in gas phase at low and high pressure and
temperature or in mass at high pressures and high or low
temperatures, characterised in that is defined by general formulas
I or II 1 wherein: R, equal to or different from each other, is
hydrogen or a radical which contains from 1 to 20 carbon atoms;
this group optionally contains heteroatoms of groups 14 to 16 of
the periodic table of the elements and boron; at least one group R
contains a group OSiR".sub.3, Q is selected from a group
comprising: boron or an element from groups 14 to 16 of the
periodic table,; m value can change from 1 to 4 and it preferably
is 1 or 2; L, equal to or different from each other, is a cyclic
organic group united to M through a .pi. bond, or it is an atom
from groups 15 or 16 of the periodic table; L.sub.1 and L.sub.2,
equal to or different from each other, have the same meaning of L;
M is a metal from groups 3, 4, 10 of the periodic table, lanthanide
or actinide. X, equal to or different from each other, is selected
from a group comprising: halogen, hydrogen, OR'.vertline.,
N(R'").sub.2, C.sub.1-C.sub.30 alkyl or C.sub.6-C.sub.20 aryl;
wherein R'" is selected from the group comprising: C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 arylalkyl, C.sub.7-C.sub.30 arylalkenyl or
alkylaryl, linear or branched; x is 1 or 2, y is 2 or 3 in such a
way that x+y=4 d ranges from 0 to 7; a, b and c are integers from 0
to 10, in such a way that a+b+c>1
Inventors: |
ROYO, JOSE SANCHO; (MADRID,
ES) ; LLINAS, GERARDO HIDALGO; (MADRID, ES) ;
LAFUENTE, ANTONIO MUNOZ-ESCALONA; (MADRID, ES) ;
NUNEZ, M. FRANCISCA MARTINEZ; (MADRID, ES) ; MARCOS,
CARLOS MARTIN; (TORREJON DE ARDOZ, ES) ; CANAS, PILAR
LAFUENTE; (MADRID, ES) ; GARCIA, BEGONA PENA;
(MADRID, ES) |
Correspondence
Address: |
LADAS & PARRY
5670 WILSHIRE BOULEVARD
SUITE 2100
LOS ANGELES
CA
90036
|
Family ID: |
8296555 |
Appl. No.: |
08/961956 |
Filed: |
October 31, 1997 |
Current U.S.
Class: |
502/117 ;
502/102; 502/103 |
Current CPC
Class: |
C08F 4/61916 20130101;
C08F 110/02 20130101; C08F 4/61922 20130101; C08F 210/16 20130101;
C07F 17/00 20130101; C08F 10/00 20130101; C08F 10/00 20130101; C08F
210/14 20130101; C08F 4/6192 20130101; C08F 210/16 20130101; C08F
4/61912 20130101 |
Class at
Publication: |
502/117 ;
502/102; 502/103 |
International
Class: |
B01J 031/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 31, 1996 |
ES |
P9602310 |
Claims
1. Catalyst component for the polymerization of alpha-olefins in
solution, in suspension, in gas phase at low and high pressure and
temperature or in mass at high pressures and high or low
temperatures, characterised in that is defined by general formulas
I or II 3wherein: R, equal to or different from each other, is
hydrogen or a radical which contains from 1 to 20 carbon atoms;
this group optionally contains heteroatoms of groups 14 to 16 of
the periodic table of the elements and boron; at least one group R
contains a group OSiR".sub.3, wherein R" is selected from the group
comprising: C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl,
C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20
arylalkyl, C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or
branched, Q is selected from a group comprising: boron or an
element from groups 14 or 16 of the periodic table, when m>1,
groups Q are equal to or different from each other; the free
valences of every Q are filled with groups R according to the value
of c index; two groups R optionally are united to form a ring from
5 to 8 atoms; in value range from 1 to 4; L, equal to or different
from each other, is a cyclic or game group united to M through a
.pi. bond, it contains a cyclopentadienyl ring, that optionally is
fused with one or more other rings, or it is an atom from groups 15
or 16 of the periodic table; L.sub.1 and L.sub.2, equal to or
different from each other, have the same meaning of L; M is a metal
from groups 3, 4, 10 of the periodic table, lauthanide or actinide.
X, equal to or different from each other, is selected from a group
comprising: halogen, hydrogen, OR'", N(R'").sub.2, C.sub.1-C.sub.20
alkyl or C.sub.6-C.sub.20 aryl; wherein R'" is selected from the
group comprising: C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20
cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkenyl,
C.sub.7-C.sub.20 arylalkyl, C.sub.7-C.sub.20 arylalkenyl or
alkylaryl, linear or branched; x is 1 or 2, y is 2 or 3 in such a
way that x 1 y 4 d ranges from 0 to 2; a, b and c are integers from
0 to 10, in such a way that a+b+c>1.
2. Catalyst component according to claim 1 characterized in that R
is selected from the group comprising: hydrogen, C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or branched or a
group Sir'.sub.3 wherein R' is C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or branched or
OSiR".sub.3; at least one group R contains a group OSiR".sub.3,
wherein R" is selected from the group comprising: C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or branched;
optionally all these groups contain heteroatoms of groups 14 to 16
of the periodic table of the elements and boron.
3. Catalyst component according to claims 1-2 characterized in that
M is selected from the group comprising: Ti, Zr or .
4. Catalyst component according to claims 1-3 characterized in that
the group R containing the group OSiR" is selected from the group
comprising: --CH.sub.2--CH.sub.2--OSiMe.sub.3,
--CH.sub.2--CH.sub.2--CH.sub.2--OSiMe.- sub.3,
--CH.sub.2--O--CH.sub.2--OSiMe.sub.3,
--O--CH.sub.2--CH.sub.2--OSiM- e.sub.3,
--SiMe.sub.2--CH.sub.2--CH.sub.2--OSiMe.sub.3.
5. Catalyst component according to claims 1-4 characterized in that
in the general formula I, L is cyclopentadienyl or indenyl, M is
zirconium; x is 2; y is 2; R is C.sub.1-C.sub.4 alkyl, wherein at
least one hydrogen of one R is substituted with OSiR".sub.3 wherein
R" is selected from the group conprising: Me, Et, Pr.
6. Catalyst component according to claims 1-4 characterized in that
in the general formula II, M is zirconium; L.sub.1 and L.sub.2 are
cyclopentadienyl or indenyl group; R is hydrogen, a C.sub.1-C.sub.4
alkyl wherein at least one hydrogen of one R is substituted with
OSiR".sub.3 or a Sir'--OSiR".sub.3 group, wherein R" is selected
from the group comprising: methyl, ethyl, propyl;
[(R).sub.cQ].sub.m is H.sub.2C--CH.sub.2, CRH--CH.sub.2,
RHC--SiR'.sub.3, R.sub.2C--SiR'.sub.2 or SiRR'.
7. Catalyst component according to claims 1-4 characterized in that
in the general formula II, M is titanium; L.sub.2 is an oxygen or a
nitrogen atom; L.sub.2 is a cyclopentadienyl, indenyl or fluorenyl
ring; [(R).sub.cQ].sub.m is H.sub.2C--CH.sub.2, CRH--CH.sub.2,
RHC--SiR'.sub.2, R.sub.2C--SiR'.sub.2 or SiRR'.
8. Solid catalyst component according to claims 1-7, characterized
in that catalyst component of formula I or II is supported on a
porous inorganic solid.
9. Solid catalyst component according to claim 8 characterized in
that the porous inorganic solid is selected from the group
comprising: silica, alumina, silica alumina, aluminium phosphates
and mixtures thereof.
10. Process for the preparation of a solid catalyst component
comprising: the following steps: impregnation, under anhydrous
conditions and inert atmosphere, of a solution of at least one
catalyst component according to claims 1-7, on the supporting
material at a temperature between -20.degree. C. and 90.degree. C.,
firation and washing with a solvent, selected from aliphatic or
aromatic hydrocarbon.
11. Process for the preparation of a solid catalyst component
comprising the following steps: depositing the catalyst component
according to claims 1-7 on the support, by using a solution of the
compound to heterogenize; eliminating the solvent through
evaporation; warming the solid residue up to temperature between 25
and 150.degree. C.
12. Process for the preparation of a solid catalyst component
according to claims 10-11 characterized in that before step a) the
catalyst component is mixed with a cocatalyst.
13. Polymerization catalyst comprising the catalyst component
according to claims 1-9 and a cocatalyst.
14. Polymerization catalyst according to claims 13, characterized
in t hat the cocatalyst is selected from a group comprising:
alkylaluminoxane, boron compound, or mixture thereof.
15. Process for the polymerization of alpha-olefins in solution, in
suspension, in gas phase at low and high pressure and temperature
or in mass at high pressures and high or low temperatures
characterized by the use of a polymerization catalyst according to
claims 13-14.
16. Process for the polymerization of alpha-olefins in solution, in
suspension, in gas phase at low and high pressure and temperature
or in mass at high pressures and high or low temperatures according
to claim 15 characterized in that the monomer is ethylene
17. Process for the polymerization of alpha-olefins in solution, in
suspension, in gas phase at low and high pressure and temperature
or in mass at high pressures and high or low temperatures according
to claim 15 characterized in that the monomer is ethylene and the
comonomer is selected from the group comprising: propylene, butene,
hexene, octene and 4-methyl-1-pentene.
18. Process for the polymerization of alpha-olefins in solution, in
suspension, in gas phase at low and high pressure and temperature
or in mass at high pressures and high or low temperatures according
to claim 17 characterized in that the comonomer is used in
proportions from 0,1 to 70% by weight of the total of the monomers.
Description
[0001] The present invention relates to new metallocene catalysts
which can be easily heterogenized on an inorganic support.
STATE OF THE ART
[0002] Organocomplexes of elements belonging to group IV, in
combination with alkyaluminoxanes and/or boron compounds, lead to
the formation of polymerization catalysts, whose activities are
sometimes better than those obtained with the typical Ziegler-Natta
catalysts (Markrom. Chem. 179, 2553 (1978) and 169, 163 (1973), DE
1022382, U.S. Pat. No. 3,184,416, U.S. Pat. No. 3,440,237, EP
277004 and EP 426637).
[0003] It is very well known that hemogeneous catalytic systems
present a disadvantage: when they are used in suspension
polymerization processes, a part of the produced polymer adheres to
the reactor walls; this effect is technically called "reactor
fouling". Besides, in most cases, the particle size of the obtained
polymer is very small and the apparent density is low, thus the
industrial production is reduced. In order to prevent the reactor
from fouling and to control the size and the morphology of the
polymer particles which are formed, the homogeneous system can be
supported on an inorganic oxide.
[0004] In the last years three different preparatory strategies
have been used in order to reach this aim: cocatalyst
heterogenization, metallocene heterogenization or heterogenization
of both components on a fit support.
[0005] Several patents describe heterogeneous catalyst synthesis
through processes initially based on the cocatalysts fixation onto
the support.
[0006] U.S. Pat. No. 4,939,217 and U.S. Pat. No. 5,064,797 patents
describe a heterogenization process based on the preparation "in
situ" of aluminoxane on the support. The method consists in
bubbling, an inert humidified gas directly inside a solution of an
aluminium alkyl in the presence of the support. When an
organocomplex solution is added to this heterogenized cocatalyst,
the catalyst is heterogenized.
[0007] Patents EP 323716, EP 361866, EP 336593, EP 367503, EP
368644 and U.S. Pat. No. 5,057,475 describe a different process
from the previous one. In this case the cocatalyst is heterogenized
through direct reaction of the aluminium alkyl with the superficial
hydration water molecules of the support. In a similar way to the
one described in the previous patents, the organocomplex fixation
is then obtained through close contact of an organocomplex solution
with a suspension of the modified support.
[0008] In both cases it may happen that part of the aluminum
cocatalyst is not homogeneously distributed on the support surface.
Besides, it is rather difficult that, going from one preparation to
another, you succeed in exactly reproducing the heterogenized
aluminoxane structure and molecular weight. Another serious
disadvantage is the migration of the active species into the
homogeneous phase during the polymerization reaction.
[0009] EP 293815 describes the metallocene fixation according to
the reactivity of the alcoxysilane functional group
(Me.sub.2(EtO)Si) with superficial hydroxy groups of the inorganic
oxide. The activity in polymerization is not very high, probably
because a high percentage of the organocomplex is deactivated. An
additional disadvantage are the low yields obtained in the
preparation of this type of functionalized organometallic
compounds.
[0010] The object of the present invention is to avoid these
disadvantages through a process for synthesizing supported
catalysts for (co)polymerization of ethylene and alpha-olefins with
3 or more carbon atoms, such as propene, 1-butene, 1-pentene,
1-hexene 4-methyl-1-pentene and 1-octene. Differently from other
more conventional methods, this heterogenization process is based
on the reactivity of OSiR".sub.3 functional groups of the
organo-complexes with the superficial reactive groups of the
catalytic support. Predictably, the fixation of this type of
metallocenes, functionalized with groups OSiR".sub.3, is due, as it
is described in FIG. IV, to the reaction between the groups
OSiR".sub.3 of the organometallic complexes and the reactive groups
of the support.
[0011] Another object of the present invention is the use of the
organometallic complexes of formula I and II and homogeneous
catalysts for olefins homopolymerization and copolymerization.
[0012] Thanks to the methods described in the present invention,
heterogeneous catalysts can be obtained; they allow to effectively
control the morphology and the distribution of particle sizes, with
a regular growth of the polymer around the catalyst particles.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention relates to homogeneous and
heterogeneous catalytic systems containing metallocene complexes of
transition metals with at least one group R-OSiR".sub.3 potentially
reactive to support.
[0014] According to the present invention the catalytic system at
least includes one metallocene complex of general formula I or II.
2
[0015] wherein:
[0016] R, equal to or different from each other, is hydrogen or a
radical which contains from 1 to 20 carbon atoms; this group
optionally contains heteroatoms of groups 14 to 16 of the periodic
table of the elements and boron; at least one group R contains a
group OSiR".sub.3; preferably it is: hydrogen, C.sub.1-C.sub.20
alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20
aryl,C.sub.7-C.sub.20 alkenyl, c.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or branched or a
group SiR'.sub.3 wherein R' is C.sub.1-C.sub.20 alkyl,
C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl,
C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or banched or
OSiR".sub.3, wherein R" is selected from the group comprising:
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl,
C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20
arylalkyl, C.sub.7-C.sub.20 arylalkenyl or alkylaryl, linear or
branched.
[0017] Non limitative examples of R containing the group
OSiR".sub.3 are:
[0018] --CH.sub.2--CH.sub.2--OSiMe.sub.3;
--CH.sub.2--CH.sub.2--CH.sub.2--- OSiMe.sub.3;
--CH.sub.2--O--CH.sub.2--OSiMe.sub.3; --O--CH.sub.2--CH.sub.2-
--OSiMe.sub.3; --SiMe.sub.2--CH.sub.2--CH.sub.2--OSiMe.sub.3,
--CH.sub.2--C.sub.3H.sub.OSi(C.sub.5H.sub.5),;
--C.sub.5H.sub.5.C.sub.5H.- sub.5
[0019] Preferably the group R that contains OSiR".sub.3 is selected
from the group comprising: --CH.sub.2--CH.sub.2--OSiMe.sub.3,
--CH.sub.2--CH.sub.2--CH.sub.2--OSiMe.sub.3,
--CH.sub.2--O--CH.sub.2--OSi- Me.sub.2,
--O--CH.sub.2--CH.sub.2--OSiMe.sub.3, --SiMe.sub.2--CH.sub.2--CH-
.sub.2--OSiMe.sub.3.
[0020] Q is selected from a group comprising: boron or an element
from groups 14 or 16 of the periodic table; when m>1, the groups
Q are qual to or different from each other; the free valences of
every Q are filled with groups R according to the value of c index;
two groups R are optionally united to form a ring from 5 to 8
atoms, m value can vary from 1 to 4 and it preferably is 1 or
2.
[0021] L, equal to or different from each other, is a cyclic
organic group united to M through a .pi. bond; it contains a
cyclopentadienyl ring, that optionally is fused with one or more
other rings to form for example: tetrahydroindenyl, indenyl,
fluorenyl or octahidrofluorenyl group; or it is an atom from groups
15 or 16 of the periodic table; when it is an atom from groups 15
or 16 of the periodic table (heteroatom), it preferably is an
oxygen or nitrogen atom, directly bonded to the metal.
[0022] L.sub.1 and L.sub.2, equal to or different from each other,
have the same meaning of L; M is a metal from groups 3, 4, 10 of
the periodic table, lanthamide or actinide; preferably it is Ti, Zr
or Hf;
[0023] X, equal to or different from each other, is selected from a
group comprising: halogen, hydrogen, OR'", N(R'"), C.sub.1-C.sub.20
alkyl or C-Caryl; wherein R'"is selected from the group comprising:
C-C.sub.20 alkyl, C-C.sub.20 cycloalkyl, C-C.sub.20 aryl,
C-C.sub.20 alkenyl, C-C.sub.20 arylalkyl, C.sub.7-C.sub.20
arylalkenyl or alkylaryl, linear or branched;
[0024] x is 1 or 2, y is 2 or 3 in such a way that x+y 4
[0025] d ranges from 0 to 2;
[0026] a, b and c are integers from 0 to 10, in such a way that
a+b+c>1, the maximum value for a and b depends on the available
positions in or ; for example, for the cyclopentadiene, in general
formula 1, 5 is the maximum value for a, on the contrary in nthe
general formula II, for cyclopentadiene, 4 is the maximum value for
a or b; for nitrogen in the general formula II, a or b is 1, for
oxygen it is 0; the value of c index depends on the gree valences
of group Q, for example, if Q is equal to a silicon atom or carbon
atom the value of c is 2; if Q is a boron atom the value of c is
1.
[0027] Examples of [R).sub.cQ].sub.m when m is equal to 1 and c is
equal to 2 are: R.sub.2Si, R.sub.2C.
[0028] Examples of [(R).sub.cQ].sub.m when m is equal to 2 and c is
equal to 2 are: R.sub.2Si--CR.sub.2, R.sub.2C--CR.sub.2,
R.sub.2Si--SiR.sub.2.
[0029] Examples of [(R).sub.cQ].sub.m when m is equal to 3 and c is
equal to 2 or 1 are: R.sub.2Si--O--SiR.sub.2,
R.sub.2Si--O--CR.sub.2, RB--O--BR.
[0030] The metallocene complexes belonging to the general formula
1, where x=2, and those belonging to formula II where d 2 can be
prepared through reaction of a metal compound of general formula
MX.sub.n(E).sub.q, wherein L is a linear or cyclic ether, q is a
number between 0 and 4 and n is 3 or 4 with another compound of
general formula [(L(R))]M' or [(R)L--((R).sub.cQ)(R)]M'.sub.2
wherein M' is an alkali metal, preferably Li, Na or K. The
preferred compound of the transition metal is tetrachloride and
sometimes, when the metal is titanium, it is trichloride or its
aduct with a cyclic ether such as tetrahydrofurane.
[0031] The reaction between the metal compound and the alkali metal
derivative is preferably carried out in a dry nitrogen atomosphere,
by using anhydrous solvents such as linear or cyclic ethers such as
dietylether, tetrahydrofurane or dioxane, or aromatic hydrocarbon
such as toluene.
[0032] The alkali metal compound of formula [(L(r).sub.a)]M' can be
prepared from the compound of formula L(R).sub.aH ghrough reaction
with a lithium alkyl, with a sodium or potassium hydride or
directly with the metal.
[0033] On its turn, the ligand L(r),H, when L is or contains a
cyclopentadienyl ring, can preferably be obtained from
cyclopenadiene or indene through reaction of its sodium salts in
the first case and potassium salt in the second case, with a
compound R--S, where R has previously been defined and S is a
proper leaving group such as halide or alkyl or aryl sulphonate.
The reaction will be repeated as many time as necessary, according
to the following scheme for a equal to 3
LM'+RS.fwdarw.LR+M'S
LRM'+RS.fwdarw.LR.sub.2+M'S
LR.sub.2M'+RS.fwdarw.LR+M'S
[0034] The alkali metal compound
[(R)--[(R).sub.cQ].sub.m--L(R).sub.b]M'.s- ub.2 can be obtained
through reaction of two equivalents of a metallizing agent such as
lithium alkyl, e.g. MeLi or BuLi, or alternatively sodium or
potassium hydride, with a compound of formula
((R).sub.aHL--[(R).sub.c- Q].sub.m--L.sub.2H(R).sub.b). When a
group L is an oxygen or nitrogen atom, the preferred metallizing
agent is lithium alkyl. The compound of formula
[(R).sub.aHL--((R).sub.cQ).sub.2(R)] cand be obtained through
reaction of the alkali metal compound [LH(R).sub.a]M' or
[LH(R).sub.a]M' or mixtures thereof with a compound of formula
S--[(R).sub.cQ].sub.m--S, where S is a proper leaving group, such
as halogen (Cl, Br, l), or aryl or alkyl sulphonate.
[0035] The preferred metallocene complexes of formula J correspond
to compounds wherein:
[0036] M is zirconium
[0037] R is C.sub.1-C.sub.4 alkyl, wherein at least one hydrogen of
one R is substituted with OSiR".sub.3, wherein R" is selected from
the group comprising: methyl, ethyl, propyl
[0038] L is a cyclopentadienyl or indenyl group
[0039] x
[0040] The preferred complexes of general formula II, wherein
L.sub.1 and L.sub.2 are cyclic organic compounds, correspond to
compounds wherein:
[0041] M is zirconium
[0042] L.sub.1 and L.sub.2 are cyclopentadienyl or indenyl
groups
[0043] R is hydrogen, a C.sub.1-C.sub.4 alkyl wherein at least one
hydrogen of one R is substituted with group OSiR".sub.3 or a group
SiR'.sub.2--OSiR".sub.3, wherein R" is selected from the group
comprising: methyl, ethyl, propyl
[0044] [(R).sub.cQ].sub.m is selected from the group comprising:
H.sub.2C--CH.sub.2, CRH--CH.sub.2, RHC--SiR'.sub.2,
R.sub.2C--SiR'.sub.2 or SiRR'.
[0045] The preferred complexes of general formula II wherein one of
L.sub.1 and L.sub.2 is an oxygen or nitrogen atom correspond to
compounds wherein:
[0046] The other group L.sub.1 or L.sub.2 is a cyclopentadienyl,
indenyl or fluorenyl ring
[0047] M is titanium
[0048] --[(R).sub.rQ].sub.m is H.sub.2C--CH.sub.2,
CRH--CH.sub.2,RC--SiR'R- C--SiR' or SiRR'.
[0049] The compounds of formula I or II can be supported on a
proper inorganic support. As supports, any type of inorganic oxides
can be used, for example inorganic oxides, such as: silica,
alumina, silica alumina, aluminium phosphates and mixtures thereof,
obtaining supported catalysts with contents in transition metals
between 0.01 and 10% by weight, preferably between 1 and 4%.
[0050] A method that can be fit for preparing supported catalysts
according to this invention consists in the impregnation, under
anhydrons conditions and inert atmosphere, of the solution of any
metallocene of formula I or II, or a mixture thereof, on the
supporting material at a proper temperature, preferably between
-20.degree. C. and 90.degree. C. The supported catalyst that
contains the metallocene can be obtained through filtration and
washing with a proper solvent, preferably an aliphatic or aromatic
hydrocarbon without polar groups.
[0051] Another method that can properly be used consists in
depositing the metallocene on the support by using a solution of
the compound that has to be heterogenized, eliminating the solvent
through evaporation and then warming the solid residue at a
temperature between 25 and 150.degree. C. Besides, the resulting
residue, obtained by this process, can be subjected to washing and
subsequent filtration.
[0052] The process can also be carried out in the presence of a
cocatalyst that for example can be mixed with a metallocene in a
proper solvent and then the resulting solution can be put in
contact with the support.
[0053] The amount of the organometallic complex which can be
anchored in these conditions directly depends on the concentration
of the reactive groups present in the support. For this reason
silica, for example, should preferably have been calcinated at a
temperature between 600.degree. C. and 800.degree. C.
[0054] An advantageous aspect of this invention is that the
fixation method, as a consequence of the reaction of groups R,
which contain the --OSiR".sub.3 entity with reactive groups of the
support surface, prevents the desorption of the
supportedmetallocene complexes. This type of interaction represents
the main difference between the organocomplexes heterogenization
mechanism and other conventional methods, where the metallocene
complex generally remains physisorbed on the support surface. The
organocomplex fixation to the inorganic support is based on the
reaction of the reactive groups of the support with the group
--OSiR".sub.3 or groups of the metallocene, as it is described in
FIG. IV.
[0055] Metallocene complexes of formula I or II, individually or
supported, can be used in the presence of a cocatlyst for olefins
polymerization or copolymerization, either in solution or
suspension process.
[0056] When X is a halogen, OR'" or N(R'") the preferred
cocatalysts are alkylaluminoxane, especially methylaluminoxane
compounds, when X is hydrogen or alkyl the preferred cocatalysts is
a Lewis acid such as B(CF).sub.3. In addition mixtures of both
aluminoxane and boron derivatives can be used as cocatalysts.
[0057] The most proper polymerization procedure can change
according to the chosen type of polymerization process (solution,
suspension or gas phase).
[0058] For the polymerization in solution, the cocatalyst can
bemixed with a solution of a metallocene of formula I or II and a
supplementary quantity of it can be added to the solution; or the
catalyst can directly be added to the polymerization medium, which
contains the cocatalyst.
[0059] For the polymerization in suspension, the cocatalyst can
previously be mixed with the supported solid catalyst, can be added
to the polymerization medium before the supported catalyst, or both
operations can be sequentially carried out.
[0060] The process consists in putting in contact the monomer, or,
in certain cases, the monomer and the comonomer, with a catalytic
composition according to the present invention, that includes at
least one metallocene complex of formula I or II, at a proper
temperature and pressure.
[0061] The alpha-olefins that can be used as comonomers to obtain
ethylene copolymers can be propylene, butene, hexene, octene or
branched ones such as the 4-methyl-1-pentene and can be used in
proportions from 0,1 to 70% by weight of the total of the monomers.
In the case of homopolymerization of ethylene the density of
polymers range between 0,950 and 0,9565 g/cm.sup.3 in the case of
copolymerization of ethylene the density is as low as 0,900
g/cm.
[0062] To control the molecular weight of the obtained polymers,
hydrogen can optionally be used as chain transfer agent in such
proportions that the hydrogen partial pressure, with respect to the
olefin one, is from 0.01 to 50%.
[0063] In the particular case of the polymerization technique known
as suspension process or controlled particle morphology process,
the used temperature will be between 30.degree. and 100.degree. C.,
the same which is typically used in gas phase, while for the
solution process the usual temperature will be between 120.degree.
and 250.degree. C.
[0064] The used pressure changes according to the polymerization
technique; it ranges from atmospheric pressure to 350 MPa.
[0065] FIG. I shows examples of compounds according to formula I;
FIG. II shows examples of compounds according to formula II,
wherein both L.sub.1 and L.sub.2 contain a cyclopentadienyl
derivative. In FIG. III there are examples of compounds according
to formula II, wherein as group L is an oxygen or nitrogen atom and
the other group contains a cyclopentadienyl derivative. FIG. IV
shows the reaction between the siloxane groups of the supports and
the groups --OSiR".sub.3 of the organo-metallic complexes.
[0066] The following examples are described in order to better
understand the invention. The materials, the chemical compunds and
the conditions used in these examples are illustrative and do not
limit the scope of the invention.
EXAMPLE 1
[0067] a) Preparation of (dimethyl)
(trimethylsiloxy)-silyl-cyclopentadien- e
[0068] To a solution of 20.9 g (187 mmol) of sodium
trimethylsilanolate in tetrahydrofurane, 30.3 g (191 mmol) of
chlorocyclopentadienyl-dimethyl-si- lane in tetrahydrofurane is
added at room temperature and a pink suspension immediately is
formed. It is left reacting 12 hours. Then, it is neutralised with
an ammonium chloride aqueous solution, the organic phase is
extracted, dried with ahydrous magnesium sykogate abd tge sikvebt
us ekunubated ybder vacyynl abd irabge iuk us recivered. This oil
is distilled and the desired product is obtained as a pale yellow
oil. (T.sub.b: 60.degree. C.; 0.014 bar (10 mmHg)). (31.6 g, 149
mmol. Yield: 80%). .sup.1H-NMR (CDCl.sub.3): 6.65 (m, 2H), 6.54
(m,2H), 3.52 (s,1H), 0.60 (s,9H), -0.2 (s,6H).
[0069] b) Preparation of potassium
(dimethyl)-(trimethylsiloxy)-silyl-cycl- opentadienide
[0070] To a suspension of 0.6 g (15 mmol) of potassium hydride in
tetrahydrofurane, a solution of 3.1 g of
(dimethyl)-(trimethylsiloxy)-sil- yl-cyclopentadiene is added at
-78.degree. C. and a strong H.sub.2 evolution is observed. It is
maintained under stirring until room temperature is achieved. It is
left reacting for about 1 hour until all the potassium hydride is
reacted. The tetrahydrofurane solution is concentrated under vacuum
and a clear yellow solid is obtained. (3.45 g, 13.8 mmol. Yield:
92%).
[0071] c) Preparation of cyclopentadienyl
[((dimethyltrinnethylsiloxy)-sil- yl)-cyclopentadienyl] sirconium
dichloride
[0072] To 5.2 g (14 mmol) of an adduct of cyclopentadienyl
zirconium trichloride with dimethoxyethane in toluene, a suspension
of 3.45 g (13.8 mmol) of potassium
dimethyltrimethylsiloxy-silyl-cyclopentadienide in toluene is added
at -78.degree. C. The suspension is maintained under stirring for
24 hours; after settling, a yellow solution is filtered. The yellow
solution is concentrated up to 20 ml; then, some hexane is added
and a crystalline white solid precipitates. (3.1 g, 7.1 mmol.
Yield: 51%). .sup.1H-NMR (C.sub.6D.sub.6): 6.45 (t,2H), 6.03
(s,5H), 5.95 (t,2H), 0.39 (s,6H), 0.09 (s,9H). .sup.13C-NMR
(C.sub.6D.sub.6): 125.4, 123.6, 117.3, 115.9, 2.0. Mass spectrum.
M.sup.+-15: m/e 422.9 (32%).
EXAMPLE 2
[0073] a) Preparation of bis[((dimethyltrimethylsiloxy)-sily)
cyclopentadienyl]zirconium dichloride
[0074] To 0.93 g (4 mmol) of zirconium tetrachloride a suspension
of 2.02 g (8 mmol) of potassium
dimethyltrimethylsiloxy-silyl-cyclopentadienide in hexane is added
at -78.degree. C. The formation of a yellow suspension is observed.
It is left under stirring for 12 hours. Then the solution is
filtered and concentrated and a yellowish crystalline solid is
obtained. (0.75 g, 1.3 mmol. Yield: 32%). .sup.1H-NMR
(C.sub.6D.sub.6): 6.58 (t,2H), 6.13 (t,2H), 0.45 (s,611), 0.14
(s,911). .sup.--C-NMR (C.sub.6D.sub.6): 126.2, 124.1, 116.5, 2.13,
2.06. Mass spectrum. M.sup.+-15: m/e 569 (15%)
EXAMPLE 3
[0075] a) Preparation of 2-bromo-1-trimethylsiloxyethane
[0076] To 125 g (888 mmol) of 2-bromo-ethanol, 95 ml (1450 mmol) of
hexamethyldisilazane are slowly added at 0.degree. C. Ammonia
evolution is immediately observed. The reaction is maintained under
stirring for 12 hours and a colourless oil is obtained. (168.8 g
856 mmol. Yield:965) .sup.1H-NMR (CDCl.sub.3): 3.66 (t,2H), 3.40
(t,2H), 0.14 (s,9H).
[0077] b) Preparation of
(2-trimethylsiloxy-ethyl)-cyclopentadiene
[0078] 15 ml of a 2.3 M sodium cyclopentadienide solution in
tetrahydrofurane (346 mmol) is slowly added to a solution of 68.2 g
(346 mmol) 2-trimethylsiloxy-1-bromo-ethane in tetrahydrofurane.
The immediate formation of a pinkish solid is observed. The
reaction is maintained under stirring for 12 hours. Then, an
ammonium chloride aqueous solution is added. The organic phase is
extracted, dried with magnesium sulphate and the volatile part is
distilled under vacuum, obtaining an orange oil. This oil is
distilled in order to obtain a colourless oil. (T.sub.b:
63-65.degree. C., 0.02 bar (15 mmHg.)). (40.3 g, 221 mmol.
Yield:64%). .sup.1H-NMR (CDCl.sub.3): 6.50-6.00 (m,3H), 3.75
(m,2H), 2.95 (m,2H), 2.65 (m,2H), 0.15 (s,9H).
[0079] Preparation of lithium
(2-trimethylsiloxy-ethyl)-cyclopen(adienide
[0080] To 7.33 g of (2-trimethylsiloxy-ethyl)-cyclopentadiene in
ether, 16 ml of a 2.5 M butyllithium solution in hexane (40 mmol)
is added. The addition is realised at -78.degree. C. The immediate
formation of a white solid and butane evolution are observed. It is
maintained reacting for 3 hours. Then it is dried; the resulting
solid washed with hexane, leaving a powdery white solid. (6.19 g,
33 mmol, Yield: 82%).
[0081] d) Preparation of
bis[(2-trimethylsiloxy-ethyl)-cyclopentadienyl]zi- rconium
dichloride
[0082] To 1.37 g (5.9 mmol) of zirconium tetrachloride, a
suspension of 2.2 g (11.7 mmol) of lithium
(2-trimethylsiloxy-ethyl)-cyclopentadienyhid- e is added at
-78.degree. C. An orange suspension is immediately formed. The
reaction is maintained under stirring for 12 hours. Finally, the
solution is filtered, concentrated to dryness, and a yellow only
solid is recovered, which is mixed with hexane and a yellow solid
is obtained. (1.05 g, 2 mmol. Yield: 34%). .sup.1H-NMR
(C.sub.6D.sub.6): 6.02 (t,2H), 5.72 (t,2H), 3.62 (t,2H), 2.89
(t,2H), 0.05 (s,9H). .sup.13C-NMR (C.sub.6D.sub.6): 117.7, 112.0,
111.2, 62.6, 34.0, -0.45. Mass spectrum. M.sup.+-15: (509).
1.24%.
EXAMPLE 4
[0083] a) Preparation of potassium
(2-trimethylsiloxy-ethyl)-cyclopentadie- nide
[0084] To a suspension of 0.5 g (12.4 mmol) of potassium hydride in
tetrahydrofurane, 2.25 g (12.4 mmol) of
(2-trimethylsiloxy-ethyl)-cyclope- ntadiene in tetrahydrofurane is
added. The reaction is maintained under stirring for 2 hours and
then the volatile compounds are eliminated, leaving an oily solid
which is washed with hexane in order to obtain a brown solid. (2.2
g Yield: 815)
[0085] b) Preparation of cyclopendadienyl
((2-trimethylsiloxy-ethyl)-cyclo- pentadienyl) zirconium
dichloride
[0086] To a suspension of 3.52 g (10 mmol) of an adduct of
cyclopentadienyl zirconium trichloride with dimethoxyethane in
toluene, a suspension of 2.2 g (10 mmol) of potassium
(2-trimethylsiloxy-ethyl)-cycl- opentadienide in toluene is added.
The addition is carried out at -78.degree. C. An orange-brown
suspension is immediately formed, it is maintained under stirring
for 12 hours; then it is left settling and it is filtered. The
obtained orange solution is concentrated up to 5 ml and hexane is
added, so that a brown solid is obtained. (1.1 g, 2.7 mmol. Yield:
27%). .sup.1H-NMR: 6.00 (t,2H), 5.87 (s,5H), 5.67 (t,2H), 3.66
(t,2H), 2.92 (t,2H), 0.11 (s,9H). Mass spectrum. M.sup.+-65: (343):
33%.
EXAMPLE 5
[0087] Preparation of 3-bromo-1-trimethylsiloxypropane
[0088] To 12.2 g (76 mmol) of hexanethyldisilazane, 21 g (151 mmol)
of 3-bromo-1-propanol is added. Ammonia evolution is immediately
observed. The reaction is maintained under stirring for 2 hours and
24.5 g (148 mmol) of the desired compound is finally obtained.
Yield: 98%. .sup.1H-NMR (CDCl.sub.3): 3.74 (t,2H), 3.55 (t,2H),
2.09 (m,2H), 0.14 (s,9H).
[0089] b) Preparation of
(3-trimethylsiloxypropyl)-cyclopentadiene
[0090] To 50 ml of a 2.3 M solution of sodium cyclopentadienylide
(115 mmol), a solution of 24.3 g (115 mmol) of
3-bromo-1-trimethylsiloxypropan- e in tetrahydrofurane is added.
The quick formation of a pinkish solid is observed. The reaction is
maintained under stirring for 12 hours and then it is neutralised
with an ammonium chloride solution; the organic phase is extracted
and concentrated to dryness in order to give an orange oil. (9.8 g.
50 mmol. Yield: 43%). .sup.1H-NMR (CDCl.sub.3): 6.47-6.00 (m,3H),
3.62 (m,2H), 2.95 (m,1H), 2.87 (m,1H), 2.43 (m,2H), 1.80 (m,2H),
0.17 (s,9H).
[0091] c) Preparation of lithium
(3-trimethylsiloxy-propyl)-cyclopentadien- ide
[0092] To a solution of 2.62 g (13.4 mmol) of
(3-trimethylsiloxypropyl)-cy- clopentadiene in ether, 5.36 ml of a
2.5 M (13.4 mmol) butyl lithium solution in hexane is added at
-78.degree. C. The immediate formation of a white solid is
observed. The reaction is maintained under stirring for 2 hours;
then, the white suspension is brought to dryness, the resulting
solid is washed twice with hexane and a powdery white solid is
obtained (2.3 g, 11.4 mmol. Yield: 85%).
[0093] d) Preparation of
bis[(3-trimethylsiloxypropyl)-cyclopentadienyl] zirconium
dichloride
[0094] To a suspension of 1.33 g (5.7 mmol) of zirconium
tetrachloride, a suspension of 2.3 g (11.4 mmol) of lithium
(3-trimethylsiloxypropyl)-cycl- opentadienylide is added at
-78.degree. C. An orange suspension is immediately formed and the
reaction is maintained under stirring for 12 hours. It is
subsequently filtered and the resulting solution is concentrated up
to 5 ml, hexane is added and a microcrystalline white solid is
formed. (1.27 g. 2.3 mmol Yield: 40%). .sup.1H-NMR
(C.sub.6D.sub.6): 5.95(t,2H), 5.77 (t,2H), 3.52 (m,2H), 2.81
(m,2H), 1.80 (m,2H), 0.15 (s,9H). Mass spectrum: M.sup.+-15: (357):
59%.
EXAMPLE 6
[0095] a) Preparation of potassium
(3-trimethylsiloxypropyl)-cyclopentadie- nide
[0096] To a suspension of 0.4 g (10 mmol) of potassium hydride in
tetrahydrofurane, 1.96 g (10 mmol) of a
(3-trimethylsiloxy-propyl)-cyclop- entadiene in tetrahydrofurane is
added. The reaction is maintained under stirring for 2 hours.
Subsequently, the resulting suspension is concentrated to dryness,
leaving an oily solid that, when it is washed with hexane, gives a
cream-coloured solid. (1.6 g, 7 mmol. Yield: 70%).
[0097] b) Preparation of [cyclopentadienyl
(3-trimethylsiloxypropyl)-cyclo- pentadienyl] zirconium
dichloride
[0098] To a suspension of 2.46 g (7 mmol) of cyclopentadienyl
zirconium trichloride in toluene, a suspension of 1.6 g (7 mmol) of
potassium (3-trimethylsiloxypropyl)-cyclopentadienide in toluene is
added. A yellow-brown-coloured suspension immediately precipitates.
The reaction is maintained for 12 hours. Subsequently, the solution
is filtered and concentrated and a crystalline white solid is
formed (0.8 g, 2 mmol, 28%). .sup.1H-NMR (C.sub.6D.sub.6): 5.87
(t,2H), 5.65 (t,2H), 3.46 (m,2H), 2.74 (m,2H), 1.73 (m,2H), 0.14
(s,9H). .sup.13C-NMR (C.sub.6D.sub.6): 116.9, 115.0, 114.7, 112.2,
61.8, 33.6, 26.8, -0.393. Mass spectrum: M.sup.+-65(3.56): 30%.
EXAMPLE 7
Heterogenization of bis[(3-trimethylsiloxypropyl)-cyclopentadienyl]
zirconium dichloride on silica
[0099] To a suspension of 12 g of silica (Graco XPO-2407, calcined
at 800.degree. C.) in 70 ml of toluene, a solution of 4.1 g of the
compound prepared according to the description in example 5d in 20
ml of toluene is added. The reaction mixture is maintained under
stirring at 25.degree. C. for 18 hours. The solution is separated
from the solid through filtration.
[0100] Then, the solid is washed with various fractions of toluene,
up to a total volume of 500 ml and dried under vacuum for 18 hours.
the Zr content in the sample was determined through ICP and
resulted to be 1.7%.
[0101] When the same sample was washed with 50 ml (in t hree
fractions) of a MAO 1,5 M solution in toluene, the Zr percentage
which was left in the sample lowered to 1.1%.
EXAMPLE 8
Heterogenization of [cyclopentadienyl
(3-trimethylsiloxypropyl)-cyclopenta- dienyl] zirconium dichloride
on silica
[0102] To a suspension of 3 g of silica, in about 70 ml of dry
toluene, 0.5 g (1.32 mmol) of a compound prepared according to
example 6b is added.
[0103] The reaction mixture was maintained under stirring at
25.degree. C. for about 18 hours. The solid was separated from the
solution through filtration. Then, the resulting solid was washed
with a total volume of 500 ml of toluene and dried under vacuum for
12 hours. The zirconium analysis through ICP gave 1.7% in the
sample.
EXAMPLE 9
Heterogenization of bis[(2-trimethylsiloxyethyl)-cyclopentadienyl]
zirconium dichloride
[0104] To a suspension of 3 g of silica (Graco XPO-2407 calcinated
at 800.degree. C.) in 70 ml of toluene, a solution of 0.5 g of the
compound described in example 3d in 20 ml of toluene is added. The
reaction mixture was maintained at 40.degree. C. for 18 hours under
stirring. The solution was separated from the solid through
filtration. The solid resulting from the reaction was analysed
through ICP, which showed that the zirconium percentage in the
sample was 2.75%.
[0105] Then, the solid was washed with three different fractions of
toluene, up to a total volume of 500 ml and dried under vacuum for
18 hours. the Zr content in the sample was determined through ICP
and gave 2.79% of zirconium.
EXAMPLE 10
Heterogenisation of bis[(3-trimethylsiloxypropyl)-cyclopentadienyl]
zirconium dichloride on aluminum phosphate
[0106] The compound was heterogenized through the same process used
to support it on silica, according to the description in example 7,
but using aluminium phosphate (Graco APGE) instead of silica (Graco
XPO 2407).
[0107] The Zr content in the sample was determined through X rays
fluorescence and gave 2% of zirconium.
EXAMPLE 11
Ethylene Polymerization
[0108] The ethylene polymerization ractions were completed in a 1
litre-capacity Buchi reactor in anhydrous conditions. The reactor,
charged with 600 ml of dry and degassed heptane, was conditioned at
70.degree. C. Before pressurising the reactor with ethylene the
cocatalyst was injected at a pressure of 1 atm. Then, the reactor
was pressurised up to 3.75 atm. At the end, the catalyst was
injected by using 0.25 atm of ethylene extra pressure. The
polymerization reactions is maintained at these pressure (4 atm)
and temperature (70.degree. C.) conditions. The suspension was
stirred with the help of a stirring bar at 1200 rpm for 15 or 30
minutes.
[0109] 13 ml (31.8 mmol Al) of MAO from a 10% solution of aluminium
in toluene (commercialized by Witco) were injected in the reactor;
0.1 g of [cyclopentadienyl (3-trimethylsiloxypropyl)
cyclopentadienyl] zirconium dichloride catalyst supported on
silica, prepared according to the description in example 8 (18.24
.mu.mol Zr), is added to this solution. Once completed, the
polymerization reaction was maintained under stirring at a
temperature of 70.degree. C. and 4 atm of ethylene pressure for 30
minutes. At the end of the reaction the pressure was rapidly
reduced and the reaction was stopped by adding acidified methanol.
5.21 g of polymer having M.sub.w=157.824 is obtained (Activity:
1.4.times.10 g PE/(mol Zr*hr*atm).
EXAMPLE 12
Ethylene Copolymerization with 1-hexane
[0110] The copolymerization reaction is carried out in the same
conditions as those described for ethylene polymerization, after
the comonomer initial addition in the reactor.
[0111] 10 ml of 1-hexene (24.2% by mol of comonomer in the feeding)
and 13 ml of MAO, from an aluminum 10% solution (31.8 mmol Al), is
injected in the reactor. 0.1 g of a [cyclopentadienyl
(3-trimethylsiloxypropyl) cyclopentadienyl] zirconium dichloride
catalyst prepared according to the description in example 8 (18.4
.mu.mol Zr) supported on silica is added to this solution. The
polymerization reaction was maintained at a temperature of
70.degree. C. and 4,132 bar (4 atm) of ethylene pressure for 30
minutes. At the end, the pressure was rapidly reduced and the
reaction was stopped by adding acidified methanol. 5.14 grams of
copolymer with: Mn=41970, Mw=220877, Mw/Mn=5.26 and 0.92% molar of
hexene is obtained. (Activity: 1.41.times.10.sup.5 g PE/(mol
Zr*hr*atm).
EXAMPLE 13
Ethylene Copolymerization with 1-hexene
[0112] Ethylene and 1-hexene were copolymerized. To do this, the
same method as the previous example (numer 12) is used, but with
the proviso that once the solvent is added and before pressurising
the reactor, 4 ml of dry and recently distilled 1-hexene (12% of
hexene in the feeding) is added. 13 ml of a MAO solution in toluene
(1.5 M of total aluminium) and 0.1 g of catalyst catalyst prepared
according to the description in example 8 are used. After 30
minutes of polymerization 1.47 g of polymer is obtained
(1.65.times.10 g PE/mol Zr*h*atm). The 1-hexene content in the
copolymer, determined by .sup.13C-RMN, was 0.49% molar, distributed
at random.
EXAMPLE 14
Ethylene Copolymerization with 1-hexene
[0113] Ethylene and 1-hexene were copolymerized. To do this, the
same method as example n 12 was used, but with the proviso that
once the solvent is added and before pressurising the reactor, 16
ml of dry and recently distilled 1-hexene (33.7% of hexene in the
feeding) is added. 13 ml of a MAO solution in toluene (1.5 M of
total aluminium) and 0.1 g of the catalyst are used. After 30
minutes of polymerization 1.80 g of polymer were obtained
(2.02.times.10.sup.8 g PE/mol Zr*h*atm). The 1-hexene content in
the copolymer, determined by .sup.13C-NMR, was 1.33% molar,
distributed at random.
EXAMPLE 15
Ethylene Polymerization
[0114] In the reactor 13 ml (31.8 mmol Al) of MAO, from a 10%
solution of aluminium in toluene (commercialised by Witco), are
injected. 0.1 g of [cyclopentadienyl (3-trimethylsiloxypropyl)
cyclopentadienyl] zirconium dichloride catalyst prepared according
to the description in example 10 (35.77 .mu.mol Zr) supported on
aluminium phosphate is added to this solution. The polymerization
reaction was kept at a temperature of 70.degree. C. a nd 4,132 bar
(4 atm) of ethylene pressure for 30 minutes. When the reaction was
considered completed, the pressure was rapidly reduced and
acidified methanol was added. 2.16 grams of polyethylene was
obtained. Activity: 0.24.times.10.sup.4 g PE/(mol Zr*hr*atm).
EXAMPLE 16
Heterogenization of bis[(3-trimethylsiloxypropyl)cyclopentadienyl]
zirconium dichloride on silica
[0115] 0.220 g of bis[(3-trimethylsiloxypropyl) cyclopentadienyl]
zirconium dichloride is dissolved in 15 ml of toluene, then, 0.7 ml
of a 10% MAO solution in toluene (commercialized by Witco) is added
and the mixture is maintained under stirring at room temperature.
15 minutes later, the resulting solution is poured in a 100 ml
flask, that contains 3 g of silica XPO-2407 (commercialized by
Graco), which has previously been calcinated at a temperature of
200.degree. C. and it is maintained under mechanic stirring for 1
hour at a temperature of 40.degree. C. Once the reaction time has
gone by, the solid is separated through filtration and washed with
consecutive fractions of toluene up to a total volume of 1 l. The
heterogeneous catalyst is finally dried under vacuum for 24 hours.
The Zr and Al content determined through ICP is 1.15% and 0.7%
respectively.
EXAMPLE 17
Heterogenization of bis[(3-trimethylsiloxypropyl) cyclopentadienyl]
zirconium dichloride on silica
[0116] The process for the heterogenization of
bis[(3-trimethylsiloxypropy- l) cyclopentadienyl] zirconium
dichloride is the one described in example 16, but the silica is
previously treated under vacuuum before being put in contact with
the premixture of the organo-metallic compound and the MAO. The Zr
and Al content determined through ICP is 1.2% and 0.7%
respectively.
EXAMPLE 18
[0117] The polymerization reaction is carried out according to the
method and the conditions described in example 11, but the reactor
temperature is 90.degree. C. 10 ml of a 10% MAO solution in toluene
(commercialized by Witco) (15 mmol of Al) and 0.079 g (0.01 mmol of
Zr) of the heterogeneous catalyst prepared according to example 16
are injected in the reacor. The polymerization reaction is
maintained at a temperature of 90.degree. C. and at an ethylene
pressure of 4 atm for 15 minutes. At the end of the reaction the
reactor pressure is reduced and acdified methanol is added. 2.4
grams of polymer with Mw 165.600 is obtained.
EXAMPLE 19
[0118] The polymerization reaction is carried out according to the
method and the conditions described in example 18. 10 ml of a 10%
MAO solution in toluene (commercialized by Witco) (15 mmol of Al)
and 0.075 g (0,01 mmol of Zr) of the heterogeneous catalyst
prepared according to example 17 are injected in the reactor. The
polymerization reaction is maintained at a temperature of
90.degree. C. and at an ethylene pressure 4 atm for 15 minutes. At
the end of the reaction the reactor pressure is reduced and
acidified methanol is added. 2.8 g of polymer is obtained.
* * * * *