U.S. patent application number 12/006938 was filed with the patent office on 2008-06-12 for process for polymerizing 1-butene.
This patent application is currently assigned to Basell Polyolefine GmbH. Invention is credited to Luigi Resconi.
Application Number | 20080139761 12/006938 |
Document ID | / |
Family ID | 44693675 |
Filed Date | 2008-06-12 |
United States Patent
Application |
20080139761 |
Kind Code |
A1 |
Resconi; Luigi |
June 12, 2008 |
Process for polymerizing 1-butene
Abstract
##STR00001## A process for polymerizing 1-butene, optionally
with up to 30% by mol of ethylene, propylene or an alpha olefin of
formula CH.sub.2.dbd.CHT wherein T is a C.sub.3-C.sub.10 alkyl
group, in the presence of a catalyst system obtainable by
contacting a metallocene compound of formula (I) Wherein M is an
atom of a transition metal; X, is a hydrogen atom, a halogen atoms
or a hydrocarbon group; R.sup.1, R.sup.2, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 are hydrogen atoms or hydrocarbon
groups; with the proviso that at least one of R.sup.6 or R.sup.7 is
a C.sub.1-C.sub.20 alkyl group; R.sup.3 and R.sup.4 are
C.sub.1-C.sub.20 alkyl groups; and an alumoxane and/or a compound
capable of forming an alkyl metallocene cation.
Inventors: |
Resconi; Luigi; (Ferrara,
IT) |
Correspondence
Address: |
Basell USA Inc.
Delaware Corporate Center II, 2 Righter Parkway, Suite #300
Wilmington
DE
19803
US
|
Assignee: |
Basell Polyolefine GmbH
Wesseling
DE
|
Family ID: |
44693675 |
Appl. No.: |
12/006938 |
Filed: |
January 7, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10556373 |
Nov 10, 2005 |
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PCT/EP2004/005078 |
May 7, 2004 |
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12006938 |
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60478099 |
Jun 12, 2003 |
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Current U.S.
Class: |
526/127 ;
526/348.6; 534/11; 534/15; 549/3; 549/43 |
Current CPC
Class: |
C08F 210/08 20130101;
C08F 110/08 20130101; C08F 4/65912 20130101; C08F 10/08 20130101;
Y10S 526/943 20130101; C08F 2500/15 20130101; C08F 2500/15
20130101; C08F 4/65927 20130101; C08F 2500/03 20130101; C08F
2500/17 20130101; C08F 2500/03 20130101; C08F 110/08 20130101; C08F
210/08 20130101; C08F 2500/17 20130101; C08F 10/08 20130101; C07F
17/00 20130101; C08F 210/16 20130101 |
Class at
Publication: |
526/127 ;
526/348.6; 534/11; 534/15; 549/3; 549/43 |
International
Class: |
C08F 4/44 20060101
C08F004/44; C08F 10/08 20060101 C08F010/08; C07F 5/00 20060101
C07F005/00; C07F 7/00 20060101 C07F007/00; C07D 333/50 20060101
C07D333/50 |
Foreign Application Data
Date |
Code |
Application Number |
May 12, 2003 |
EP |
03101304.8 |
Claims
1. A process for preparing 1-butene polymers, said process
comprising polymerizing 1-butene or copolymerizing 1-butene with
ethylene, propylene or an alpha-olefin of formula CH.sub.2.dbd.CHT
wherein T is a C.sub.3-C.sub.10 alkyl group, in the presence of a
catalyst system obtainable by contacting: (A) a metallocene
compound having the following formula (I) ##STR00015## wherein: M
is an atom of a transition metal selected from those belonging to
group 3, 4, or to the lanthanide or actinide groups in the Periodic
Table of the Elements; X, equal to or different from each other, is
a hydrogen atom, a halogen atoms or R, OR, OR'O, OSO.sub.2CF.sub.3,
OCOR, SR, NR.sub.2 or PR.sub.2 group, wherein R is a linear or
branched, saturated or unsaturated 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-alkylaryl or C.sub.7-C.sub.20-arylalkyl radical,
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and the R' is a
C.sub.1-C.sub.20-alkylidene, C.sub.6-C.sub.20-arylidene,
C.sub.7-C.sub.20-alkylarylidene, or C.sub.7-C.sub.20-arylalkylidene
radical. R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9, equal to or different from each other, are hydrogen atoms,
or linear or branched, saturated or unsaturated
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-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or R.sup.5 and R.sup.6, and/or R.sup.8 and R.sup.9 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.20 alkyl radicals as substituents;
with the proviso that at least one of R.sup.6 or R.sup.7 is a
linear or branched, saturated or unsaturated C.sub.1-C.sub.20-alkyl
radical, optionally containing heteroatoms belonging to groups
13-17 of the Periodic Table of the Elements; R.sup.3 and R.sup.4,
equal to or different from each other, are linear or branched,
saturated or unsaturated C.sub.1-C.sub.20-alkyl, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; and (B) an alumoxane and/or a compound
capable of forming an alkyl metallocene cation.
2. The process according to claim 1 wherein in the metallocene of
formula (I) R.sup.7 is preferably a linear or branched, saturated
or unsaturated C.sub.1-C.sub.20-alkyl radical, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; otherwise when R.sup.6 is different from a
hydrogen atom, R.sup.7 is a hydrogen atom.
3. The process according to claims 1 or 2 wherein the catalyst
system is obtained by further contacting the components (A) and
(13) with: (C) an organo aluminum compound.
4. The process according to anyone of claims 1-3 wherein in the
metallocene of formula (I) X is a hydrogen atom, a halogen atom or
a OR'O or R group wherein R is a linear or branched, saturated or
unsaturated 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-alkylaryl, or
C.sub.7-C.sub.20-arylalkyl radical, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements and R' is a divalent radical selected from the group
consisting of C.sub.1-C.sub.20-alkylidene,
C.sub.6-C.sub.20-arylidene, C.sub.7-C.sub.20-alkylarylidene, and
C.sub.7-C.sub.20-arylalkylidene radicals.
5. The process according to anyone of claims 1 to 4 wherein in the
metallocene of formula (I) R.sup.1 and R.sup.2 are the same and are
C.sub.1-C.sub.10 allyl radicals optionally containing one or more
silicon atoms.
6. The process according to anyone of claims 1 to 5 wherein in the
metallocene of formula (I) R.sup.8 and R.sup.9, equal to or
different from each other, are C.sub.1-C.sub.10 alkyl or
C.sub.6-C.sub.20 aryl radicals; R.sup.5 is hydrogen atoms or methyl
radicals and R.sup.6 is a hydrogen atom or a methyl, ethyl or
isopropyl radical.
7. The process according to anyone of claims 1 to 6 wherein in the
metallocene of formula (I) R.sup.3, R.sup.4 and R.sup.7, equal to
or different from each other, are C.sub.1-C.sub.10 alkyl
radicals.
8. The process according to anyone of claims 1 to 7 wherein the
compound of formula (I) has formula (Ia) or (Ib): ##STR00016##
Wherein M, X, R.sup.1, R.sup.2, R.sup.8 and R.sup.9 have the
meaning described in claim 1; R.sup.3 and R.sup.4, equal to or
different from each other, are linear or branched, saturated or
unsaturated C.sub.1-C.sub.20-alkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; R.sup.6 and R.sup.7 are a linear or branched, saturated
or unsaturated C.sub.1-C.sub.20-alkyl radical, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements.
9. The process according to claim 8 wherein R.sup.3, R.sup.4,
R.sup.6 and R.sup.7 are C.sub.1-C.sub.10-alkyl radicals.
10. The process according to anyone of claims 1-9 wherein 1-butene
and ethylene are copolymerized in the presence of the catalyst
system reported above.
11. The process according to claim 10 wherein the amount of
ethylene in the liquid phase ranges from 0.01 to 30% by weight.
12. The process according to anyone of claims 1-12 wherein said
process is carried out in the presence of hydrogen.
13. The process according to claim 12 wherein the concentration of
hydrogen in the liquid phase ranges from 0.5 ppm to 20 ppm.
14. A 1-butene homopolymer having the following characteristics:
isotactic pentads (mmmm)>90; intrinsic viscosity (I.V.) measured
in tetrahydronaphtalene (THN) at 135.degree. C.>1.2; melting
point (D.S.C.) higher than 100.degree. C.; and molecular weight
distribution Mw/Mn<4;
15. A 1-butene homopolymer having the following characteristics:
isotactic pentads (mmmm)>95; intrinsic viscosity (I.V.) measured
in tetrahydronaphtalene (THN) at 135.degree. C.>1.5; melting
point (D.S.C.) higher than 100.degree. C.; and molecular weight
distribution Mw/Mn<4.
16. A 1-butene/ethylene copolymer having an ethylene content
comprised between 0.2% by mol and 15% by mol obtainable by the
process of claim 1 having the following characteristics: isotactic
pentads (mmmm)>90 intrinsic viscosity (I.V.) measured in
tetrahydronaphtalene (THN) at 135.degree. C.>1.2 wherein
ethylene content in the polymer (C.sub.2) (% by mol) and the
melting point of the polymer (Tm) meet the following relation:
Tm<-4.4C.sub.2+92.0.
17. A metallocene compound of formula (II): ##STR00017## wherein: M
is an atom of a transition metal selected from those belonging to
group 3, 4, or to the lanthanide or actinide groups in the Periodic
Table of the Elements; X, equal to or different from each other, is
a hydrogen atom, a halogen atom, a R, OR, OR'O, OSO.sub.2CF.sub.3,
OCOR, SR, NR.sub.2 or PR.sub.2 group wherein R is a linear or
branched, saturated or unsaturated 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-alkylaryl or C.sub.7-C.sub.20-arylalkyl radical,
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and R' is a
C.sub.1-C.sub.20-alkylidene, C.sub.6-C.sub.20-arylidene,
C.sub.7-C.sub.20-alkylarylidene, or C.sub.7-C.sub.20-arylalkylidene
radical; R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9, equal to or different from each other, are hydrogen atoms,
or linear or branched, saturated or unsaturated
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-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or R.sup.8 and R.sup.9 can optionally form a saturated or
unsaturated, 5 or 6 membered ring; R.sup.3 and R.sup.4, equal to or
different from each other, are linear or branched, saturated or
unsaturated C.sub.1-C.sub.20-alkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; R.sup.6 is a linear or branched, saturated or unsaturated
C.sub.1-C.sub.20-alkyl radical, optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements; or
it can optionally form with R.sup.5 a saturated or unsaturated, 5
or 6 membered ring, said ring can bear C.sub.1-C.sub.20 alkyl
radicals as substituents.
18. The metallocene compound according to claim 17 wherein:
R.sup.1, R.sup.2, are the same and are C.sub.1-C.sub.10 alkyl
radicals optionally containing one or more silicon atoms; R.sup.8
and R.sup.9, equal to or different from each other, are
C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.20 aryl radicals; R.sup.5
is a hydrogen atom or a methyl radical; R.sup.7 is a hydrogen atom;
R.sup.3 and R.sup.4 equal to or different from each other are
C.sub.1-C.sub.10-alkyl radicals; R.sup.6 is a
C.sub.1-C.sub.10-alkyl radical.
19. A ligand of formula (III): ##STR00018## wherein R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and
R.sup.9 have the meaning described in claim 12.
Description
[0001] The present invention relates to a process for polymerizing
1-butene by using metallocene compounds and to the isotactic
1-butene polymers obtained thereby.
[0002] Isotactic 1-butene polymers are well known in the art. In
view of their good properties in terms of pressure resistance,
creep resistance, and impact strength they have a lot of uses such
as the manufacture of pipes to be used in the metal pipe
replacement, easy-open packaging and films.
[0003] 1-Butene (co)polymers are generally prepared by
(co)polymerzing 1-butene in the presence of TiCl.sub.3 based
catalysts components together with diethylaluminum chloride (DEAC)
as cocatalyst. In some cases diethyl aluminum iodide (DEAI) is also
used in mixtures with DEAC. The thus obtained polymers, however,
generally do not show satisfactory mechanical properties.
Furthermore, in view of the low yields obtainable with the
TiCl.sub.3 based catalysts, the 1-butene polymers prepared with
these catalysts have a high content of catalyst residues (generally
more than 300 ppm of Ti) which lowers the properties of the
polymers making it necessary a deashing step.
[0004] 1-Butene (co)polymers can also be obtained by polymerizing
the monomers in the presence of a stereospecific catalyst
comprising (A) a solid component comprising a Ti compound and an
electron-donor compound supported on MgCl.sub.2; (B) an
alkylaluminum compound and, optionally, (C) an external
electron-donor compound. A process of this type is disclosed, for
instance, in EP-A-172961 and in WO99/45043. Recently, metallocene
compounds have been proposed for producing 1-butene polymers. In
Macromolecules 1995, 28, 1739-1749,
rac-dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium
dichloride and methylaluminoxane have been used for polymerizing
1-butene. The yield of the process is not indicated and the
molecular weight of the obtained polymer (Mn) is very low. In
Macromol. Rapid Commun. 18, 581-589 (1997), rac- and
meso-[dimethylsilylenebis(2,3,5-trimethyl-cyclopentadienyl)]zirc-
onium dichloride have been used for the polymerization of 1-butene.
The yields of the process and the molecular weight of the obtained
polymers are rather low.
[0005] In WO 02/16450, 1-butene polymers endowed with low
isotacticity are described. These polymers are obtained by using a
specific class of double-bridged metallocene compounds.
[0006] In the international application WO 03/042258, 1-butene
polymers obtained with metallocene compounds wherein a .pi. ligand
is a cyclopentadithiophene moiety are described. It has now been
found that, by selecting a specific substitution pattern in the
other n moiety of the metallocene compound, the molecular weight of
the obtained polymers can be further increased and, at the same
time, obtained in high yields.
[0007] Thus, according to a first aspect, the present invention
provides a process for preparing 1-butene polymers, said process
comprising polymerizing 1-butene or copolymerizing 1-butene with
ethylene, propylene or an alpha-olefin of formula CH.sub.2.dbd.CHT
wherein T is a C.sub.3-C.sub.10 alkyl group, in the presence of a
catalyst system obtainable by contacting: [0008] (A) a metallocene
compound belonging to the following formula (I):
##STR00002##
[0008] wherein: M is an atom of a transition metal selected from
those belonging to group 3, 4, or to the lanthanide or actinide
groups in the Periodic Table of the Elements; preferably M is
zirconium titanium or hafnium; X, equal to or different from each
other, is a hydrogen atom, a halogen atom, a R, OR, OR'O,
OSO.sub.2CF.sub.3, OCOR, SR, NR.sub.2 or PR.sub.2 group wherein R
is a linear or branched, saturated or unsaturated
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-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radical, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; and R' is a C.sub.1-C.sub.20-alkylidene,
C.sub.6-C.sub.20-arylidene, C.sub.7-C.sub.20-alkylarylidene, or
C.sub.7-C.sub.20-arylalkylidene radical; preferably X is a hydrogen
atom, a halogen atom, a OR'O or R group; more preferably X is
chlorine or a methyl radical; R.sup.1, R.sup.2, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9, equal to or different from each
other, are hydrogen atoms, or linear or branched, saturated or
unsaturated 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-alkylaryl or
C.sub.7-C.sub.20-arylalkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or R.sup.5 and R.sup.6, and/or R.sup.8 and R.sup.9 can
optionally form a saturated or unsaturated, 5 or 6 membered rings,
said ring can bear C.sub.1-C.sub.20 alkyl radicals as substituents;
with the proviso that at least one of R.sup.6 or R.sup.7 is a
linear or branched, saturated or unsaturated C.sub.1-C.sub.20-alkyl
radical, optionally containing heteroatoms belonging to groups
13-17 of the Periodic Table of the Elements; preferably a
C.sub.1-C.sub.10-alkyl radical; preferably R.sup.1, R.sup.2, are
the same and are C.sub.1-C.sub.10 alkyl radicals optionally
containing one or more silicon atoms; more preferably R.sup.1 and
R.sup.2 are methyl radicals; R.sup.8 and R.sup.9, equal to or
different from each other, are preferably C.sub.1-C.sub.10 alkyl or
C.sub.6-C.sub.20 aryl radicals; more preferably they are methyl
radicals; R.sup.5 is preferably a hydrogen atom or a methyl
radical; R.sup.6 is preferably a hydrogen atom or a methyl, ethyl
or isopropyl radical; R.sup.7 is preferably a linear or branched,
saturated or unsaturated C.sub.1-C.sub.20-allyl radical, optionally
containing heteroatoms belonging to groups 13-17 of the Periodic
Table of the Elements; preferably a C.sub.1-C.sub.10-alkyl radical;
more preferably R.sup.7 is a methyl or ethyl radical; otherwise
when R.sup.6 is different from a hydrogen atom, R.sup.7 is
preferably a hydrogen atom R.sup.3 and R.sup.4, equal to or
different from each other, are linear or branched, saturated or
unsaturated C.sub.1-C.sub.20-alkyl radicals, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; preferably R.sup.3 and R.sup.4 equal to or different from
each other are C.sub.1-C.sub.10-alkyl radicals; more preferably
R.sup.3 is a methyl, or ethyl radical; and R.sup.4 is a methyl,
ethyl or isopropyl radical; [0009] (B) an alumoxane or a compound
capable of forming an alkyl metallocene cation; and optionally
[0010] (C) an organo aluminum compound.
[0011] Metallocene compounds of formula (I) have been described,
for example, in WO 01/47939.
[0012] Preferably the compounds of formula (I) have formula (Ia) or
(Ib):
##STR00003##
Wherein
[0013] M, X, R.sup.1, R.sup.2, R.sup.8 and R.sup.9 have been
described above; R.sup.3 and R.sup.4, equal to or different from
each other, are linear or branched, saturated or unsaturated
C.sub.1-C.sub.20-alkyl radicals, optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements;
preferably R.sup.3 and R.sup.4 equal to or different from each
other are C.sub.1-C.sub.10-alkyl radicals; more preferably R.sup.3
is a methyl, or ethyl radical; and R.sup.4 is a methyl, ethyl or
isopropyl radical; R.sup.6 and R.sup.7 are linear or branched,
saturated or unsaturated C.sub.1-C.sub.20-alkyl radicals,
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; preferably C.sub.1-C.sub.10-alkyl
radicals; more preferably R.sup.7 is a methyl or ethyl radical; and
R.sup.6 is a methyl, ethyl or isopropyl radical.
[0014] Alumoxanes used as component B) can be obtained by reacting
water with an organo-aluminium compound of formula
H.sub.jAlU.sub.3-j or H.sub.jAl.sub.2U.sub.6-j, where U
substituents, same or different, are hydrogen atoms, halogen atoms,
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-alkylaryl or or
C7-C20-arylalkyl radical, optionally containing silicon or
germanium atoms with the proviso that at least one U is different
from halogen, and j ranges from 0 to 1, being also a non-integer
number. In this reaction the molar ratio of Al/water is preferably
comprised between 1:1 and 100:1. The molar ratio between aluminium
and the metal of the metallocene generally is comprised between
about 10:1 and about 20000:1, and more preferably between about
100:1 and about 5000:1. The alumoxanes used in the catalyst
according to the invention are considered to be linear, branched or
cyclic compounds containing at least one group of the type:
##STR00004##
wherein the substituents U, same or different, are described
above.
[0015] In particular, alumoxanes of the formula:
##STR00005##
can be used in the case of linear compounds, wherein n.sup.1 is 0
or an integer from 1 to 40 and the substituents U are defined as
above, or alumoxanes of the formula:
##STR00006##
can be used in the case of cyclic compounds, wherein n.sup.2 is an
integer from 2 to 40 and the U substituents are defined as above.
Examples of alumoxanes suitable for use according to the present
invention are methylalumoxane (MAO), tetra-(isobutyl)alumoxane
(TIBAO), tetra-(2,4,4-trimethyl-pentyl)alumoxane (TIOAO),
tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and
tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO). Particularly
interesting cocatalysts are those described in WO 99/21899 and in
WO01/21674 in which the alkyl and aryl groups have specific
branched patterns. Non-limiting examples of aluminium compounds
according to WO 99/21899 and WO01/21674 are:
[0016] tris(2,3,3-trimethyl-butyl)aluminium,
tris(2,3-dimethyl-hexyl)aluminium,
tris(2,3-dimethyl-butyl)aluminium,
tris(2,3-dimethyl-pentyl)aluminium, tris(2,3
dimethyl-heptyl)aluminium, tris(2-methyl-3-ethyl-pentyl)aluminium,
tris(2-methyl-3-ethyl-hexyl)aluminium,
tris(2-methyl-3-ethyl-heptyl)aluminium,
tris(2-methyl-3-propyl-hexyl)aluminium,
tris(2-ethyl-3-methyl-butyl)aluminium,
tris(2-ethyl-3-methyl-pentyl)aluminium,
tris(2,3-diethyl-pentyl)aluminium,
tris(2-propyl-3-methyl-butyl)aluminium,
tris(2-isopropyl-3-methyl-butyl)aluminium,
tris(2-isobutyl-3-methyl-pentyl)aluminium,
tris(2,3,3-trimethyl-pentyl)aluminium,
tris(2,3,3-trimethyl-hexyl)aluminium,
tris(2-ethyl-3,3-dimethyl-butyl)aluminium,
tris(2-ethyl-3,3-dimethyl-pentyl)aluminium,
tris(2-isopropyl-3,3-dimethyl-butyl)aluminium,
tris(2-trimethylsilyl-propyl)aluminium,
tris(2-methyl-3-phenyl-butyl)aluminium,
tris(2-ethyl-3-phenyl-butyl)aluminium,
tris(2,3-dimethyl-3-phenyl-butyl)aluminium,
tris(2-phenyl-propyl)aluminium,
tris[2-(4-fluoro-phenyl)-propyl]aluminium,
tris[2-(4-chloro-phenyl)-propyl]aluminium,
tris[2-(3-isopropyl-phenyl)-propyl]aluminium,
tris(2-phenyl-butyl)aluminium,
tris(3-methyl-2-phenyl-butyl)aluminium,
tris(2-phenyl-pentyl)aluminium,
tris[2-(pentafluorophenyl)-propyl]aluminium,
tris[2,2-diphenyl-ethyl]aluminium and
tris[2-phenyl-2-methyl-propyl]aluminium, as well as the
corresponding compounds wherein one of the hydrocarbyl groups is
replaced with a hydrogen atom, and those wherein one or two of the
hydrocarbyl groups are replaced with an isobutyl group.
[0017] Amongst the above aluminium compounds, trimethylaluminium
(TMA), triisobutylaluminum (TIBAL),
tris(2,4,4-trimethyl-pentyl)aluminum (TIOA),
tris(2,3-dimethylbutyl)aluminium TDMBA) and
tris(2,3,3-trimethylbutyl)aluminum (TTMBA) are preferred.
[0018] Non-limiting examples of compounds able to form an
alkylmetallocene cation are compounds of formula D.sup.+E.sup.-
wherein D.sup.+ is a Bronsted acid, able to donate a proton and to
react irreversibly with a substituent X of the metallocene of
formula (I) and E.sup.- is a compatible anion, which is able to
stabilize the active catalytic species originating from the
reaction of the two compounds, and which is sufficiently labile to
be able to be removed by an olefinic monomer. Preferably, the anion
E.sup.- comprises of one or more boron atoms. More preferably, the
anion E.sup.- is an anion of the formula BAr.sub.4.sup.(-), wherein
the substituents Ar which can be identical or different are aryl
radicals such as phenyl, pentafluorophenyl or
bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is
particularly preferred examples of these compounds are described in
WO 91/02012. Moreover, compounds of the formula BAr.sub.3 can
conveniently be used. Compounds of this type are described, for
example, in the published International patent application WO
92/00333. Other examples of compounds able to form an
alkylmetallocene cation are compounds of formula BAr.sub.3P wherein
P is a substituted or unsubstituted pyrrol radicals. These
compounds are described in WO01/62764. Other examples of cocatalyst
can be found in EP 775707 and DE 19917985. Compounds containing
boron atoms can be conveniently supported according to the
description of DE-A-19962814 and DE-A-19962910. All these compounds
containing boron atoms can be used in a molar ratio between boron
and the metal of the metallocene comprised between about 1:1 and
about 10:1; preferably 1:1 and 2.1; more preferably about 1:1.
[0019] Non limiting examples of compounds of formula D.sup.+E.sup.-
are: [0020] Triethylammoniumtetra(phenyl)borate, [0021]
Tributylanunoniumtetra(phenyl)borate, [0022]
Trimethylammoniumtetra(tolyl)borate, [0023]
Tributylammoniumtetra(tolyl)borate, [0024]
Tributylammoniumtetra(pentafluorophenyl)borate, [0025]
Tributylammoniumtetra(pentafluorophenyl)aluminate, [0026]
Tripropylammoniumtetra(dimethylphenyl)borate, [0027]
Tributylammoniumtetra(trifluoromethylphenyl)borate, [0028]
Tributylammoniumtetra(4-fluorophenyl)borate, [0029]
N,N-Dimethylaniliniumtetra(phenyl)borate, [0030]
N,N-Diethylaniliniumtetra(phenyl)borate, [0031]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)boratee, [0032]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate, [0033]
Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, [0034]
Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate, [0035]
Triphenylphosphoniumtetrais(phenyl)borate, [0036]
Triethylphosphoniumtetrakis(phenyl)borate, [0037]
Diphenylphosphoniumtetrakis(phenyl)borate, [0038]
Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate, [0039]
Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate, [0040]
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate, [0041]
Triphenylcarbeniumtetrais(pentafluorophenyl)aluminate, [0042]
Triphenylcarbeniumtetr-akis(phenyl)aluminate, [0043]
Ferroceniumtetrakis(pentafluorophenyl)borate, [0044]
Ferroceniumtetrakis(pentafluorophenyl)aluminate. [0045]
Triphenylcarbeniumtetrais(pentafluorophenyl)borate, [0046]
N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate.
[0047] Organic aluminum compounds used as compound C) are those of
formula H.sub.jAlU.sub.3-j or H.sub.jAl.sub.2U.sub.6-j described
above. The catalysts of the present invention can also be supported
on an inert carrier. This is achieved by depositing the metallocene
compound A) or the product of the reaction thereof with the
component B), or the component B) and then the metallocene compound
A) on an inert support such as, for example, silica, alumina,
Al--Si, Al--Mg mixed oxides, magnesium halides,
styrene/divinylbenzene copolymers, polyethylene or polypropylene.
The supportation process is carried out in an inert solvent such as
hydrocarbon for example toluene, hexane, pentane or propane and at
a temperature ranging from 0.degree. C. to 100.degree. C.,
preferably the process is carried out at a temperature ranging from
25.degree. C. to 90.degree. C. or the process is carried out at
room temperature.
[0048] A suitable class of supports which can be used is that
constituted by porous organic supports functionalized with groups
having active hydrogen atoms. Particularly suitable are those in
which the organic support is a partially crosslinked styrene
polymer. Supports of this type are described in European
application EP-633272. Another class of inert supports particularly
suitable for use according to the invention is that of polyolefin
porous prepolymers, particularly polyethylene. A further suitable
class of inert supports for use according to the invention is that
of porous magnesium halides such as those described in
International application WO 95/32995.
[0049] With the process of the present invention it is possible to
obtain 1-butene polymers having high molecular weight, measured in
terms of their intrinsic viscosity (I.V.) and in high yields. Thus,
according to another aspect, the present invention provides
1-butene homopolymers having the following characteristics: [0050]
isotactic pentads (mmmm)>90, preferably >95; [0051] intrinsic
viscosity (I.V.) measured in tetrahydronaphtalene (THN) at
135.degree. C.>1.2, preferably .gtoreq.1.5, more preferably
>1.9; even more preferably >2.4; [0052] melting point
(D.S.C.) higher than 100.degree. C.; and [0053] molecular weight
distribution Mw/Mn<4, preferably <3.5.
[0054] The 1-butene homopolymers of the present invention do not
have 4,1 insertions (regioerrors) detectable with a 400 MHz
spectrometer operating at 100.61 MHz.
[0055] When 1-butene is copolymerized with ethylene, propylene or
alpha olefins of formula CH.sub.2.dbd.CHT wherein T is a
C.sub.3-C.sub.10 alkyl group, a copolymer having a content of
comonomer derived units of up to 50% by mol can be obtained,
preferably up to 20% by mol, more preferably from 0.2% by mol to
15% by mol. Examples of alpha-olefins of formula CH.sub.2.dbd.CHT
are 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene,
4,6-dimethyl-1-heptene, 1-decene, 1-dodecene. Preferred comonomers
to be used in the process according to the present invention are
ethylene, propylene and 1-hexene.
[0056] In particular, the 1-butene ethylene copolymers obtainable
by the process of the present invention are endowed with a very low
melting point with respect to the ethylene content thus it is
possible to lower the melting point of the 1-butene/ethylene
polymer by adding small amount of ethylene. furthermore ethylene is
used as comonomer in the process of the present invention the
resulting copolymer shows a higher molecular weight with respect to
the homopolymers and the yield of the process is improved.
Therefore a further embodiment of the present invention is a
process for preparing copolymer of 1-butene and ethylene,
comprising the step of copolymerizing 1-butene and ethylene in the
presence of the catalyst system reported above. Preferably the
amount of ethylene in the liquid phase ranges from 0.01 to 30% by
weight; preferably from 1% to 10% by weight.
[0057] Preferably the 1-butene/ethylene copolymers have an ethylene
content comprised between 0.2% by mol and 15% by mol; preferably
comprised between 1% by mol and 10% by mol; more preferably
comprised between 2% by mol and 8% by mol.
[0058] Therefore a further object of the present invention is a
1-butene/ethylene copolymer having an ethylene content comprised
between 0.2% by mol and 15% by mol; preferably comprised between 1%
by mol and 10% by mol; more preferably comprised between 2% by mol
and 8% by mol., obtainable by the process of the present invention,
having the following characteristics: [0059] isotactic pentads
(mmmm)>90, preferably >95; [0060] intrinsic viscosity (I.V.)
measured in tetrahydronaphtalene (THN) at 135.degree. C.>1.2,
preferably .gtoreq.1.5, more preferably >1.9; even more
preferably >2.4; wherein the percent by mol of the ethylene
content in the polymer (C.sub.2) and the melting point of the
polymer (Tm) meet the following relation:
[0060] Tm<-4.4C.sub.2+92.0.
Preferably the relation is Tm<4.4C.sub.2+90.2; more preferably
it is Tm<4.4C.sub.2+89.2.
[0061] The polymerization process of the present invention can be
carried out in liquid phase, optionally in the presence of an inert
hydrocarbon solvent, or in gas phase. Said hydrocarbon solvent can
be either aromatic (such as toluene) or aliphatic (such as propane,
hexane, heptane, isobutane, cyclohexane and
2,2,4-trimethylpentane). Preferably, the polymerization process of
the present invention is carried out by using liquid 1-butene as
polymerization medium. The polymerization temperature preferably
ranges from 0.degree. C. to 250.degree. C.; preferably comprised
between 20.degree. C. and 150.degree. C. and, more particularly
between 50.degree. C. and 90.degree. C.; The molecular weight
distribution can be varied by using mixtures of different
metallocene compounds or by carrying out the polymerization in
several stages which differ as to the polymerization temperature
and/or the concentrations of the molecular weight regulators and/or
the monomers concentration. Moreover by carrying out the
polymerization process by using a combination of two different
metallocene compounds of formula (I) a polymer endowed with a broad
melting is produced. The polymerization yield depends on the purity
of the transition metal organometallic catalyst compound (A) in the
catalyst, therefore, said compound can be used as such or can be
subjected to purification treatments before use.
[0062] The polymerization process of the present invention can be
carried out in the presence of hydrogen in order to increase the
yield. Preferably the concentration of hydrogen in the liquid phase
ranges from 0.5 ppm to 20 ppm; more preferably from 1 ppm to 6 ppm.
The effect of improving the yield of the process is additive with
the effect of ethylene explained above.
[0063] A further object of the present invention is a metallocene
compound of formula (II):
##STR00007##
wherein: M is an atom of a transition metal selected from those
belonging to group 3, 4, or to the lanthanide or actinide groups in
the Periodic Table of the Elements; preferably M is zirconium
titanium or hafnium; X, equal to or different from each other, is a
hydrogen atom, a halogen atom, a R, OR, OR'O, OSO.sub.2CF.sub.3,
OCOR, SR, NR.sub.2 or PR.sub.2 group wherein R is a linear or
branched, saturated or unsaturated 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-alkylaryl or C.sub.7-C.sub.20-arylalkyl radical,
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; and R' is a
C.sub.1-C.sub.20-alkylidene, C.sub.6-C.sub.20-arylidene,
C.sub.7-C.sub.20-alkylarylidene, or C.sub.7-C.sub.20-arylalkylidene
radical; preferably X is a hydrogen atom, a halogen atom, a OR'O or
R group; more preferably X is chlorine or a methyl radical;
R.sup.1, R.sup.2, R.sup.5, R.sup.7, R.sup.8 and R.sup.9, equal to
or different from each other, are hydrogen atoms, or linear or
branched, saturated or unsaturated 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-alkylaryl or C.sub.7-C.sub.20-arylalkyl radicals,
optionally containing heteroatoms belonging to groups 13-17 of the
Periodic Table of the Elements; or R.sup.8 and R.sup.9 can
optionally form a saturated or unsaturated, 5 or 6 membered ring;
preferably R.sup.1, R.sup.2, are the same and are C.sub.1-C.sub.10
alkyl radicals optionally containing one or more silicon atoms;
more preferably R.sup.1 and R.sup.2 are methyl radicals; R.sup.8
and R.sup.9, equal to or different from each other, are preferably
C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.20 aryl radicals; more
preferably they are methyl radicals; R.sup.5 is preferably a
hydrogen atom or a methyl radical; R.sup.7 is preferably a hydrogen
atom; R.sup.3 and R.sup.4, equal to or different from each other,
are linear or branched, saturated or unsaturated
C.sub.1-C.sub.20-alkyl radicals, optionally containing heteroatoms
belonging to groups 13-17 of the Periodic Table of the Elements;
preferably R.sup.3 and R.sup.4 equal to or different from each
other are C.sub.1-C.sub.10-alkyl radicals; more preferably R.sup.3
is a methyl, or ethyl radical; and R.sup.4 is a methyl, ethyl or
isopropyl radical; R.sup.6 is a linear or branched, saturated or
unsaturated C.sub.1-C.sub.20-alkyl radical, optionally containing
heteroatoms belonging to groups 13-17 of the Periodic Table of the
Elements; or it can optionally form with R.sup.5 a saturated or
unsaturated, 5 or 6 membered ring, said ring can bear
C.sub.1-C.sub.20 alkyl radicals as substituents; preferably R.sup.6
is a C.sub.1-C.sub.10alkyl radical; more preferably R.sup.6 is a
methyl, ethyl or isopropyl radical;
[0064] By using this class of compounds in the process according to
the present invention polybutene homo or copolymers endowed with a
higher molecular weight measured in terms of their intrinsic
viscosity (I.V.) and in high yields are obtained.
[0065] A further object of the present invention is a ligand of
formula (III):
##STR00008##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8 and R.sup.9 have the meaning described above.
[0066] Metallocene compounds of formula (II) can be obtained by
reacting the ligand of formula (III) with a compound capable of
forming a corresponding dianionic compound thereof and thereafter
with a compound of formula Mx.sub.4, wherein M and X have the
meaning described above. Example of compound able to form the
dianionic compound are alkyl lithium such as methyl lithium or
butyl lithium, Grignard reagents or metallic sodium and
potassium.
[0067] The following examples are for illustrative purpose and do
not intend to limit the scope of the invention.
EXAMPLES
Experimental Section
[0068] The intrinsic viscosity (I.V.) was measured in
tetrahydronaphtalene (THN) at 135.degree. C.
[0069] The melting points of the polymers (T.sub.m) were measured
by Differential Scanning Calorimetry (D.S.C.) on a Perkin Elmer
DSC-7 instrument, according to the standard method. A weighted
sample (5-7 mg) obtained from the polymerization was sealed into
aluminum pans and heated to 180.degree. C. at 10.degree. C./minute.
The sample was kept at 180.degree. C. for 5 minutes to allow a
complete melting of all the crystallites, then cooled to 20.degree.
C. at 10.degree. C./minute. After standing 2 minutes at 20.degree.
C., the sample was heated for the second time to 180.degree. C. at
10.degree. C./min. In this second heating run, the peak temperature
was taken as the melting temperature (T.sub.m) and the area of the
peak as melting enthalpy (.DELTA.H.sub.f).
[0070] Molecular weight parameters and molecular weight
distribution for all the samples were measured using a Waters 150C
ALC/GPC instrument (Waters, Milford, Mass., USA) equipped with four
mixed-gel columns PLgel 20 .mu.m Mixed-A LS (Polymer Laboratories,
Church Stretton, United Kingdom). The dimensions of the columns
were 300.times.7.8 mm. The solvent used was TCB and the flow rate
was kept at 1.0 mL/min. Solution concentrations were 0.1 g/dL in
1,2,4 trichlorobenzene (TCB). 0.1 g/L of 2,6-di-t-butyl-4-methyl
phenol (BHT) was added to prevent degradation and the injection
volume was 300 .mu.L. All the measurements were carried out at
135.degree. C. GPC calibration is complex, as no well-characterized
narrow molecular weight distribution standard reference materials
are available for 1-butene polymers. Thus, a universal calibration
curve was obtained using 12 polystyrene standard samples with
molecular weights ranging from 580 to 13,200,000. It was assumed
that the K values of the Mark-Houwink relationship were:
K.sub.PS=1.21.times.10.sup.-4, dLg and
K.sub.PB=1.78.times.10.sup.-4 dL/g for polystyrene and
poly-1-butene respectively. The Mark-Houwink exponents a were
assumed to be 0.706 for polystyrene and 0.725 for poly-1-butene.
Even though, in this approach, the molecular parameters obtained
were only an estimate of the hydrodynamic volume of each chain,
they allowed a relative comparison to be made.
[0071] .sup.13C-NMR spectra were acquired on a DPX-400 spectrometer
operating at 100.61 MHz in the Fourier transform mode at
120.degree. C. The samples were dissolved in
1,1,2,2-tetrachloroethane-d2 at 120.degree. C. with a 8% wt/v
concentration. Each spectrum was acquired with a 90.degree. pulse,
15 seconds of delay between pulses and CPD (waltz16) to remove
.sup.1H-.sup.13C coupling. About 3000 transients were stored in 32K
data points using a spectral window of 6000 Hz. The isotacticity of
metallocene-made PB is measured by .sup.13C NMR, and is defined as
the relative intensity of the mmmm pentad peak of the diagnostic
methylene of the ethyl branch. This peak at 27.73 ppm was used as
internal reference. Pentad assignments are given according to
Macromolecules, 1992, 25, 6814-6817. After baseline correction,
this region is integrated between 28.60-27.27 ppm (mmmm+mmmr+mmrr)
and 26.78-26.48 ppm (mrrm). The phase of the two integrals is then
corrected and the first integral splitted at 27.4 ppm to separate
the mmrr pentad contribution. The mmmr peak overlaps with the base
of the mmmm pentad and cannot be separated. Statistical modelling
of pentad distributions was done using a model based on.
enantiomorphic site control as a function of the probability
parameter b (for the insertion of the preferred enantioface), as
described in Chem. Rev. 2000, 100, 1253-1345.
[0072] Taking into account the overlap between the mmmm and the
mmmr pentads, the following expression were used:
mmmm+mmmr=b.sup.5+(1-b).sup.5+2[b.sup.4(1-b)+b(1-b).sup.4]
mmrr=2[b.sup.4(1-b)+b(1-b).sup.4]
mrrm=b.sup.4(1-b)+b(1-b).sup.4
Assignments of 4,1 insertion were made according to V. Busico, R.
Cipullo, A. Borriello, Macromol. Rapid. Commun. 1995, 16,
269-274.
Preparation of Catalyst Components
[0073] Rac
dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclo-
penta[1,2-b:4,3-b']-dithiophene)}zirconium dichloride (A-1);
dimethylsilyl{(1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithio-
phene)}zirconium dichloride (A-2);
dimethylsilyl{(2-methyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b-
']-dithiophene)}zirconium dichloride (A-3) were prepared according
to WO 01/47939.
Synthesis of
dimethylsilyl[1-(2,4,6-trimethyl-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2--
b:4,3-b']-dithiophenyl)]zirconium dichloride (A-4)
a) Synthesis of chloro(2,4,6-trimethyl-indenyl)dimethylsilane
##STR00009##
[0075] A 2.5 M n-BuLi solution in hexane (37.2 mL, 0.093 mol) was
added dropwise at 0.degree. C. under nitrogen atmosphere to a
solution of 14.00 g of 2,4,6-trimethyl-indene (prepared according
to Eur. Pat. Appl. 693,506) in 100 mL of Et.sub.2O in a 500 mL
3-necked round flask. During the addition a white suspension was
formed. The mixture was then allowed to warm up to r.t. and stirred
for 30 min, with final formation of a white suspension. Then a
solution of Me.sub.2SiCl.sub.2 (98%, d=1,064, 11.28 mL, 0.093 mol.)
in 30 mL of THF was cooled to 0.degree. C. and slowly added to the
lithium salt suspension, also cooled to 0.degree. C. The reaction
mixture was allowed to warm up to r. t. and stirred for 2 h with
final formation of a light yellow suspension. The solvents were
then removed in vacuo and the residue was extracted with 150 mL of
toluene to remove the LiCl. The light yellow filtrate was brought
to dryness in vacuo to give 21.53 g of a yellow oil, characterized
by .sup.1NMR analysis as the target product, yield 97.5%. This
product was used as such in the next step without further
purification.
b) Synthesis of
1-(2,4,6-trimethyl-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']dithi-
ophene) dimethylsilane
##STR00010##
[0077] A 2.5 M n-BuLi solution in hexane (16.74 mL, 41.85 mmol) was
added dropwise at 0.degree. C. under stirring to a solution of 8.21
g of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b']-dithiophene (39.79
mmol) in 150 mL of Et.sub.2O in a 500 mL 3-necked round flask. At
the end of the addition, the resulting dark suspension was stirred
for 30 min at r. t. A solution of
chloro(2,4,6-trimethyl-indenyl)dimethylsilane (10.00 g, 39.87 mmol)
in 20 mL of THF was cooled to 0.degree. C. and slowly added to the
above suspension, with final formation of a dark suspension. The
latter was allowed to warm up to room temperature and stirred for 3
h. Then the reaction mixture was concentrated under reduced
pressure to give a dark solid, which was extracted at r. t. with
150 mL of toluene to remove the LiCl. The extract was dried in
vacuo to give 17.37 g of a dark colored sticky foam. The .sup.1NMR
analysis showed the presence of the desired ligand together with
some impurities. The product was used as such in the next step
without further purification.
c) Synthesis of
dimethylsilyl[1-(2,4,6-trimethyl-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2--
b:4,3-b']-dithiophenyl)]zirconium dichloride (A-4)
##STR00011##
[0079] A 2.5 M n-BuLi solution in hexane (33.86 mL, 84.65 mmol) was
added dropwise at 0.degree. C. under stirring to a solution of
17.37 g of
1-(2,4,6-trimethyl-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dith-
iophene)dimethylsilane (41.29 mmol) in 200 mL of Et.sub.2O in a 500
mL 3-necked round flask. The resulting dark suspension was allowed
to warm up to r.t and stirred for 1 h. Then a suspension of 9.55 g
of ZrCl.sub.4 (40.98 mmol) in 100 mL of toluene was prepared,
cooled to 0.degree. C. and slowly added to the lithium salt
mixture, previously cooled to 0.degree. C. too. The resulting
reaction mixture was stirred at r. t. for 12 h. The solvents were
removed in vacuo yielding a residue, which was treated at r. t.
with toluene (2.times.150 mL) and filtered on a G4 frit. The
residue was further washed with toluene, while the filtrates were
collected and discarded. The residue was dried in vacuo to give
17.24 g of a brick-red powder, which resulted to be the desired
complex by NMR analysis, containing about 20% wt. of LiCl (yield
57.8%).
Synthesis of
dimethylsilanediyl{1-(2-methyl-4,6-disopropylindenyl)-7-(2,5-dimethyl-cyc-
lopenta[1,2-b:4,3-b']-dithiophene)}zirconium dichloride (A-5)
a) Synthesis of
chloro(2-methyl-4,6-disopropyl-1-indenyl)dimethylsilane
##STR00012##
[0081] A 2.3 M HexLi solution in hexane (6.00 mL, 13.80 mmol) was
added dropwise at 0.degree. C. to a solution of 2.93 g of
2-methyl-4,6-diisopropyl-1-indene (13.67 mmol) in 30 mL of
Et.sub.2O. At the end of the addition, the resulting white
suspension was allowed to warm up to room temperature and stirred
for 1 h. A solution of Me.sub.2SiCl.sub.2 (99%, 1.68 mL, d=1.064,
13.68 mmol) in 10 mL of Et.sub.2O was added at 0.degree. C. to the
lithium salt solution, previously cooled to 0.degree. C. The
reaction mixture was allowed to warm up to room temperature and
stirred for 3 h with final formation of a white suspension. The
solvents were removed in vacuo and the residue was extracted with
30 mL of toluene to remove the LiCl. The filtrate was brought to
dryness in vacuo at 40.degree. C. to give 3.33 g of a thick orange
oil. Crude yield=79.4%.
[0082] .sup.1H NMR (.delta., ppm, CDCl.sub.3): 0.12 (s, 3H,
Si--CH.sub.3); 0.45 (s, 3H, Si--CH.sub.3); 1.28-1.36 (m, 12H,
CH.sub.3); 2.31 (m, 3H, CH.sub.3); 2.97 (m, 1H, J=7.43 Hz, CH);
3.24 (m, 1H, J=7.43 Hz, CH); 3.58 (s, 1H, CH); 6.77 (m, 1H, Cp-H);
7.01 (bm, 1H, Ar); 7.20 (bm, 1H, Ar).
b) Synthesis of
1-(2-methyl-4,6-disopropylindenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b-
']-dithiophene) dimethylsilane
##STR00013##
[0084] A 2.3 M HexLi solution in hexane (3.00 mL, 6.90 mmol) was
added dropwise at 0.degree. C. to a suspension of 1.41 g of
2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b']-dithiophene (6.83 mmol) in
30 mL of Et.sub.2O. The resulting brown solution was stirred at
0.degree. C. for 1 h and then a solution of 2.10 g of
chloro(2-methyl-4,6-disopropyl-1-indenyl)dimethylsilane (6.84 mmol)
in 20 mL of Et.sub.2O was added at the same temperature. The
reaction mixture was then allowed to warm up to room temperature
and stirred for 3 h with final formation of a brown suspension. The
solvents were evaporated under reduced pressure and the residue was
extracted with 30 mL of toluene. The extract was dried in vacuo to
give 2.79 g of a sticky dark-brown solid, which was analyzed by
.sup.1H-NMR spectroscopy. The latter showed the presence of the
expected ligand, crude yield=68.5%. The product was used as such in
the next step without further purification.
[0085] .sup.1H NMR (.delta., ppm, CD.sub.2Cl.sub.2): -0.34 (s, 3H,
Si--CH.sub.3); -0.32 (s, 3H, Si--CH.sub.3); 1.27-1.39 (m, 12H,
CH.sub.3); 2.60 (s, 3H, CH.sub.3); 2.62 (s, 3H, CH.sub.3); 2.67 (s,
3H, CH.sub.3); 2.96 (m, 1H, J=7.24 Hz, CH); 3.29 (m, 1H, J=7.24 Hz,
CH); 3.87 (s, 1H, CH); 4.04 (s, 1H, CH); 6.82 (bs, 1H, Cp-H); 6.92
(m, 1H, CH); 6.94 (m, 1H, CH); 7.03 (bs, 1H, Ar); 7.23 (bs, 1H,
Ar).
c) Synthesis of
dimethylsilanediyl{1-(2-methyl-4,6-disopropylindenyl)-7-(2,5
dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)}zirconium dichloride
(A-5)
##STR00014##
[0087] A 2.3 M HexLi solution (5.1 mL, 11.73 mmol) was added
dropwise at 0.degree. C. to a solution of 2.79 g of
1-(2-methyl-4,6-disopropylindenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b-
']-dithiophene) dimethylsilane (5.85 mmol) in 30 mL of Et.sub.2O.
At the end of the addition, the resulting brown solution was
stirred for 1 h at room temperature. Then it was cooled again to
0.degree. C. to add a suspension of 1.36 g of ZrCl.sub.4 (5.83
mmol) in 15 mL of toluene, previously cooled to 0.degree. C. The
reaction mixture was then allowed to warm up to room temperature
and stirred for 16 h with final formation of a light brown
suspension. The solvents were removed in vacuo and the crude
residue was treated with 25 mL of toluene. The obtained suspension
was filtered: the filtrate was eliminated, while the residue was
dried to give 2.25 g of an orange powder, which resulted to be the
target complex, yield=60.6% with LiCl. 0.9 g of this powder were
treated with a mixture of 10 mL of toluene and 2 mL of isobutanol
and stirred for 15 min at room temperature. The mixture was then
filtered: the filtrate containing LiCl and by-products due to
decomposition was discarded, while the residue was concentrated in
vacuo yielding 0.5 g of an orange powder free from LiCl. This
powder resulted to be the pure complex by .sup.1H NMR analysis.
[0088] .sup.1H NMR (.delta., ppm, CD.sub.2Cl.sub.2): 1.18 (s, 3H,
Si--CH.sub.3); 1.34 (s, 3H, Si--CH.sub.3); 1.19 (d, 3H, J=6.85 Hz,
CH.sub.3); 1.20 (d, 3H, J=6.85 Hz, CH.sub.3); 1.26 (d, 3H, J=6.85
Hz, CH.sub.3); 1.35 (d, 3H, J=6.85 Hz, CH.sub.3); 2.39 (s, 3H,
CH.sub.3); 2.42 (d, 3H, J=1.17 Hz, CH.sub.3); 2.61 (d, 3H, J=1.17
Hz, CH.sub.3); 2.82 (m, 1H, J=6.85 Hz, CH); 3.06 (m, 1H, J=6.85 Hz,
CH); 6.64 (q, 1H, J=1.17 Hz, CH); 6.78 (q, 1H, J=1.17 Hz, CH); 6.80
(s, 1H, Cp-H); 6.93 (bt, 1H, Ar, H5); 7.32 (bq, 1H, Ar, H7).
Synthesis of rac
dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2--
b:4,3-b']-dithiophene)}zirconium dimethyl (A-6)
[0089] The ligand,
[3-(2,4,7-trimethylindenyl)][7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dit-
hiophene)]dimethyl silane, was prepared as described in WO
01/47939. 30.40 g of this ligand (72.26 mmol) and 170 ml of
anhydrous THF were charged under nitrogen in a cylindrical glass
reactor equipped with magnetic stirring bar. The brown solution so
obtained was cooled and maintained at 0.degree. C., while 58.4 ml
of n-BuLi 2.5M in hexane (146 mmol) were added dropwise via
dropping funnel. At the end of the addition, the dark brown
solution was stirred for 1 hour at room temperature, then cooled to
-50.degree. C., and then 48.6 ml of MeLi 3.05 M in diethoxymethane
(148.2 mmol) were added to it. In a Schlenk, 16.84 g of
ZrCl.sub.1-4 (72.26 mmol) were slurried in 170 ml of toluene. Both
mixtures were kept at -50.degree. C. and the ZrCl.sub.4 slurry was
quickly added to the ligand dianion solution. At the end of the
addition, the reaction mixture was allowed to reach room
temperature and stirred for an additional hour. A yellow-green
suspension was obtained. .sup.1H NMR analysis shows complete
conversion to the target complex. All volatiles were removed under
reduced pressure, and the obtained free flowing brown powder was
suspended in 100 ml of Et.sub.2O. After stirring for a few minutes,
the suspension was filtered over a G4 frit. The solid on the frit
was then washed twice with Et.sub.2O (until the washing solvent
turns from brown to yellow), then dried under vacuum, and finally
extracted on the frit with warm toluene (60.degree. C.), until the
filtering solution turns from yellow to colorless (about 650 ml of
toluene); The extract was dried under reduced pressure to give 28.6
g of yellow powder, which .sup.1H-NMR showed to be the target
complex, free from impurities. The yield based on the ligand was
73.3%.
[0090] .sup.1H-NMR: (CD.sub.2Cl.sub.2, r.t.), ppm: -2.09 (s, 3H),
-0.79 (s, 3H), 1.01 (s, 3H), 1.04 (s, 3H), 2.38 (s, 3H), 2.39 (s,
3H), 2.43 (d, 3H, J=1.37 Hz), 2.52 (s, 3H), 2.57 (d, 3H, J=1.37
Hz), 6.61 (dq, 1 H, 3=7.04 Hz, J=0.78 Hz), 6.81 (q, 1H, J=1.37 Hz),
6.85 (dq, 1H, J=7.04 Hz, J=0.78 Hz), 6.87 (q, 1H, J=1.37 Hz), 6.91
(s, 1H).
Polymerization Examples 1-5 and Comparative Examples 6-7
[0091] The cocatalyst methylalumoxane (MAO) was a commercial
product which was used as received (Witco AG, 10% wt/vol toluene
solution, 1.7 M in Al). The catalyst mixture was prepared by
dissolving the desired amount of the metallocene with the proper
amount of the MAO solution, (Al/Zr ratio=500) obtaining a solution
which was stirred for 10 min at room temperature before being
injected into the autoclave.
Polymerization (General Procedure)
[0092] 6 mmol of Al(i-Bu).sub.3 (as a 1M solution in hexane) and
1350 g of 1-butene were charged at room temperature in a 4-L
jacketed stainless-steel autoclave, equipped with magnetically
driven stirrer and a 35-mL stainless-steel vial, connected to a
thermostat for temperature control, previously purified by washing
with an Al(i-Bu).sub.3 solution in hexanes and dried at 50.degree.
C. in a stream of nitrogen. The autoclave was then thermostated at
the polymerization temperature, and then the toluene solution
containing the catalyst/cocatalyst mixture was injected in the
autoclave by means of nitrogen pressure through the stainless-steel
vial, and the polymerization carried out at constant temperature
for the time indicated in Table 1. Then stirring is interrupted;
the pressure into the autoclave is raised to 20 bar-g with
nitrogen. The bottom discharge valve is opened and the
1-butene/poly-1-butene mixture is discharged into a heated steel
tank containing water at 70.degree. C. The tank heating is switched
off and a flow of nitrogen at 0.5 bar-g is fed. After cooling at
room temperature, the steel tank is opened and the wet polymer
collected. The wet polymer is dried in an oven under reduced
pressure at 70.degree. C. The polymerization conditions and the
characterization data of the obtained polymers are reported in
Table 1.
TABLE-US-00001 TABLE 1 time Yield kg/ I.V. mmmm 4,1 T.sub.m EX Met
mg T.sub.pol (min) (g) (g.sub.cat*h) (dL/g) M.sub.w/M.sub.n %
regioerrors (Form II) 1 A-1 2 60 60 130 65.0 2.4 3.1 95.8 n.d.
105.5 2 A-1 2 70 60 125 62.5 2.0 3.9 95.3 n.d. 104.4 3 A-1 2 80 60
100 50.0 1.3 3.7 95.2 n.d. 103.9 4 A-4 3 70 60 82.5 27.5 1.7 n.a.
n.a. n.a. 101 5 A-5 2 70 60 86.6 43.3 1.5 n.a. n.a. n.a. 100.2 3*
A-2 4 60 15 80 80.0 0.5 n.a. 85.5 n.d. 78 4* A-3 3 70 60 109 36.3
1.3 3.1 89.0 n.d. 84 *= comparative n.d. = not detectable n.a. =
not available
Examples 6-8 Influence of Hydrogen
[0093] The procedure of examples 1-5 has been repeated with the
metallocene compound A-1 and an Al(MAO)/Zr ratio of 200, with the
exception that an amount of H.sub.2 reported in table 3 is injected
into the autoclave before the injection of the catalyst solution.
The results are reported in table 3
TABLE-US-00002 TABLE 3 I.V. T.sub.pol time H.sub.2 H.sub.2
kg.sub.PB/ dL/g, M.sub.v Ex mg .degree. C. (min) NmL ppm .sup.+
(g.sub.mtcene .times. h) (THN) (IV.sub.THN) 6 2 70 60 0 0 82.5 2.34
479 800 7 2 70 60 100 2 163 n.a. n.a. 8 2 70 60 200 4 220 1.44 245
600 n.a. not available .sup.+ ppm in liquid phase
From these examples result that hydrogen can be used as activating
agent in order to increase the final yield.
Examples 9-12 ethylene/1-butene copolymers
[0094] The cocatalyst methylalumoxane (MAO) was a commercial
product which was used as received (Crompton 10% wt/vol 1.7 M in
Al). The catalyst mixture was prepared by dissolving 2 mg of A-1
with the proper amount of the MAO solution, (Al/Zr ratio=200)
obtaining a solution which was stirred for 10 min at room
temperature before being injected into the autoclave.
[0095] A 4.25 litres steel autoclave, equipped with magnetically
stirred anchor (usual stirring rate 550 rpm) and with different
Flow Record & Control systems (FRC), among which a FRC having
maximum flow rate of 9000 gr/hour for 1-butene and two FRC having
maximum flow rate of 500 and 30 g/h for ethylene is cleaned with
warm nitrogen (1.5 barg N.sub.2, 70.degree. C., 1 hour). After the
above mentioned autoclave cleaning, the stirring starts, 1-butene
is fed into the reactor (1350 gr at 30.degree. C.) with the amount
of ethylene reported in table 4, together with 6 mmol of
Al(i-Bu).sub.3 (TIBA) (as a 1 M solution in hexane). Subsequently,
the reactor inner temperature is raised from 30.degree. C. to
70.degree. C., the polymerisation temperature; as a consequence the
pressure increases. When pressure and temperature are constant, the
catalytic solution is fed into the reactor with a nitrogen
overpressure and the polymerisation pressure is kept constant
feeding only ethylene (amount indicated in table 3). The
polymerisation is run for 60 minutes. Then the stirring is
interrupted; the pressure into the autoclave is raised to 20 bar-g
with nitrogen. The bottom discharge valve is opened and the
1-butene/poly-1-butene mixture is discharged into the steel heated
tank containing water at 70.degree. C. The tank heating is switched
off and a flux of 0.5 bar-g nitrogen is fed. After 1 hour cooling
at room temperature the steel tank is opened and the wet polymer
collected. The wet polymer is dried in a oven under nitrogen at
70.degree. C. The polymerization conditions and the
characterization data of the obtained polymers are reported in
Table 4
TABLE-US-00003 TABLE 4 C.sub.2 in liq. activity C.sub.2 in copol. R
I.V. phase C.sub.2 fed kg.sub.PB/ mol % (C.sub.2/C.sub.4).sub.copo/
dL/g T.sub.m mmmm .DELTA.H Ex % wt g (g.sub.mtcene .times. h) (NMR)
(C.sub.2/C.sub.4).sub.liq. phase THN (Form II) % J/g 9 0.19 2.6 58
2.28 6.1 2.61 77.8 >90 19.4 10 0.38 4.1 88 2.99 4.0 2.65 75.7
>90 15.7 11 0.64 7.4 122 6.24 5.2 2.56 60.9 >90 0.8 12 0.38 9
191 n.a. n.a. n.a. n.a. n.a. n.a. n.a. not allowable
From table 4 it results that the yield of the process of the
present invention can be increased by using ethylene or both
ethylene and hydrogen (example 16). In addition the use of ethylene
further increases the molecular weight of the polymer.
* * * * *