Note: Descriptions are shown in the official language in which they were submitted.
CA 02253804 2004-04-26
TITLE: CATALYST SYSTEM CONTAINING REACTION PRODUCT
OF LIQUID SILICONE AND POLYAMINE
The invention relates to novel catalyst systems and the use of such
catalyst systems in the polymerization of olefins. The catalyst system of the
invention contains an olefin polymerization catalyst and, as a catalyst
support,
the reaction product of a liquid silicone and a polyamine. A preferred liquid
silicone is one having a viscosity at 25_degrees C. of less than 1,000 cst.
The
catalyst system of the invention is homogeneous. As such, it has particular
applicability in the production of polyolefins of narrow molecular weight
distribution.
Polyolefrns are useful for a large variety of applications. These polymers
are used to fabricate articles under conventional film blowing, injection
molding
and blow molding techniques. The molecular weight distribution of the polymer
is a determinant in assessing whether the polymers are suitable for these
various
applications. For example, in injection molding, polyolefin polymers having a
narrow molecular weight distribution are preferred. On the other hand, in blow
molding, polyolefins having a broad molecular weight distribution are
preferred.
Typically, unsupported catalysis systems have too small a particle size for
commercial use. Supported catalysis systems are characterized by larger
particle sizes and offer improved catalytic efficiency. Further, they ace
generally
more stable and render higher molecular weight polymers.
CA 02253804 2004-04-26
Supports of the catalysis systems of the prior art, typified by silica gel,
traditionally are used under slung polymerization conditions. Unfortunately,
it is
often difficult to control the amount of catalyst on a silica get support. In
addition,
silica gel is capable of deactivating certain catalysts and further may leave
high
concentrations of ash in the resulting polymer.
Further, the supported catalysis systems of the prior art are ~generalty
incapable of producing polyolefins with the requisite narrow molecular weight
distribution needed for injection molding. tn addition, such supported
catalysis
systems are heterogeneous in nature. As such, it is not uncommon for solid
particulates or gels to become either deposited within the reactor or engulfed
in
the resultant polyolefin. The former, referred to as fouling,. is often
detrimental to
the overall process since heat transfer is lost and the reactors typically
must be
shut down for a difficult cleaning process.
A need therefore exists for the development of a catalysis system which is
homogeneous in nature, i.e., either liquid or capable of remaining in solution
in
the presence of an inert hydrocarbon, and which exhibits high thermal
stability
and which is capable of producing polyolefins of narrow molecular weight
distribution.
The invention relates to a catalyst system containing an olefin
polymerization catalyst containing at least one Group 3 to Group 10 transition
metal and an organic support. The support is the reaction product of a liquid
silicone and a polyamine. .
The resulting catalyst system exhibits a high degree of thermal stability.
In addition, the catalyst system is homogeneous. Such homogeneity offers
greater control over the concentration of polymerization catalyst during the
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CA 02253804 2004-04-26
production of the polymer. The resulting polyolefin has a narrow molecular
weight
distribution and further has a diminished ash content.
According to one aspect of the present invention there is provided a
catalyst system comprising the combination of: a support which is the reaction
product of a liquid silicone and a polyamine containing between 2 and 35
carbon
atoms reacted in an organic solvent; and an olefin polymerization catalyst
containing a Group 3 - 10 metal or one of the Lanthanide series of the
Periodic
Table.
According to a further aspect of the present invention there is provided a
homogeneous supported catalyst system comprising the product of reaction of:
a support which is the reaction product of a liquid silicone having a
viscosity at
25°C of less than 10,000 cst. And a polyamine having between 2 and 35
carbon
atoms reacted in an organic solvent, as the support; and an olefin
polymerization
catalyst containing a Group 4b, 5b or 6b metal wherein the liquid silicone is
a
silicone containing the repeating units of the formula:
R R
R~ Si O Si R~ (I)
R R
m
wherein each R is individually selected from alkyl (or aryl) groups having
from 1 to
12 carbon atoms, R~ is halogen or -OR, and m is generally an integer of from 1
to
about 10,000.
The catalysis system of the invention comprises an olefin polymerization
catalyst and a support. The support is the reaction product of a liquid
silicone and
a polyamine. The homogenous catalysis system exhibits high thermal stability
thereby permitting the production of polyolefins at increased operating
temperatures over those previously realized in the art.
The silicone for use in the invention is one wherein the viscosity at 25
degrees C. is less than 10,000 cst, preferably less than about 1,000 cst, most
preferably less than 10 cst.
Exemplary of the liquid silicone for use in the invention are those containing
the repeating units of the formula:
-3-
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R R
R~ Si O Si R~
R R
m
wherein each R is individually selected from alkyl (or aryl) groups having
from 1 to
about 12 carbon atoms, R~ is halogen or -OR, and m is generally an integer of
from about 1 to about 10,000, preferably about 2 to about 5,000. Specific
examples include halogenated or alkoxylated derivatives of
hexamethyldisiloxane,
octamethyltrisiloxane, methylethyl-polysioloxane, dimethylpolysiloxane,
hexamethylcyclotrisiloxane, octamethylcyclo-tetrasioloxane and the like.
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In a particularly preferred embodiment, the silicone may be of the formula
(I) above where R is methyl or ethyl, and m is 1 to about 100, most preferably
between 1 to 6. Particularly desirable results have been demonstrated wherein
R is methyl and R, is chlorine.
The polyamine that is reacted with the liquid silicone typically contains
from 2 to about 35, preferably about 2 to about 20, carbon atoms. Since
diamines reduce the amount of crosslinking, they are preferred. However, tri-
and tetra- amines may also be employed.
Representative polyamines are of the generic formula:
H2N - R 2 - (T - R 2)c - NH2 (ll)
wherein RZ is a hydrocarbyl group such as an alkyl, aryl, alkaryl or aralkyl
(typically of 1 to about 12 carbon atoms) which further may be optionally
substituted with a group selected from NH2, NHRZ, N(R2)2, haloalkyl or halogen
(preferably -CI or -Br); t is O, 1 or 2 (preferably O or 1 } and T is -O-,
carbonyl,
sulfonyl, sulfide, or
3
Si -O p SI -- (lll)
R3 R3
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wherein p is 1 to 200, preferably to 100, most preferably 3 to 12, and R3 is a
C,-
C,z, preferably C,-C3, hydrocarbyl group, most preferably methyl or a .
halogenated hydrocarbyl group containing up to 12 carbon atoms.
The low color of aliphatic amines makes them a particularly preferred
species. Most preferred are those amines having between from about 5 to about
12 carbon atoms. Amines having fewer than 5 carbon atoms typically bring the
transition metals bonded to them too close together for effective catalysis.
Amines having more than 12 carbon atoms tend to lower the concentration of
transition metal to support polymer.
Examples of suitable aromatic amines include m-phenylenediamine;
p-phenylenediamine; 2,5-dimethyl-1,4-phenylenediamine; 2,4, 2,5- and 2,6-
diaminotoluene; p-xylyienediamine; m-xylylenediamine; 4,4'-diaminobiphenyl;
4,4'-diaminodiphenyl ether (or 4,4'-oxydianiline); 3,4'-oxydianiline; 4,4'-
diaminobenzophenone; 3,3-diaminophenyl sulfone ; 3,4'-diaminophenyl suffone;
4,4-diaminophenyl sulfone; m,m-sulfone dianiline; m,p-sulfone dianiline; p,p-
sulfone dianiline; 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenyf sulfone;
3,3'
or 4,4'-diaminodiphenylmethane; m,m-methylenedianiline; p,p-methylene
dianiline; 3,3'-dimethylbenzidine; 2,2'-bis[(4-aminophenyl)-1,3-diisopropyl]
benzene; 4,4'-isopropylidenedianiline (or bisaniline); 2,2'-bis[(4-
aminophenyl)-
1,3-diisopropyl]benzene or 3,3'- isopropylidenedianifine (or bisaniline M);
methylene dianiline; 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(4-aminophenoxy)
benzene; 4,4'-bis(4-aminophenoxy) biphenyl; 1,3-bis(3-aminophenoxy)benzene;
4,4'-bis(4-aminophenoxy)biphenyl; 2,4-diamine-5-chlorotoluene; 2,4-diamine-fi-
chlorotoluene; 2,2-bis-[4(4-aminophenoxy)phenyl]propane; trifluoromethyl-2,4-
diaminobenzene; trifluoromethyl-3,5-diaminobenzene; 2,2-bis(4-aminophenyl)-
hexafluoropropane; 2,2-bis(4-phenoxy aniline) isopropylidene; 2,4,6-trimethyl-
1,3-diaminobenzene; 4,4'-diamino-5,5'-trifluoromethyl diphenyloxide; 3,3'-
diamino-5,5'-trifluoromethyl diphenyloxide; 4,4'-tri-fluoromethyl-2,2'-diamino
-5-
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biphenyl; 2,4,6-trimethyl-1,3-diaminobenzene; 4,4'-oxybis[(2-trifluoromethyl)
benzeneamine]; 4,4'-oxybis[(3-trifluoromethyl) benzeneamine]; 4,4'-thiobis[(2-
trifluoromethyl)benzeneamine]; 4,4'=thiobis[(3-trifluoromethyl)benzeneamine];
4,4'-sulfoxylbis[(2-trifluoromethyl)benzene-amine]; 4,4'-sulfoxylbis[(3-
trifluoro-
methyl)benzeneamine]; 4,4'-ketobis((2-trifluoromethyl)benzeneamine]; 4,4'-
[(2,2,2-trifluoromethyl-1-(trifluoro-methyl)-ethylidine)bis(3-trifluoromethyl)
benzeneamine]; and 4,4'-dimethyl-silylbis[(3-trifluoromethyl)benzeneamine].
Specific examples of suitable aliphatic amines include 2-methyl-1,5-
diamino pentane, 1,6-hexanediamine, 1,8-octanediamine, 1,12-diamino-
dodecane, 1,4-diaminocyclohexane, and 1,4-bis-(aminomethyl)-cyclohexane.
Examples of diamines includes those of formula (IV):
Rs Rs
HzN- RZ I i - O i- R2 NHZ (IV)
Rs Rs
P
where R3 is --CH3, --CF3, --CH=CH 2; --(CHZ)9CF3, where g is 1 to 12, --C6H5,
and
--CHF- CF3. Examples of the RZ group include --(CH2)q--, --(CF2)q, --
(CH2)q(CF2)q -, and --C6H 4--, where each q is independently chosen from 1 to
10.
The polyamine may further be a diaminoanthraquinone.
The reaction between polyamine and the liquid silicone is conducted in
the presence of an organic solvent. Organic solvents which are preferred as
the
media for conducting the reaction of polyamine and silicone include toluene,
hexane, diethyl ether and tetrahydrofuran (THF). Hexane is particularly
preferred. In a preferred embodiment, the organic solvent is the same solvent
employed in the polymerization of the olefin(s).
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The reactivity of the polyamine and liquid silicone may be increased by
further conducting the reaction in the presence of a compound capable of .
abstracting a proton from the primary amine group. Examples of such proton-
abstraction compounds include alkyl lithium compounds, e.g., methyl lithium or
butyl lithium, or trialkylamines such as triethyl amine. The former is
particularly
effective in scavenging the acid byproduct.
The reaction of the polyamine with the liquid silicone is generally
conducted in the organic solvent at a temperature ranging between from about -
78°C to about room temperature. Stoichiometric quantities of the
polyamine and
silicone are preferably used. While the reaction proceeds rapidly, it should
be
left overnight to ensure completion. The resulting reaction product is a
liquid.
The reaction product may be represented by the general formula
R3 R 3
(V)
NH - R2 - NH Si O Si
R3 m R
3
n
where R3, Rz, and m are as defined above, and n is between from about 2 to
about 500, preferably between from about 4 to about 50.
The olefin polymerization catalyst, which when combined with the support
constitutes the catalysis system of the invention, may be any conventional
polyolefin catalyst which contains a a Group 3 to Group 10 metal or one of the
- -7-
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Lanthanide secies of the Periodic Table. . Preferred are those containing a
Group
4b, 5b or 6b transition metal; preferably Ti, Zr, Cr and V; most preferably Ti
and
Zr.
Included within such metallic olefin polymerization catalysts are trivalent or
tetravalent metallic compounds of the general formula M(R,~)y wherein M is a
Group 3 to Group 10 rn~etal or one of the Lanthanide series as specified
above,
preferably titantium, vanadium, chromium or zirconium and y is either 3 or 4
and
further wherein R, is independently selected from halogen (preferably chlorine
or
bromine), a C,-C2o alkyl, an aryl (preferably a Cs - C,e aryl), a C,-C2o
alkaryl or
aryalkyl, a C, - C~ siloxy and an amide.
The olefin polymerization catalyst may further contain n - bonded ligands,
such as the mono--, bi-- or tri- cyclopentadienyl or substituted
cyctopentadienyt
metal compounds. Preferred are the monocyclopentadienyl metal compounds or
substituted derivatives thereof. Preferred amongst the cyclopentadienyl metal
compounds are those represented by the general formulae:
(CsR'W)r RZs (C s R' W) MQs.s (Ul)~ and
R2s(CsR'W)zMQ' (VII)
wherein
(CSR'W) is a cyclopentadieny! or substituted cyclopentadienyl; each R' is the
same or different and is hydrogen or a hydrocarbyl radical such as
alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical containing from 1 to 20
carbon atoms or two carbon atoms are joined together to form a C,-C6
ring;
_g_
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R_2 is a C,-C4 alkylene radical, a dialkyl germanium or silicon [such as silyl
or a compound of the formula -Si(R5), wherein t is 2 or 3 and further
wherein each R5 is -H, a C;-C,o (preferably a C ,-C 4) alkyl group, an
aryl such as benzyf or phenyl or a benzyl or phenyl group substituted
with one or more C,-C4 alkyl groups] or an alkyl phosphine or amine
radical bridging two (C5R'W) rings;
Q is a hydrocarbyf radical such as aryl, alkyl, alkenyl, alkylaryl or
arylalkyl
radical having from 1-20 carbon atoms or halogen and can be the same
or different,
Q' is an alkylidene radical having from 1 to about 20 carbon atoms,
s is O~or 1;
f is 0, 1 or 2
provided that when f is 0, s is 0;
when w is 4 s is 1;
when w is 5 s is 0;
at least one R' is a hydrocarbyl radical when Q is an alkyl radical and
M is preferably a Group 4b, 5b or 6b metal, desirably Ti or Zr, most
preferably Ti.
Illustrative but non-limiting examples of such metallocenes are
monocyclopentadienyl titanocenes such as cyclopentadienyl titanium
trichioride,
pentamethylcyclopentadienyl titanium trichloride; bis(cyclo-pentadienyl)
titanium
diphenyl, the carbene represented by the formula CpzTi=CH2 AI(CH3)ZCI and
derivatives of this reagent such as Cp2Ti=CHZ~AI(CH3)3, (CpzTiCH2)z.
Cp2TICH2CH(CH3)CH2, Cp2Ti=CHCHZCH2, and
_g_
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Cp2Ti=CH2~AIR"'2C1 wherein Cp is a cyclopentadienyl or substituted
cyclopentadienyl radical and R"' is an alkyl, aryl or alkylaryl radical having
from
1-18 carbon atoms; substituted bis(Cp)Ti(I~ compounds such as
bis(indenyl)titanium diphenyl or dichloride,
bis(methylcyclopentadienyl)titanium
diphenyl or diahalides and other dihalide complexes; dialkyl, trialkyl,
tetraalkyl
and pentaalkyl cyclopentadienyl titanium compounds such as bis(1,2-dimethyl-
cyclopentadienyl}titanium diphenyl or dichloride, bis(1,2-
diethylcyclopentadienyl)
titanium diphenyl or dichloride and other dihalide complexes silicone,
phosphine,
amine or carbon bridged cycfopentadiene complexes such as dimethyl
silyldicyclo-pentadienyl titanium diphenyl or dichloride, methyl phosphine
dicycfo-
pentadienyl titanium Biphenyl or dichloride, methylenedicyclopentadienyl
titanium
Biphenyl or dichloride, ethylene bis(4,5,6,7-tetrahydroindenyl) titanium
dichloride
and other dihalide complexes and the like.
Illustrative but non-limiting examples of the zirconocenes which can be
employed in accordance with this invention are cyclopentadienyl zirconium
trichloride, pentamethylcyciopentadienyf zirconium trichloride, bis(cyclo-
pentadienyl)zirconium Biphenyl, bis(cyclopentadienyl)zirconium dimethyl, the
alkyl substituted cyclopentadienes duch as bis(ethylcyclopentadienyl)
zirconium
dimethyl, bis((3-phenylpropyfcyclopentadienyl)zirconium dimethyl,
bis(methylcyclopentadienyl) zirconium dimethyl and dihalide complexes of the
above; dialkyl, trialkyl, tetraalkyl, and pentaalkyl cyclopentadienes such as
bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(1,2-dimethyl-
cyclopentadienyl)zirconium dimethyl, bis(1,3-diethylcyclopentadienyl)
zirconium
dimethyl and dihalide complexes of the above; silicone, phosphorous, and
carbon bridged cyclopentadiene complexes such as dimethylsilyldicyclo-
pentadienyl zirconium dimethyl or dihalide, methylphosphine dicyclopentadienyl
zirconium dimethyl or dihalide and methylene dicyclopentadienyl zirconium
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dimethyl or dihalide, carbenes represented by the formulae
CpzZr=CHZP(CsHs)ZCH3 and derivatives of these compounds such as
Cp2ZrCH2CH(CHa)CH2
!n a further preferred embodiment, the catalyst may be described by the
formulae (VI) and (Vlij above wherein f is 0 or 1 and RZ is independently
selected
from the group consisting of methylene, ethylene, 1,2-phenylene, dimethyl
silyl,
Biphenyl siiyl, diethyl silyhand methyl phenyl silyl.
The olefin polymerization catalyst for use in the invention may
further be any of those defrned as the "constrained geometry catalysts" set
forth
in U.S. Patent Nos. 5,272,236 and 5,278,272. Such catalysts comprise a metal
coordination complex of a metal and a delocalized pi-bonded moiety substituted
with
a constrain-inducing moiety; the complex having a constrained geometry about
the
metal atom such that the angle at the metal between the centroid of the
delocalized,
substituted pi-bonded moiety and the center of at least one remaining
substituent is
less than such angle in a similar complex containing a similar pi-bonded
moiety
lacking in such constrain-inducing substituent; provided further that for such
complexes comprising more than one delocalized, substituted pi-bonded moiety,
wherein only one thereof for each metal atom of the complex is a cyclic,
delocalized
substituted pi-bonded moiety.
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Preferred catalyst complexes correspond to the formula:
Z Y
(VIII)
Cp M
~X)v
wherein:
Cp, the cyciopentadienyl or substituted cyclopentadienyl group, is
bound in an ~5 bonding mode to M;
Z is a moiety comprising boron, or a member of Group 14 and
optionally sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms,
and optionally Cp and Z together form a fused ring system;
X independently each occurrence is an anionic ligand group or neutral
Lewis base ligand group having up to 30 non-hydrogen atoms;
v is 0, 1, 2, 3, or 4 and is 2 less than the valence of M; and
Y is an anionic or nonanionic ligand group bonded to Z and M
comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20
non-hydrogen atoms; optionally Y and Z together form a fused ring system.
In a preferred mode, such complexes correspond to the formula:
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R"
Z Y
(lX)
R
R"
tX)v
R"
wherein:
each occurrence of R" is independently selected from the group
consisting of hydrogen, alkyl, aryl, silyl, germyl, cyano, halo and
combinations
thereof having up to 20 non-hydrogen atoms;
each occurrence of X is independently selected from the group
consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy,
amide, siloxy,
neutral Lewis base ligands and combinations thereof having up to 20
non-hydrogen atoms;
Y is -O-, -S-, -NR*-, -PR*-, or a neutral two electron donor ligand
selected from the group consisting of OR*, SR*, NR* Z or PR* 2;
M is as previously defined; and
Z is SiR* 2, CR* 2, SiR*z SiR* z, CR* Z CR* z, CR*=CR*, CR* 2SiR* 2,
GeR* z, BR*, BR* 2;
wherein
each occurrence of R* is independently selected from the group
consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated
aryl
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groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or
more R* groups from Y, Z, or both Y and Z form a fused ring system; and
- v is 1 or 2.
Most highly preferred complex compounds are amidosilane- or
amidoalkanediyl-compounds corresponding to the formula:
R"
a ~ N-R"
R.. M
(X)
R"
wherein:
(X)
M is titanium, zirconium or'hafnium, bound in a r~5 bonding mode to the
cyclopentadienyl group;
each occurrence of R" is independently selected from the group
consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up
to 10
carbon or silicon atoms;
E is silicon or carbon;
each occurrence of X is independently hydride, halo, alkyl, aryl, aryloxy
or alkoxy of up to 10 carbons;
d is 1 or 2; and v is 2.
Examples of the above most highly preferred metal coordination
compounds include compounds wherein the R" on the amido group is methyl,
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ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbomyl, benzyl,
phenyl,
etc.; the cyclopentadienyl group is cyclopentadienyl, indenyl,
tetrahydroindenyl,
fluorenyl, octahydrofluorenyl, etc.; R" on the foregoing cyclopentadienyl
groups
each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,
(including isomers), norbornyl, benzyl, phenyl, etc.; and X is chloro, bromo,
iodo,
methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbomyl,
benzyl,
phenyl, etc. Specific compounds include (tert-butylamido)(tetramethyl-ris
-cyclopentadienyl)-1,2-ethanediylzirconium dichloride, (tertbutylamido)
(tetramethyl- ~s - cyclopentadienyl) 1,2-ethanediyltitanium dichloride,
(methylamido)(tetramethyl- ~5 -cyclopentadienyl)-1,2-ethanediylzirconium
dichloride, (methylamido) (tetramethyl-r)s- cyclopentadienyl)-1,
2-ethanediyltitanium dichloride, (ethylamido)(tetramethyl-r)s -
cyclopentadienyl)
-methylenetitanium dichloro, (tertbutylamido)dibenzyl(tetramethyl-~s-
cyclopentadienyl) silanezirconium dibenzyl, (benzyiamido)dimethyl
(tetramethyl-rls-cyclopentadienyl) silanetitanium dichloride,
(phenylphosphido)
dimethyl(tetramethyl r)s-cyclopentadienyl) silanezirconium dibenzyl,
(tertbutylamido)dimethyl (tetramethyl-r)5-cyclopentadienyl) silanetitanium
dimethyl, and the like.
Still further the catalyst for use in the catalysis system of the invention
may be one of those set forth in either U.S. Patent No. 5,434,116 or U.S.
Patent
No. 5,539,124. Such catalysts include those represented by the general
formula
I~PIq,
I
ILIm, - M - IKh, (XI)
IBIp,
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where L is a ligand, or mixture of ligands, each having 4 to 30 carbon atoms
and
containing at least two fused rings, one of which is a pyrrolyl ring, Cp is a
li~and
containing a cyclopentadienyl ring, where two L ligands or an L and a Cp
ligand
can be bridged, B is a Lewis base, K is halogen, alkoxy from C, to C2o, siloxy
from C, to C2o, N(RZ)2, or mixtures thereof, RZ is as defined above, M is
preferably titanium, zirconium, or mixtures thereof, m1 is a number from 1 to
4,
n1 is a number from 0 to 2, p1 is a number from 0 to 2, q1 is a number from 0
to
1, and m1...+ n1 + q1 = 4. In the formula, K is preferably halogen and is more
preferably either chlorine or bromine, but alkoxy groups, such as methoxy
(CH30-), ethoxy (CH3CHz0-), or siloxy (R6)3Si0-, where R6 is alkyl from C, to
CZO,
should also be mentioned. Also, m1 is preferably 4.
Examples of L groups that can be used include alkyl substituted pyrrolyl
rings,
(XII)
N
(R3) P1
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such as 2-methylpyrrolyl, 3-methylpyrrolyl, 2,5-dimethylpyrrolyl, 2,5-di-tert-
butylpyrrolyl, aryl substituted pyrrolyl rings such as 2-phenylpyrrolyl, 2,5-
diphenylpyrrolyl, indolyl, alkyl substituted indolyls
O
(XIlI)
~R3) P1
such as 2-methylindolyl, 2-tert-butylindolyl, 3-butylindolyl, 7-methylindolyl,
4,7-
dimethyiindolyl, aryl substituted indolyls such as 2-phenylindolyl, 3-
phenylindolyl,
2-naphthylindolyl, isoindolyl, and alkyl and aryl substituted isoindolyls
(Rs ) P 1 ~XI~
N
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and carbazolyl and alkyl substituted carbazolyls
3
{R )P1 ~X~
In the formulas, each R3 is preferably independently selected from hydrogen,
alkyl from C, to C,o, and aryl from C6 to C,o and p1 is the number of
substituents
on the ring. {1n formula XV, for instance, p is 8.) The alkyl and aryl
substituents
on the pyrro(yl ring-containing ligand are not on the nitrogen atom in the
ring but
are on the carbon atoms of the ring. Particularly preferred L ligands are the
carbazolyl and C, to C4 alkyl indolyls in the 2 or 7 position, or in both
positions.
Examples of Lewis bases, B, which can be used include diethyl ether,
dibutyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. The Lewis base B is
residual solvent and the bond between B and M is not a covalent bond.
The Cp ligand can be a cyclopentadienyl ring with 0 to 5 substituent
groups,
_1 g_
CA 02253804 2004-04-26
X~l
(R4)~
where each substituent group, R', is independently selected from a C, to C~
hydrocarbyl group and r is a number from 0 to 5.
!n the case in which two R' groups are adjacent, they can be joined to
produce a ring which is fused to the Cp ring. Examples of alkyl substituted Cp
rings include butyl cyclopentadienyl, methyl cyclopentadienyl, and
pentamethylcyclo-pentadienyl. Examples of fused Cp ring ligands include
indenyl, tetrahydroindenyl, fluorenyl, and 2-methylindenyl.
Groups that are preferably used to bridge two ligands include
methylene, ethylene, 1,2-phenylene, dimethyl silyl, Biphenyl silyl, diethyl
silyl,
and methyl phenyl silyl. Normally, only a single bridge is used in a catalyst.
Still further, the catalyst used in this invention may be ane of those
represented by the general formula
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L* X*
. \/
M , L*B (XV11)
I1
b L*' X*
where L* is a ligand having the formula
Rio
(XVIII)
B
N,~~
R2o ~ (Rso) **
n
L*' is L*, Cp, Cp~, indenyl, fluorenyl, NR2, OR25, or halogen, L* can be
bridged to
L*', X* is halogen, NRZ, OR25, or alkyl from C , to C ,z, M is preferably
titanium,
zirconium, or hafnium, n** is 0 to 3, Rzs is alkyl from C, to C,2 or aryl from
C6 to
C,2, R,o is R2S, alkaryl from C6 to C,2, aralkyl from C6 to C,2, hydrogen, or
S1(R25)3,
Rzo is R,o, halogen, COR25, COORzs SOR25, or SOOR25, R3o is Rzfl, OR25,
N(Rzs),
SR25, or a fused ring system, Cp is cyclopentadienyl, and Cp~ is
pentamethylcyclopentadienyl.
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The X* group is preferably halogen and most preferably chlorine as
those compounds are more readily available. The R25 group is preferably alkyl
from C, to C4, the R,o group is preferably alkyl from
C3 to C,2 or aryl, the R2o group is preferably t-butyl or trimethylsilyl, and
the R3o
group is preferably hydrogen or methyl as those compounds are easier to make.
Examples of fused ring structures that can be used include
CH3
O N - R2o O O O N - Ryo
N RZ°
Rio I Rio
Rio
(XIX) (XX) (XXI)
The metal M is most preferably zirconium, as the zirconium catalysts offer a
good combination of activity and stability.
Optionally, L * can be bridged to L*'. Groups that can be used to
bridge the two ligands include methylene, ethylene, 1,2-phenylene,
dimethylsilyl,
diphenylsilyl, diethylsilyl, and methylphenylsilyl. Normally, only a single
bridge is
used.
In the general formula, L*B is an optional Lewis base. Up to an
equimolar amount (with M) of base can be used. The use of the Lewis base is
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CA 02253804 2004-04-26
generally not preferred because it tends to decrease catalyst activity.
However,
it also tends to improve catalyst stability, so its inclusion may be
desirable,
depending upon the process in which the catalyst is to be used. The base may
be residual solvent from the preparation of the azaboroline containing
compound
or it may be added separately in order to enhance the properties of the
catalyst.
Examples of bases that can be used include ethers such as diethylether,
dibutylether, tetrahydrofuran, 7,2-dimethoxyethane, esters such as n-
butylphthalate, ethylbenzoate, and ethyl p-anisate, tertiary amines such as
triethylamine, and phosphines such as triethyf phosphine, tributyl phosphine,
and
triphenyi phosphine.
The catalyst for use in the invention may further be a bora-benzene ring
structure which contains a metal such as those described in U.S. Patent No. 5
554 775. Included within this group are those catalysts represented by the
general
formula
q5 X"
i
BB - M - L" ~ B* (XXII)
I
Xn
wherein BB is a ligand containing a bora-benzene ring. A born-benzene ring has
the structure
(XXIII)
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where R4o can be N(R 5o)z, OR so. or R 50, where each R So is independently
selected from alkyl from C, to C,o, aryl from C 6 to C ,5, alkaryl from C, to
C,S, and
aralkyl from C ~ to C ,5. The R 4o group is preferably -N(Rso)2 or phenyl, as
those
catalysts have the best properties and, if R4o is -N(R So)2, then the R So in -
N(R 50)
2 is preferably methyl. Examples of BB ligands include
~Rso)m~
(Reo)m~~
B
g R40 ~R60} m~~
Rao
R4o
(bora-benzene) (bora-naphthalene) (bora-naphthalene)
(XXIV) (XXV) (XXVI)
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WO 97/41157 PCT/US97/07483
(Rso)
m*.
(R60) m* ~ B
B
R4o
R4o
(bora-anthracene) (bora-phenanthrene)
(XXVII) (XXVIII)
where "m*" is 0 to the maximum number of substitutable positions, and is
preferably 0 as those catalysts are easier to make. Each Rso is independently
selected from halogen, alkoxy from C, to C,o, and RSO. The preferred BB
ligands
are bora-benzene, bora-naphthaleng, and bora-anthracene.
In the general formula, each X' is independently selected from
hydrogen, halogen, alkoxy from C, to C,o, dialkylamino from C, to C,o, methyl,
1 1
(R60) n*, ~~C1~ n*,
and
(XXIX) (XXX)
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where "n'" is 0 to 5 and preferably is 0. The X' group is preferably chlorine
or
methyl, as those catalysts are easy to prepare and have good properties.
Also, L" in the general formula can be
c~a
~(Rso) ~* ,
c~
cRso) ~* , C
I
R4o R4o
~(R6a n* ~ ~ cR60) ~*
~C
R40
R4o
BB, or X". Preferably, L" is BB, cyclopentadienyl, or chlorine because those
catalysts are easiest to prepare and have good properties.
Optionally, L" can be bridged to BB. Groups that can be used to bridge
two ligands include methylene, ethylene, 1,2-phenylene, dimethyl silyl,
diphenyl
silyl, diethyl silyl, and methyl phenyl silyl. Normally, only a single bridge
is used
in a catalyst.
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The M group in the general formula can be titanium, zirconium, or
hafnium, but is preferably zirconium as those catalysts have a good
combination
of high activity and good stability.
In the general formula, B* is an optional Lewis base. Up to an
equimolar amount (with M) of base can be used. The use of a Lewis base is
generally not preferred because it tends to decrease catalyst activity.
However,
it also tends to improve catalyst stability, so its inclusion may be desirable
depending, upon the process in which it is being used. The base can be
residual
solvent from the preparation of the catalyst, or it can be added separately in
order to enhance properties of the catalyst. Examples of bases that can be
used
in this invention include ethers such as diethyl ether, dibutyl ether,
tetrahydrofuran, and 1,2-dimethoxyethane, esters such as n-butyl phthalate,
ethyl benzoate, and ethyl p-anisate, and phosphines such as triethylphosphine,
tributylphosphine, and triphenylphosphine.
The catalyst system of the invention may optionally be used in
combination with a co-catalyst. Such cocatalysts or activators are any
compound or component which can activate the olefin polymerization catalyst
containing either a bulky ligand transition metal compound or a metallocene.
Representative co-catalysts include alumoxanes and aluminum alkyls of the
formula AI(R')3 where R' independently denotes a C,-C8 alkyl group, hydrogen
or
halogen. Exemplary of the latter of such co-catalysts are triethylaluminum,
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CA 02253804 2004-04-26
trimethylaluminum and tri-isobutylaluminum. ethylalumoxane, or diisobutyl
alumoxane. The alumoxanes are polymeric aluminum compounds typically.
represented by the cyclic formulae (R°-AI-O)b and the linear formula R
°(R 8 AI-O)b
AlR ° wherein R° is a C,-CS alkyl group such as methyl, ethyt,
propyl, butyl and
pentyl and b i~ an integer from 1 to about 20. Preferably, R° is methyl
and b is_
about 4. Representative but non-exhaustive examples of alumoxane co-
catalysts are (poly)methylalumoxane (MAO), ethylalumoxane and
diisobutylalumoxane. The co-catalyst can further be tri- alkyl or aryl
(substituted or unsubstituted) boron derivative, such as perfluoro-
triphenylboron
as weN as an ionizing activator, neutral or ionic, or compounds such as tri (n-
butyt)ammoniumtetrabis (pentaf(uorophenyl) boron or
trityltetrakisperfiuorophenylboron which ionize the neutral metallocene
compound. Such ionizing compounds may contain an active proton, or some
other ration associated with but not coordinated or only loosely coordinated
to
the remaining ion of the ionizing compound. See, for instance, U.S. Patent
Nos.
5,153,157; 5,198,401; and 5,241,025 .
The catalyst and co-catalyst may be injected separately into the reactor
containing the monomers) to be polymerized. The molar ratio of co-catalyst to
catalyst may range from about 0.01:1 to about 100,000:1, preferably from about
1:1 to about 1,000:1, most preferably from about 5:1 to about 200:1.
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The catalyst systems of the invention are useful in the production of
homo- and co- polymers of olefins. Preferred as olefins are ethylene,
propylene,
butene and octene. Most preferred as olefin is ethylene. The catalyst is
particularly useful in the production of copolymers of ethylene and
unsaturated
monomers such as 1-butane, 1-hexane, 1-octane; mixtures of ethylene and di-
olefins such as 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene; and mixtures of
olefins and unsaturated comonomers such as norbornene, ethylidene
norbornen.~, and vinyl norbornene.
The catalyst systems of the invention are homogeneous and, as such,
are either liquids or are readily soluble in inert hydrocarbons. Such
homogeneity
offers greater control over the catalyst concentration and may be attributed
to the
production of a polyolefin exhibiting less ash. They can be utilized in a
variety of
different polymerization processes. For instance, they can be used in a liquid
phase polymerization process (slurry, solution, suspension, bulk or a
combination), or gas phase polymerization process. The processes can be used
in series or as individual single processes. The pressure in the
polymerization
reaction zones can range from about 103kPa (15 psia) to about 345 kPa (50,000
psia). The temperature can range from about 40°C to about 300°C.
Gas phase
and slurry polymerizations of olefins are typically conducted at about
70°C to
about 105° C. Solution, suspension and bulk phase polymerizations of
olefins is
normally conducted at temperatures of about 150°C to about
300°C.
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The homogeneous catalyst systems of the invention further exhibit
unusually high thermal stability, enabling their use over a very wide range of
temperatures. In light of the homogeneity of the catalyst systems, they are
particularly useful for the polymerization of olefins in solution phase.
The following examples will illustrate the practice of the present
invention in its preferred embodiments. The examples are provided to
illustrate
the invention and not to limit it. Other embodiments within the scope of the
claims herein will be apparent to one skilled in the art from consideration of
the
specification and practice of the invention as disclosed herein. It is
intended that
the specification, together with the examples, be considered exemplary only,
with
the scope and spirit of the invention being indicated by the claims which
follow.
EXAMPLES
In the Examples below, the melt index (Ml) of the resulting polymers
was measured according to ASTM D-1238, Condition E and Condition F. MI is
the melt index measured with a 2.16 kg weight (Condition E). HLMI is the melt
index measured with a 21.6 kg weight (Condition F). MFR is the ratio of HLMI
to
MI.
example 1
To a solution of 1.00 g (0.0086 mole) 2-methyl-1,5-diaminopentane in
20 cc toluene, cooled to -78°C, was added 10.8 cc (0.0172 mole) of a
1.6 M
solution of n-butyl lithium in hexane. After the addition, the slurry was
stirred and
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allowed to warm to room temperature, then stirred an additional 30 minutes at
room temperature. The slurry was again cooled to -78°C and a solution
of 2.39 g
(0.0086 mole) 1,5-dichlorohexamethyltrisiloxane in 20 cc of toluene was added.
Cooling was stopped, the slurry was stirred 16 hours at room temperature and
was filtered, which removed 1.3 g of a white solid. To the filtrate, cooled to
-
78°C, was added 8.4 cc of a 1.6 M solution of n-butyl lithium in
hexane. The
reaction mixture was stirred for 16 hours at room temperature and was diluted
with toluera,e to a total volume of 60 cc. This solution was divided into
three
equal portions which were used in Examples 2 to 4 below.
Examale 2
To 20 cc of the solution from Example 1, cooled to -78°C, was
added
1.18 g cyclopentadienyl zirconium trichloride (1:1 N:Zr). The reaction mixture
was stirred for 16 hours at room temperature and toluene was removed in vacuo
to yield a solid catalyst used for polymerizations numbered Run 1.
Example 3
To 20 cc of the solution from Example 1, cooled to -78°C, was
added
0.59 g cyclopentadienyl zirconium trichloride (2:1 N:Zr). The reaction mixture
was stirred for 16 hours at room temperature and toluene was removed in vacuo
to yield a solid catalyst used for polymerizations numbered Run 3.
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Example 4
To 20 cc of the solution from Example 1, cooled to -?8°C, was
added
0.393 g cyclopentadienyl zirconium trichloride (3:1 N:Zr). The reaction
mixture
was stirred for 16 hours at room temperature and toluene removed in vacuo to
yield a solid catalyst used for polymerizations numbered Runs 2, 4 and 5.
Example 5
Polkmerizations
911 polymerizations in this study were conducted in a 1.7 liter reactor.
Prior to conducting a polymerization, the reactor was "baked-out" by heating
to
130°C and holding at that temperature for 30 minutes under a nitrogen
purge.
Ethylene, hydrogen, hexene, butene and nitrogen were treated by passage
through columns containing 13X molecular sieves. For a typical polymerization,
the reactor was charged with 0.850 1 of hexane or toluene and, using a
syringe,
the required volume of diluted polymethylalumoxane, commercially available
from Akzo Chemie. The desired amount of hydrogen was added to the reactor
by monitoring the pressure drop (DP) from a 1 liter stainless steel vessel
pressurized with hydrogen. A toluene solution containing 5 mg of catalyst was
added to the reactor by nitrogen over pressure. The reactor was maintained at
80°C throughout the run. Ethylene containing 10 gms butene was admitted
to
the reactor and controlled at 1 mPa (150 psia) with feed on demand via a
pressure regulator. After the reactor temperature and pressure stabilized, the
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CA 02253804 2004-04-26
catalyst slurry was charged into the reactor and polymerization initiated.
Ethylene flow was monitored via a Brooks~mass flow meter.
Polymerization was terminated by venting the reactor and the polymer
recovered by filtration. The polymer was stabilized by the addition of about
1000
ppm of butylated hydroxytoluenelhexane (BHT) and further devolatilized 2 hours
at 80°C in a vacuum oven.
Table l below summarizes the reaction conditions for each of Runs 1
through 5_. In the table AIIM is the ratio of moles of aluminum in polymethyl-
alumoxane to moles of metal (zirconium) in the catalyst. Melt flow properties
of
the polymer were determined in accordance with ASTM D-1238. Table il
presents the results from each of the catalyst preparations.
Catalyst Molar Ratio Reaction Time
Run Preparation Solvent AIIM H ,DP (minutes)
1 Ex 2 toluene 1242 5 15
2 Ex 4 toluene 1841 5 15
3 Ex 3 toluene 1203 5 15
4 Ex 4 toluene 1473 0 15
5 Ex 4 hexane ii67 5 60
~' Trade-mark
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TAB I
Catalyst Productivity
Run (kglgMlhr) MI HLMI MFR
1 151 4.6 117 26
2 1090 26 451 18
3 246 4.5 110 24
4 489 0.14 4.8 34
5 25 >100
Example 6
To a solution of 0.930 g (0.0086 moles) of 1,4-phenylenediamine in 20
ml of toluene, cooled to -78°C, is added 10.8 ml, (0.0172 motes) of 1.6
M n-butyl
lithium in hexane. After the addition is complete, the slurry is stirred and
allowed
to warm to room temperature. The slurry is then cooled to -78°C again
and a
solution of 2.39 g (0.0086 moles) 1,5-dichlorohexamethyltrisiloxane in 20 ml,
of
toluene is added. The mixture is thin allowed to warm to room temperature and
stirred 16 hours. The slurry is then filtered to remove the by product and the
filtrate is cooled to -78oC. To the cooled filtrate, 8.4 ml of 1.6 M n-butyl
lithium in
hexane is added. After the addition is complete, the mixture is warmed to room
temperature and stirred for 16 hours. This solution is then diluted with
toluene to
a total volume of 60 ml.
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Example 7
A 20 ml sample of the solution from Example 6 is cooled to -78oC and
1.18 g cyclopentadienyi zirconium trichloride is added. The reaction mixture
is
allowed to warm to room temperature while stirring for 16 hours. Removal of
the
toluene by vacuum yields a solid catalyst.
Exama~le 8
A 20 ml sample of the solution from Example 6 is cooled to -78oC and
1.68 g diisopropylaminoboratabenzene zirconium trichloride is added. The
reaction mixture is allowed to warm to room temperature while stirring for 16
hours. Removal of the toluene by vacuum yields a solid catalyst.
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