Note: Descriptions are shown in the official language in which they were submitted.
CA 02344994 2001-04-25
HIGH TEMPERATURE OLEFIN POLYMERIZATION PROCESS
This application is a division of PCT International Application No. PCT/US
96/20544
bearing Canadian Application Serial No. 2,234,816 with the international
filing date of
December 18, 1996.
I( field of the Invention
This invention relates to catalyst system selection and high temperature
process
conditions for polymerization of monomers containing ethylenic or acetylenic
unsaturation
wherein the catalyst system is single-sited and comprises a transition metal
ration and a
stabilising, compatible non-coordinating anion.
Background of the Invention
Ionic catalyst systems for olefin polymerization based. on transition metal
compounds such as metallocene compounds are recent but now well-known. Such
metallocene compounds are based on transition metals capable of supporting at
least one
pi-bound aromatic ligand, typically a cyclopentadienyl or substituted
cyclopentadienyl
ligand and at least one additional iigand which can be abstracted so as to
form a
catalytically active cafion structure. Co-catalyst anions are needed to
stabilize these
rations, which are highly reactive, but those anions must be capable of doing
so without
either closely coordinating with the canon that its reactivity, and thus
polymerization
activity, is diminished, or transferring an anionic fragment to the canon so
as to alter its
polymerization capability. Single coordination complexes and mufti-nuclear
coordination
complexes based on the Group IIIA or 13 elements, such as boron or aluminum,
have
shown particular suitability as effective co-catalyst anion sources. See, the
disclosures in
EP-A-0 277 003, EP-A-0 277 004 and their equivalents, L.S. patents 5,198,401
and
5,278,119, particularly Examples 27 and 32. Example 3? of '119 discloses the
use of
bis(trimethylsilylcyclopentadienyl) hafnium dimethyl as the metallocene
compound.
Example 27 of '401 lists dimethylsilylbis l indenyl) zirconium dimethyl in
column 9, line 16.
CA 02344994 2001-04-25
__ _ _ 2
Homogeneous processes such as high pressure, high temperature polymerization
processes, such as those at 500 bar and above, have shown particular
suitability with such
catalyst systems since these systems exhibit greater stability than those
using alumoxanes
co-catalysts at 160 °C and above. This allows for the greater
productivity that occurs with
greater reactivities at high temperature, the high pressure maintaining an
essentially single
phase reaction medium while permitting the higher temperatures. See U.S.
patent
5,408,017 and equivalent WO-A-93/05732. A generic, broad description of
suitable
metallocene compounds is given as is a generic description of suitable anion
precursors.
The examples include the metallocene compounds dimethylsilylbis (4,5,6,7
tetrahydro-
indenyl) zirconium dimethyl and dimethylsilyIbis (4,5,6,7 tetrahydro-indenyl)
hafnium
dimethyl. The former showed significantly higher catalyst productivity
(expressed as kg-
PEIg-activator) in Table 2, ranging from 100 to 160, while that of the-
hafnium compound
exhibited only 60. A similar olefin polymerization process that can be
operated at high
temperature and pressure is 'disclosed in WO 95/07941. The principal problem
addressed is
build up of polar material in recycle streams of the reactor, the solution is
the use of bulky
scavengers, e.g., those having at least one tertiary carbon atom, such as
triisobutyl
alumoxane. Me=Si(Ind)2Hf MeZ is shown in Comparative Example 3 and Example 4,
and
said to be active Longer and illustrative of hiLh conversions.
The selection of substituents on the hi-bound, cyclopentadienyl ligands in the
metallocene compounds has been identified as a means of increasing performance
in olefin
polymerization processes. For example, see U.S. patent 5,304,614 where
specifically
substituted indenyl ligands and their methods of preparation are described.
Very high
molecular weight polyethylene at high activity is said to be possible by use
of the described
metallocene compounds based on any of the group IVB, Vb or VIb metals.
Zirconium and
hafnium are said to be preferred and the preferred substituent structure is
characterized by
1) alkylene or silylene groups bridging two cyclopentadienyl ligands bound to
the metal
atoms and 2) 4,7-substituted benzo groups fused on the respective sides
opposite the H- or
CZ to C, 2-substituent on those same cyclopentadienyl groups. Examples I4-18
are of
homopolvmer polyethylene using specifically substituted
bis(indenyl)zirconocenes with an
CA 02344994 2001-04-25
3
alumoxane co-catalyst at a temperature of 70 °C and ethylene pressure
of 5 bar.
Productivity ranged from 35 to 56 g PE for 1 hour of polymerization reaction.
The highest
production was reported for MeZ Si (3,4,7-Me~Ind)3 Zr C12.
$ In EP-A1-0 612 768, brideed and unbridged hafnium metallocene compounds
stabilized by non-coordinating anions after activated with alkyl-aluminum
co~catalysts are
said to demonstrate high catalyst activity over the zirconium analoQUes when
utilized in
processes at temperatures at or exceeding 120 °C. The medium pressure
solution
processes are preferably to be conducted at pressures of 500 to 3500 kg/cm2.
All listed
hafnocenes are dichloride-substituted embodiments and each of the working
examples of
the invention is alkylene bridged, with cyclopentadienyl, indenyl or fluorenyl
pi-bound
ligands.
Catalyst systems based on monocyclopentadienyl titanium compounds
activated with alumoxane suitable for the preparation of ethylene-cc-olefin
copolymers
of high molecular weight and high a-olefin content are described in U.S.
patent
5,264,405. This patent teaches that the cyclopentadienyl group should be fully
substituted with methyl groups and bridged to an amido group having an
aliphatic or
alicyclic hydrocarbyl ligand bonded through a 1 ° or 2° carbon.
Copolymerization of
ethylene with propylene in Example 45 with a bridged monocyclopentadienyl
Group 4
metal catalyst compound at 80 °C produced a copolymer with 20 wt.%
ethylene
having an M~? of about 20,080. In each Example SS with the same catalyst as
with
Example 45, at a reaction temperature of 140 °C, an ethylene-propylene
copolymer
having a density of 0.863, indicative of an amorphous ethylene copolymer,
exhibited an
Mn of about 46,500.
Due to the sensitivities of ionic catalyst systems to polar impurities,
solution
polymerization processes utilizing scavenging compounds, for example alkyl
aluminum
compounds or alkyl alumoxanes, have been described. See, for example, U.S.
patents
5,153,157 and 5,341.025, describing Group-IIIA metal scavenger compounds and
processes. WO-A-94/07927 addresses a similar process as adapted for
_ _.
CA 02344994 2001-04-25
_ x
monocyciopentadienyl catalyst systems, it describes advantages of bulky
scavengers
when the monocyclopentadienyl catalyst compounds do not contain bulky
substituents
to impede interaction with the scavenging compounds. Triisoprenyl aluminum is
exemplified and triisobutyl aluminum is listed along with tri-n-octyl and tri-
n-hexyl
aluminum as suitable bulky scavengers.
In view of the breadth of the disclosures concerning the use of metallocenes
for
olefin polymerization, and the general industrial need to employ the most
effective
catalysts and processes so as to have increased productivities while
maintaining both
comonomer incorporation and high molecular weight polymer preparation
capability,
additional investigative efforts were required. In particular general
knowledge based on
observations in the field gave rise to the traditional understanding that
under temperatures
exceeding about 80 °C increased comonomer incorporation using
metallocene catalysts
resulted in lower molecular weight polymer.
Invention Disclosure
It has been discovered in resulting investigations that even when subjected to
the
demanding conditions of high temperature in solution and high pressure
processes, high
molecular weight ethylene copolymers (M.I.<_ I 0, preferably, M.I. _< 1 ) can
be pelwnerized
in the presence of stable, single-sited discrete ionic catalyst systems, for
example, those
having rations derived from the transition metal compound group consisting of
1) bridged,
unsubstituted- or substituted-indenyl, or fluorenyl group containing, hafnium
compounds;
2) bridged hetero-atom containing, substituted or unsubstituted
monocyclopentadienyl
titanium compounds; 3) unbrideed, bulky Group 15 containing, bulky
monocyclopentadienyl titanium compounds; 4) Group 4 or 5 compounds containing
bulky
chelating diamide ancillary ligands; and 5) Group 8 metal diimine compounds
wherein the
metal is in a =2 oxidation state, such as Pd(II) and Ni(II). Accordingly the
invention is in
part a process for copoiymerizing ethylene and at least one higher olefin,
that is C~ to Cue,
preferably C~ to C~~ alpha-olefin, diolefcn, or C, to C~, cyclic olefin,
comprising the step of
contacting said monomers with one or more of the stable, sinele-sited ionic
catalysts with a
CA 02344994 2001-04-25
-5-
ration above and a stabilizing, compatible non-coordinating anion in a
polymerization
reaction with a reaction medium temperature of 90 °C or above, and
optionally at a
pressure exceeding 50 bar, preferably exceeding 75 bar for solution processes
and 500 bar
for high pressure supercritical phase processes. T'he invention is also in
part a modified
process comprising the additional step of introducing into either the reaction
medium,
recycle stream or the monomer feedstocks prior to the polymerization reaction,
a
scavenger for polar impurities, most preferably a trialkyl aluminum each alkyl
being a long-
chain, linear-alkyl.
Detailed Description and Best Mode of the Tnvention
The bridged hafnium compounds of the invention include those having one or
more
carbon, silicon, or germanium atoms bridging two cyclopentadienyl (Cp) ligands
of the
hafnium metal centers, said ligands optionally containing one or more
hydrocarbon
I S substituents. When the Cp ligand is an indenyl or fluorenyl group,
substitutions can be
made either on the 5 or 6 member ring carbon atoms. Substituents typically
include one or
more C1 to C3o hydrocarbon groups selected from linear, branched, cyclic,
aliphatic,
aromatic or combined groups, whether in a fused-ring or pendant configuration.
For the
purposes of this application the term "hydrocarbon" is meant to include those
compounds
or groups that have essentially hydrocarbon characteristics but optionally
contain not more
than about 10 mol.% non-carbon, polar atoms, such as oxygen, sulfur, nitrogen
and
phosphorous. Similarly the use of hetero-atom containing cyclopentadienyl
rings, where a
non-carbon atom replaces one of the ring carbons, is considered for this
specification to be
within the terms "cyciopentadienyl", "indem~l", and "fluorenyl".
Specific bridged hafnium catalysts include those derived from: ( 1 ) indenyl-
based
complexes such as the rac- or meso- isomer of dimethylsilyl bis
(indenyl)hafnium dimethyl,
dimethylsilyl bis(4,5,6,7- tetrahydro-indenvl) hafnium dimethyl, dimethylsilyl
bis(2-methyi-
indenyl) hafnium dimethyl, dimethylsilyl bis(2-propyl-indenyl) hafnium
dimethyl,
dimethylsilvl bis(4-methyl, . 2-phenyl-indenyl) hafnium dimethyl; (2)
cyclopentadienyl
complexes.such as dimethylsilyl (cyclopentadienvl)(tetramethyl
cyclopentadienyl) hafnium
CA 02344994 2001-12-06
-6-
dibenzyl, dimethylsilyl bis(cyclopentadienyl) hafnium dimethyl; and (3)
fluorenyl-based
complexes such as dibutylsilyl (fluorenyl) (cyclopentadienyl) hafnium dimethyl
and
dimethyisilyl (indenyi) (fluorenyl) hafnium dihvdride, or i-propyl
(cyclopentadienyl)
(fluorenyl) hafnium dimethyi.
In particular, for the bridged bis indenyl hafnium compounds, it has been
found that
increasing the degree of substitution on the indenyl Iigands is effective for
increased
comonomer incorporation, an effect surprising in view of the general knowledge
in the art.
Thus when the indenyl substituents include at least two sigma bound
hydrocarbon radicals
replacing hydrogen atoms on the ring atoms, the performance exceeds that where
either of
zero subsrituents or just one substituent are present. For~example
dimethylsilyl bis(2-
methyl, 4-phenyl-indenyl) hafnium dimethyl has been found to provide one or
both of
higher comonomer _incorporation and hieher molecular weight as compared to
dimethylsilyl bis(2-methyl-indenyl) hafnium dimethyl, which is better in one
or both of
these features than dimethylsiiyl bis(indenyl) hafnium dimethyl. Thus
preferably the
Iigation on the indenyl radicals in the bulky hafnium compounds will generally
comprise
two or more C~ to C3o hydrocarbon substituents as defined above.
The silicon bridged hetero-atom containing, substituted or unsubstituted
monocyclopentadienyl titanium compounds of the invention are any of those
described in
the art, see for example those described in U.S. patent 5,264,405, WO 92100333
and U.S.
patent 5,408,017. The substituted ,cyclopentadienyl ,ligand, is one having
hydrocarbon
substituents as defined for the cyclopentadienyl, indenyl and fluorenyl
ligands of the
bridged hafnium compounds above.
The unbridged; bulky Group 1. containing_. bulky monocyclopentadienyl titanium
compounds of the invention are unbrideed titanium compounds having ancillary
ligands
including a substituted, bulky cyclopentadienvl li_and, a substituted, bulky
Group 15
heteroatom ligand, and two uninegative. activation reactive ligands at least
one of which
that can be abstracted for activation of the remaining metal compound to a
catalytically
....
CA 02344994 2001-04-25
_. . .
active state and one of which is either similarly abstractable or has a a-bond
to the
transition metal into which an olefin or diolefin can insert for coordination
polymerization.
Typically, for any of the catalysts of this invention, uninesative, activation
reactive ligands
are selected from the group comprising hydride, lower alkyl, e.g., C1 to C,,
or silyl. The
bulky cyclopentadienyl ligand is one having substituents as defined for the
cyclopentadienyl, indenyl or fluorenyl iigands of the bridged hafnium
compounds above,
particularly lower alkyl-substituted ligands, such as tetramethyl and
pentamethyl
cyclopentadierryl ligands. The bulky Group 15 heteroatom ligand is typically a
hydrocarbon substituted Group 15 element, preferably nitrogen, wherein the
hydrocarbon
substituents are covalently bound to the heteroatom through a secondary or
tertiary carbon
or silicon atom.
Ionic catalysts derived from Group IVB metal precursors where the ancillary
ligand
system does not contain a cyclopentadienyl ligand may also be employed in this
invention.
In general, these systems will be prepared from an ionic activator or Lewis
Acid activator
and a Group IVB metal containing precursor of the following general formula:
M1
A . ~ R'''
- L.,
wherein:
A is an optional bridging substituent,
L, and LZ are the same or different non-Cp ancillary ligands,
M is a Group IVB metal, and
R, and R= are the Same or different a-bonded groups such as hydride or
hydrocarbyl.
CA 02344994 2001-04-25
_.v _ 8
An example of a suitable non-Cp anciliarv ligand system is described in
"Conformationally Rigid Diamide Complexes: Synthesis and Structure of
Tantalum(III)
Alkyne Derivatives", D. H. McConville, cu al, Organonretallics 1995, !-i, 3154-
3156.
Among the Group 4 metals, the Group 4 metals are preferred especially those of
titanium.
The Group 4 metal compounds will additionally comprise at least two
uninegative,
activation reactive ligands at least one of which that can be abstracted for
activation of the
remaining metal compound to a catalyticaily active state and one of which is
either
similarly abstractable or has a a-bond to the transition metal into which an
olefin or
diolefin can insert for coordination polymerization. The Group 4 metal
compounds having
the descn'bed ligands can be prepared as illustrated in the Or~anommallics
article except
that the Group 5 metal halide is replaced with a Group 4 tetrahalide
The Ni2~ and Pdz~ complexes of the invention are diimine complexes that can be
prepared by methods equivalent to those used for the compounds, described in
"New
Pd(II)- and N(II)- Based Catalysts for Polymerization of Ethylene and a.-
Olefins", M.
Brookhart, et al, J. Am. Chem. Soc., 1995, 117, 6414-6415. These can be either
the
dialkyl ether adducts as described, or alkylated reaction products of the
described' dihalide
complexes that can be activated to a cationic state by the anion precursors
according to the
invention.
In general effective scavengine compounds for ionic polymerization catalysts
include those aluminum alkyl compounds listed in L;.S. patents 5,153,157 and
5,241,025.
The term "scavenges' is used in its art-recognized sense of being sufficiently
Lewis acidic
to coordinate with polar contaminates and impurities adventiously occurring in
the
polymerization feedstrcams or reaction medium. In particular, for processes
utilizing
recycle streams of unconverted monomer for reprocessing, the necessity to use
polar
compounds as catalyst deactivators, or "killers", such as water or lower
alcohols,
effectively necessitates the use of scaven~=ers. as does the naturaloccurrence
of polar
impurities in monomer feedstreams. It has been discovered, however, that the
use of
excess scavenger has a deleterious effect on catalyst performance, and that
the proper
choice of scaveneer is important to minimize the effects. Addition of excess
scavenger
CA 02344994 2001-04-25
_9_
causes lower productivity, molecular weight and comonomer incorporation. This
effect
can~be easily seen by comparing Examples 1.2, 1.6, 1:7, and 1.8 in Table 1 of
the examples
section, when the addition of 6 equivalents of triethylaluminum (TEAL) caused
an increase
in productivity but as more TEAL was added productivity decreased as did the
molecular
weight and comonomer content of the product. Replacing TEAL with triisobutyl
aluminum (TIBA) (Examples 1.9 - 1.12) improved the catalyst performance under
excess
scavenger conditions but did not completely remedy the situation.
. _ : Experiments under high temperature conditions showed similar trends. In
order to
further improve the performance of the ionic catalyst system, a systematic
study of more
substituted scavengers was carried out. Based on the observation that TIBA
performed
better than TEAL, it was expected that more highly substituted aluminum alkyl
compounds, such as AI(CHZCMe3)2Me, where Me is methyl, would be superior to
TIBA
because of the increase ~teric bulk around the AI atom. Comparative tests
under high
temperature conditions showed that AI(CH~CMe,~Me was inferior ~to TIBA and
caused
sudden loss of productivity at very low levels of scavenger. Further studies
showed that
the preferred scavenger is a long chain, linear tri-alkyl aluminum compound,
and that
longer chains are preferred over shorter chains.
Non-limiting examples of effective long chain, linear tri-alkyl ligand-
containing
scavengers include those comprised in the group defined by the formula
M'R'R"R'", where
M' is Al, and each of the R groups independently is a C, or higher linear,
br~artched or
cyclic alkyl group, preferably C~ or higher, most preferably C= or higher. The
long chain,
linear alkyl aluminums where each alkyl substituent was of a length of Ca or
higher,
preferably C9 and higher were observed to exhibit optimal performance, that
defined as
having the least deleterious effect when used at a level in excess of the
optimum level as
described in the following paragraph. Specifically included are: tri-n-octyl
aluminum, tri-n-
decyl aluminum, tri-n-dodecyl aluminum. tri-n-hexadecvl aluminum, and the
higher carbon
number equivalents, e.g., (CZO):Al, including those with mixed ligation, and
mixed
scavenger compounds as well. The hydrolyzed derivatives of these alkyl-liLand
containing
organoaluminum compounds will additionally be suitable. Additionally, it will
be apparent
CA 02344994 2001-04-25
_ .. . ~ O , .._
that those scavenging cotnpounds comprising both long-chain, linear and bulky
ligands or
mixed linear ligands, each ligand as described above, will also be suitable,
but perhaps less
desirable due to more involved or expensive syntheses.
The long chain, linear-alkyl ligand-containing scavengers of the foregoing
paragraph will be useful in any insertion polymerization process for
olefinically or
acetylenically unsaturated monomers with any of the ionic catalyst systems
known in the
art or those in development, where such make use of non-coordinatins anions
and the
resulting catalyst sensitivities require elimination of polar impurities.
Suitable catatvst
systems appear in the catalyst references listed in the Backgound in this
application,
additional catalysts include those Group 5 and 6 transition metal catalyst
systems of U.S. Patent
No. 5,504,049. Examples of suitable process conditions include those of gas
phase, solution,
slurry or bulk polymerization processes for any polymers or copolymers of .two
or more
monomers selected from the group consisting of ethylene, propylene, C4-C~
a=olefins, strained
I S ~g cYclic olefins, macromers of up to 100 or more mer units having
olefinic unsaturation in
the 1-position, or acetylenically unsaturated monomers. Such processes utilize
-50 °C to 300 °C
temperature and 0 to 3000 bar pressure. Polymers and copolymers having
molecular weights
equivalent to an M.I. of 100 and below can be prepared in these processes.
The scavengers, whichever are selected. should be utilized in a manner
consistent
with the sought productivity, polymer molecular weight, and polymer ~comonomer
content.
In particular, only that amount sufficient to neutralize the effects of the
adventitious
catalyst poisons should be utilized, the better purified the comonomer
feedstreams into the
reactor and as well the other feedstreams or added reactants and recycle, the
less
scavenger will be required. The amount is preferably as little as possible and
can be
adjusted empirically by observing the rates of reaction, adiabatic
,temperature rise, and
other indicators of reaction efficiencies obser<~able in the polymerization
process, each
being maximized holding all variables other than the addition of scavenger
constant.
CA 02344994 2001-04-25
Excess scavenger has been observed to cause a reduction in productivity,
molecular weight
and comonomer incorporation.
Means of preparing the ionic catalyst systems comprising cations of the
described
transition metal compounds and suitable non-coordinating anions are
conventionally
known, see for example U.S. patent 5,198,401 and WO 92/00333. Typically the
methods
comprise obtaining from commercial sources or synthesizing the selected
transition metal
compounds comprising an abstractable ligand, e.g., hydride, alkyl or silyl
group, and
contacting them with an ionizing non-coordinating anion source or precursor in
an
aromatic solvent. The anion source acts to ionize the transition metal
compounds by
abstracting the univalent -hydride, alkyl or silyl ligand that complements its
total valency.
The abstraction leaves the transition metal compounds in a +1 cationic state,
which is
counterbalanced by the stable, compatible and bulky, non-coordinating anion.
See the
fuller description in U.S.' patent S,I98,401, referred to above. Conditions of
adiabatic
polymerization processes such as practiced at high pressure, result in
temperatures
exceeding I60 °C and above. These higher operating temperatures lead to
increasing
instability that is reflected in more difficult higher olefin comonomer
incorporation and
reduced molecular weight polymer. However, the single site catalysts of this
invention
under those .same conditions evidence higher stability, greater comonomer
incorporation
and higher retained molecular weight as evidenced in the tabulated
observations below.
The non-coordinating anion sources of the 'invention includes any of those
conventionally known to be useful for olefin polymerization with metailocenes,
including those knovEm to be useful with the single cyclopentadienyl
containing Group
4 transition metals. A representative listing of suitable anions is in U.S.
5,198,401, EP-
A-0 426 637, EP-A-0 427 697, EP-A-0 530 732, EP-A-0 573 403, WO 95/24268 and
U.S. patent 5,387,568. Those may be introduced into the catalyst preparation
step as
either ionic compounds having a cation which abstracts a non-cyclopentadienyl
ligand
of the transition metal compounds or as neutral compounds which upon
abstraction of
the non-cyclopentadienyl ligand, leave as a by-product the non-coordinating
anion
portion. Additionally, it is known that the use of alkylatin~_ compounds along
with an
CA 02344994 2001-04-25
j2
._ __. ;
anion source enables the use of transition metal compounds having ligands too
strongly
bound to the transition metal center to be abstracted by the anion source,
e.g.,
transition metal dihalides. Typical alkylating sources may be any of the
strongly Lewis
acidic organoaluminum compounds such as the lower carbon number alkyl
aluminums
and alkylalumoxanes. See EP-A-0 500 944, EP-A-0 570 982 and EP-A1-0 612 768
for in situ processes describing the reaction of alkyl aluminum compounds with
dihalo-
substituted metallocene compounds prior to or with the addition of activating
anion
precursor compounds. Most preferably transition metal compounds not having
halide ligands
on the metal center are used for the ionic catalyst systems of this invention
since in situ
alkylation processes may result in competing reactions and interactions that
tend to interfere
with the overall polymerization efficiency under conditions of high
temperature in accordance
with this invention.
I S A class of preferred anion precursor compounds are hydrated salts
comprising a
Group 1 or 2 cation and a non-coordinating anion as described above. The
hydrated salts
can be prepared by reaction of the metal canon-non-coordinating anion salt
with water, for
example, by hydrolysis of the commercially available or readily synthesized
La'B(pfp)y
which yields [Li ~ H=OJ [B(pfp).~J, where (pfp) is penta- or perfluorophenyl.
The by-
product of ionization of the abstractable li~and-containing transition metal
compounds
with this precursor is LiOH which is non-volatile and thus is not recycled in
the separation
phase wherein the polymer is removed from monomer and any diluent prior to
recycle.
Tests-have shown that this low-cost precursor operates to form ionic catalysts
having
properties essentially equivalent to those formed with the preferred precursor
compounds
represented by [Ph3C j[B(pfp),,] and [Phlle,NHJ[B(pfp),~J, Ph representing
phenyl and Me
representing methyl. As with the lone chain, linear-alkyl lis~and-containing
scavengers
noted above, this non-volatile by-product anion precursor will be suitable for
use with any
of the ionic catalyst systems known in the art or those in development, where
such make
use of non-coordinatine anions. Cataiwicallv suitable transition metal
compounds capable
of canonization include those Group .1 to 6 and 8 compounds addressed above.
Again,
examples of such include gas phase. solution, slurry and bulk polymerization
processes for
CA 02344994 2001-04-25
_1 : _ .. _ 13 -
any polymers or copolymers of two or monomers selected from the group
consisting of
eth~rlene, propylene, Cs-C=o ct-olefins, strained ring cyclic olefins,
macromers of up to 100
or more mer units having olefinic unsaturation in the 1-position, or
acetylenically
unsaturated monomers. Such processes utilize -50 °C to 300 °C
temperature and 0 to
S 3000 bar pressure.
Known alkylalumoxanes are additionally suitable as catalyst activators for the
invention single-site transition metal compounds comprising halide ligands,
however
these are less preferred since the alumoxane activators are less temperature
stable at or
above about 160 °C. The alumoxane component includes all those useful
as a catalyst
activator, typically such will be an oligomeric aluminum compound represented
by the
general formula (R-Al-O)n, which is a cyclic compound, or R(R-Al-O)nAIR,,
which is
a linear compound. In the general alumoxane formula R is a C1 to CS alkyl
radical, for
example, methyl, ethyl, propyl, butyl or pentyi and "n" is an integer from 1
to about 50.
1 S Most preferably, R is methyl and "n" is at least 4. Alumoxanes can be
prepared by
various procedures known in the art. For example, an aluminum alkyl may be
treated
with water dissolved in an inert organic solvent, or it may be contacted with
a hydrated
salt, such as hydrated copper sulfate suspended in an inert organic solvent,
to yield an
alumoxane. Generally, however prepared, the reaction of an aluminum alkyl with
a
limited amount of water yields a mixture of the linear and cyclic species of
the
alumoxane.
A preferred process of polymerization is that conducted at high pressure, that
is at
from 200 to 3000 bar, preferably from 500 to 2500 bar in a homogeneous single
phase or
two fluid phases, with or without unreactive diluents or sulvents at
temperatures generally
above the melting point of the polymer being produced. Such processes are
typically
known and may include the use of scavenger compounds and catalyst deactivation
or
killing steps, see for example U.S. patent 5.408.017, WO 95/07941, and WO
92/14766.
Preferred catalyst deactivators, or killers, include high molecular weight,
non recyclable
compounds, such as poly vinyl alcohol which exhibit the
CA 02344994 2001-04-25
- 14
functional capacity to complex with the catalysts so as to deactivate them
while not
forming volatile polar by-products or residual unreacted compounds.
Another preferred process in which any of the catalyst, cocatalyst and
scavenger
selections disclosed in this application can be advantageously practiced is
that of a
continuous, solution process operated at or above 90 °C to 120
°C, even above 150 °C or
above 160 °C, up to about 300 °C. Typically this process is
conducted in an inert
hydrocarbon solvent, linear, cyclic or branched aliphatic, or aromatic, at a
pressure of from
20 to 200 bar.
15 For optimal polymerization results the processes should be designed or
conducted
such that the cocatalyst components, that is the uansition metal compounds and
the anion
precursor compounds, are maintained separately until just prior to or during
polymerization use in the chosen reactor. An example is the use of dual
injection of each
catalyst component directly into the reactor or the use of T- or mufti joint
mixing
chambers just prior to injection into the reactor. Alternatively the catalyst
may be formed
in-situ by the independent addition of ionic activator, Iigand stabilized
metal halide, and
scavenger directly into the reactor or the use of T- or mufti joint mixing
chambers just
prior to injection into the reactor. Additional optimization can be achieved
when the
scavenger compound is introduced into the reactor independently of the
catalyst system, or
compounds.
Though directed specifically for hi~_h temperature, particularly high pressure
or
solution, processes, it will be apparent that the use of heteroeeneous'support
material such
as polymeric and metal or n'tetalloid oxide supports will enable slurry or eas
phase use of
the process steps and components described and will likely achieve similar
benefits of
higher productivities. higher molecular weights, and higher levels of
comonomer
CA 02344994 2001-04-25
_.., . _ ._ _ 15 -
incorporation for the ethylene copolymer products capable of production using
the
disclosed copolymerizable monomers. Illustrative support methods appear in WO
91/09882, W0.94/00500, WO 94/03506, WO 94/07928, and in WO 96/04319 based on
U.S. Patent No. 5,643,847. A suitable slurry process is described in U.S.
patent 5,229,478.
The following examples are presented to illustrate the foresoing discussion.
All
parts, proportions and percentages are by weight unless otherwise indicated.
Although the
examples may be directed to certain embodiments of the present invention, they
are not to
be viewed as limiting the invention in any specific respect. Methods of
determining MW
and monomer contents by GPC and NMR for the illustrative ~PC examples of the
invention are described in U.S. patent 5,229,478. For the following examples
certain
abbreviations have been utilized for convenience : Cp (cyclopentadienyl),
Me(methyl),
Ind (indenyl), ~ Ph (phenyl), pfp (pentafluorophenyl), r- (racemic), Et
(ethyl),
Cp* (permethylated cyclopentadienyl), Cod (cyclododecyl), TOA (tri-n-octyl
aluminum), TEAL
(triethyl aluminum) and TIBA (triisobutyl aluminum).
a
CA 02344994 2001-04-25
__ - 16 -
EXAMPLES
Part I: Laborntorv Screenine Eaoeriments
The data from batch laboratory tests is summarized in Table 1. All
polymerizaiions in Table I were carried out in a one liter stainless steel
autoclave in
400 cc hexane with 45 cc hexene under 75 psi (517.11 kPa) ethylene head
pressure at
60 °C.
In each case the autoclave was filled with the solvent and hexene and heated
under 75 psi (517.11 kPa) of ethylene until equilibrium was reached under
rapid
stirring. The catalyst was introduced into the reactor under these conditions
and the
temperature was maintained at 60 °C +/- 5 °C for the duration of
the run. The product
was recovered and analyzed by GPC and 'aC NMR spectroscopy to determine the
molecular weight and comonomer content. An example of continuous process use
of
the information contained in Table 1 follows Example 1.1.
Eaamole 1.1
A one Iiter mechanically stirred stainless steel autoclave was filled with 400
ml
dry and deoxygenated hexane, 45 ml dry and deoxygenated hexene. The reactor
was
stirred rapidly, pressurized to 75 psi (517.11 kPa) with ethylene, and heated
to 60 °C.
A catalyst solution in toluene containing 1.42 X 10's moles of r-
Me2Si(Ind)~HlIvie2 and
4.99 X 10's [PhMeziVH][B(pfp),] was added to the reactor causing a
polymerization
reaction to occur. After 30 minutes the reactor was vented and the contents
were
poured into a flask. The solvent was evaporated to yield S gams of and
ethylenelhexene copolymer having a V4" = 151,000 Daltons, a M" = 74,000
Daltons,
and 47.4 wt.% hexene. This represents a productivity of 714 grams PFJgrarrt
metallocene.
CA 02344994 2001-04-25
The results of the screening experiments collected in Table I demonstrate
scveral important trends. These include the following observations.
~ Bridged vs. Unbridged Metallocenes
+ Bridged have 2-3 times the comonomer incorporation (see
CpzHfMez vs. EtzSiCpzHfMez or CpCp*I-ifMez vs.
MezSiCpCp*HfMez).
+ Bridged complexes produce higher MW products.
+ Bridged complexes typically show higher activities.
_
~ (PhMezNH](Bpfp)'] vs. [Ph;C]Bpfp),] vs. [Li~H20][Bpfp),]
+ All appear to produce the same polymer at similar rates.
~ The Effect of scavengers on Catalyst Performance
+ I-~gh levels cause lower MW and comonomer content.
+ Low levels improve productivity without affecting product.
+ TIBA better than TEAL in terms of effect on product at high levels
of scavenger.
+ high levels depress productivity. .
~ MezSi(Ind)zHfMez vrs. MezSi(4-Me,2-PhInd)zHfMez
+ Substituted system shows higher MW even at high comonomer
content.
+ Substituted system shows significant increases in comonomer
incorporation.
~ The metallocene dichloride route vrs. the metallocene dialkyl route
+ The chloride free approach produces high MW and comonomer
content products.
~ Zr vrs. Hf
CA 02344994 2001-04-25
_ 18 -
+ Hf systems superior in terms of MW and comonomer incorporation.
~ Mono-Cp Ti vrs. bis-Cp Hf Catalysts
+ The bis-Cp Hf systems can be modified to have similar performance
S to the mono-Cp systems.
Part 2: Continuous High Pressure Oneration
The polymerization reactions in Table 2 were performed in a stirred 1.5 L
steel
autoclave reaction vessel which was equipped to perform continuous Ziegler
polymerization reactions at pressures up to 2000 bar and temperatures up to
300 °C.
The reaction system was supplied with a thermocouple and pressure transducer
to
measure temperature and pressure continuously, and with means to supply
continuously purified compressed ethylene and 1-butene. Pressure was
controlled by
_ pressure reduction valve. Equipment for continuously introducing a measured
flow of
catalyst solution, and equipment for rapidly veining and quenching the
reaction, and of
collecting the polymer product were also a part of the reaction system. The
ability to
add scavenger to the fresh feed prior to the reactor was provided by a high
pressure
pump. The polymerization was performed with a specified molar ratio of
ethylene to
comonomer and without the addition of a solvent. The temnerarmrP .,f rt,p
ra".fnr
containing ethylene and comonomer was equilibrated at the desired reaction
temperature. The catalyst solution was prepared by mixing a specified amount
of solid
metallocene component with the activator component in toluene under an inert
atmosphere. This catalyst solution was continuously fed by a high pressure
pump into
the reactor at a rate which resulted in the desired reactor temperature. The
reactor
contents were stirred at 1000 rpm and the reactor feed mass flow rate
typically used
was 40 kg/hr. Exact run conditions including catalyst preparation metallocene
component (M) (g), activator component (A) (g), and total volume of solution
(L)
scavenger aluminum compound to transition metal compound with molar rate
(A1:M),
catalyst production polymer production rate (k~ polymer/hr) average, comonomer
molar feed ratio (e.g. C~/C~), reactor mass flow rate (kg/hr), and polymer
CA 02344994 2001-04-25
- 19 -
characteristics including melt index (g/10 minutes at 190 °C), and
weight percent
cotnonomer (determined by IR), are also collected in Table 2. All
polymerizaiions
were carried out at 225 °C and I300 bar. The catalyst solutions were
prepared using
dry and deoxygenated toluene. An example of how to use the information
contained in
Table 2 follows Example 2.1.
Example 2.1
Using the reactor design as described above, and using a molar ratio of the
ethylene to 1-butene of 0.55 without the addition of a solvent, the
temperature of the
cleaned reactor containing ethylene and I-butene was equilibrated at the
desired
reaction temperature of 225 °C. The catalyst solution was prepared by
mixing 0.496 g
of solid compound r-MezSi(Ind)ZHfMe2 with 0.9788 activator compound
(Ph~C~'B(pfp)i in 20 liter toluene. 'This catalyst solution was continuously
fed by a
high pressure pump into the reactor at a rate which resulted in a temperature
of 225 °C
in the reactor. During this run, ethylene and 1-butene was pressured into the
autoclave
at a total pressure of 1300 bar. The reactor contents were stirred at 1000
rpm, and the
mass feed flow rate through the reactor was held constant at 40 kg/hr.
Polymerization
was conducted for a 60 to 90 sec. residence time. The yield of polymer product
was
6.6 kglhr. of an ethylene-1-butene copolymer which had a MI of 2.85 and a
comonomer incorporation of 13 weight percent butene as measured by IR.
Transition
metal productivity was calculated at 267 kg polymer/g metallocene.
CA 02344994 2001-08-28
20
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CA 02344994 2001-04-25
== - ZZ -
Part 3: Continuous Aigh Temperature Solution Process
The polymerization reaction was performed in a stirred, liquid filled 2 L
jacketed
steel reactor equipped to perform continuous insertion polymerization in
presence of an
inert C6 hydrocarbon (naphta) solvent at pressures up to 120 bar and
temperatures up to
240 °C. , The reactor was typically stirred at 1000 rpm during the
polymerization. The
reaction system was supplied with a thermocouple and a pressure transducer to
monitor
changes in temperature and pressure continuously, and with means to supply
continuously
purified ethylene, 1-octene, and solvent. In this system, ethylene dissolved
in the
hydrocarbon solvent, I-octene, tri-n-octyl aluminum (TOA) used as a scavenger,
and
optionally Hz, are pumped separately, mixed, and fed to the reactor as a
sinsle stream,
refrigerated to -40 °C using liquid NH_ as a coolant. The transition
metal component
(TMC) was dissolved in a solvent/toluene mixture (9/I vol/vol) whereas the non-
coordinating anion (NCA) activator was dissolved in toluene or slurried in the
hydrocarbon solvent. Both components were pumped separately, mixed at ambient
temperature, and cooled to -1 °C prior to entering the reactor. The
reactor temperature
was set by adjusting the temperature of an oil bath used as a reservoir for
the oil flowing
thmugh the reactor wall jacket. Next, the polymer molecular weight (MW) or MI
was
controlled independently by adjusting the ethylene conversion (% CZ) in the
reactor via the
catalyst flow rate. Finally, the polymer density was controlled by adjusting
the ethylenell-
octene weight ratio in the feed.
The results of ten polymerization experiments performed in the reactor
described
above with three different TMC's (A = rac-dimethylsilyl bis(1-indenyl) hafnium
dimethyl,
B = dimethyisilyl bis(2-methyl-4-phenyl-1-indenyl) hafnium dirnethyl, and C =
dimethyISilyl
(tetramethylcyclopentadienyl)butyIamino titatium dimethyl) and
[PhMe2NH]B(pfp),] used
as the activator (NCA) are summarized in Table 1. For example, the
polymerization
reaction in run #1 was carried out at 150 °C and 86.4 bar with A.
Solvent, ethylene, and
I-octene were continuously fed to the reactor at a rate of 7 kg/hr., and 0.53
kg/hr.,
respectively, The 1-octene/ethylene wei;ht ratio in the feed was 0.431 in this
case. 3.5
mg/hr. of A dissolved in a 9/1 solvent/toluene (volivol) mixture and 4.9
m,,r/hr. of NCA
dissolved in toluene were continuously fed to the reactor, resulting in an
ethylene
conversion of 80.5% and a 1-octene conversion of 4;°~0. For a reactor
residence time of 8
minutes, the polymer yield was 1.22 ke/hr. under these conditions. By adding
TOA at a
rate of 0.08 mmol/hr. to the feed, the catalyst productivity lined out around
348 kgPFJg A.
This experiment resulted in an ethylenei 1-octene copolymer containing I 8.77
weight
comonomer (FZ'IR) with a weight-avera~__=e MW of 88,000 glmol (GPC), a
polydispersity
CA 02344994 2001-04-25
_. ,,
- 23 -
index of 2.1 (GPC), a MI of 1.4 dg/min., a density of 0.8991 S/cc, and a MIR
(I21.6/I2) of
34.
At constant reactor temperature and feed composition, the polymer MW can be
adjusted in this low pressureJhigh temperature polymerization process by
controlling the
ethylene conversion in the reactor via the catalyst flow rate; typically, the
higher the
ethylene conversion, the lower the polymer MW (the higher the MI). The above
examples
showed that surprisingly both bridged bis (Cp) hafnocenes (A and B) exhibit
superior MW
and comoaomer incorporation capability than the bridged mono(Cp) titanocene
(C) does.
For sample, at 140 °C and .with a I-octeae/ethylene weight ratio in the
feed equal to
about 0.43 to 0.44, A and B produced, respectively, a 1.6 MI/0.8937 g/cc
copolymer at
87.9% ethylene conversion (run #3) and a 0.62 MIl0.8880 g/cc copolymer at
80.7%
ethylene conversion (run #6), whereas (C) produced a 1.5 MI/0.9035 g/cc
copolymer at a
substantially lower ethylene conversion of 77.1 % (run #9). Similarly, at 130
°C and with a
I-oc;teaeleihylene weight ratio in the feed equal to about 0.93 to 0.94, A
produced a 1.23
MI/0.8761 glcc copolymer at 73.9% ethylene conversion (run #4), whereas (C)
made a 3.2
MI10.8866 g/cc copolymer at a lower ethylene conversion of 69.2% (run #10).
CA 02344994 2001-04-25
_. _ 24
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CA 02344994 2001-04-25
- 25 -
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