Note: Descriptions are shown in the official language in which they were submitted.
~ W0 94/03~092 1 ~ 1 6 1 6 PCr/l~S93/07358
GAS PHASE PQLYMERIZATION OF ETFIYLENE . -~
AND C7 TO Clo OLEFINS - ~ -
ELI) OF T~E ~NVENTlON :::
This invention relates to a method for preparin, ethylene- C6 to C10 a- :
olefin copolymers by gas phase polymerization-in the presence of a transition metal . ;
catalyst system which is activated by an organoaluminum cocatalyst or an ion j : -
exchange reagent containing a stable non-coordinatin, anion. 'l :~
BACKGROUND OF THE INVENTION
o Copolymers of ethylene and an a-olefin having 6 to 10 carbon atoms aredesired for a variety of applications. The nature, content and distribution of the
comonomer in the copolymer significantly influences its physical and chemical . ~: ~
properties. Ethylene homopolymers such as high density polyethylene (HDPE) ~ :.
have a density of 0.94 to 0.96 g/cc and are generally linear -- without any - .
5 substantial side chain branching --whereas low density polyethylenes (LDPE) have
a density of 0.915 to 0.940 g/cc is a highly branched polyethylene, i.e., relatively
large numbers of long chain branches extend from the main polymer backbone. In
contrast, a linear type of ethylene polymer may be produced havingJ a density in the -~
range of low density polyethylene, or less, by copolymerizing ethylene with an a-
20 olefin comonomer -- such as hexene~ octene or decene -- to introduce enough
short chain branches into the otherwise linear ethylene polymer to reduce its
density in an amount which is proportional to that amount of comonomer which is
incorporated into the polymer. In a linear copolvmer of ethylene density decreases
with increasing amounts of incorporated comonomer. A polymer of ethylene
2~ which incorporates an amount of a-olefin comonomer tO provide a density of
0.915 to 0.94 glcc is referred tO as linear low density polyethylene (LLDPE), even
higher levels of a-olefin comonomer incorporation provide a polymer of density ~ -~
ranging from 0.85 to 0.90 g/cc and this material is referred to as very low density -~
polyethylene (VLDPE). For applications such as extrusion coating or blown film,
30 a low or very low density linear polyethylene is preferred.
The nature of the cornonomer utilized in preparint~ a linear copolymer of
ethylene may exert a significant influence on other properties of the polymer, such
as impact strength and g~au~Jeability. For instance. a copolyme" p. epared with 1-
octene as the comonomer has greater impact stren ,th and gaugeability than does
3s an ethylene copolymer prepared with l-hexane or l-butane at a similar level of
comonomer incorporation Further, the manner and randomness with which a
214161~
WO 94/03509 ~. PCI/US93/07358',
comonomer is distributed throughout the polymer molecules affects other polymer
properties such as tear strength, surface properties, cling development, and levels
of extractables. Still fiurther, the uniformity of comonomer content between
polymer fractions of different molecular weight -- compositional distribution --affects various properties of the copolymeric material. For instance, linear lowdensity polyethylenes heretofore produced under low or moderate pressures with aconventional Ziegler-Natta type catalyst have a relatively broad molecular weight
distribution, i.e., Mw/Mn greater than about 3, while also having a relatively broad
compositional distribution in that the mole % proportion of_-olefin comonomer
lo incorporated into molecules of lower molecular weight is greater than the amount
incorporated into polymers of higher molecular weight. LLDPE resins of such
characteristics are subject to anisotropic properties in the machine versus
transverse direction of a fabrication process. The lower molecular weight fraction
of such LLDPE resins, in which the copolymer is concentrated, tends to exhibit
high block and tackiness and interferes with the proper function of certain additives
compounded in the resin and increases the percentage of extractable polymer. Therelatively high comonomer content of these low molecular weight polymers
molecules causes such polymer molecules to be generally amorphous and migrate
to the surface of fabricated parts, thereby producing an undesirable sticky surface.
The randomness with which a comonomer is distributed within a polymer
chain -- sequence distribution -- also influences proper~ies of the polymer such as
tear strength and film clarity.
Further influencing the properties of a polymer resin is its weight average
molecular weight(Mw) and molecular wei~~ht distribution (MWD). Generally, a
2~ greater strength is achieved with a polymer of higher molecular weight andnarrower molecular weight distribution. The molecular weight and molecular
weight distribution of the polymer affects its rheologic characteristics, modulus and
yield strength.
The molecular characteristics of a polymer, particularly a copolymer, in
significant part, are dictated by the nature of the catalyst used in its production.
For example, a conventional Ziegler-Natta catalyst is a multi-site catalyst, which
typically produces a polyolefin of a high molecular weight but of broad molecular
weight distribution (l~ D; namcly. Mw/Mn ~ 5). In contrast, an alumoxane-
activated metallocene catalyst system is a single-site catalyst which typically
produces a polymer of narrow molecular weight distribution (i.e., MWD ~ 3), but
at the cost of a typically high content of metallic catalyst residue because of the
21~1616 ` ~ ~`
W094/03~09 PCr/US93/073~8 j;
- 3 ~
high content of alumoxane required tO render the metallocene component ~ ~;
sufficiently catalytically active for practical use.
Recently a single-site metallocene type of catalyst has been developed
which preserves the desirable characteristics of an alumoxane activated
s metallocene catalyst system while eliminating the need for iarge amounts of
alumoxane to achieve sufficient catalytic activity. The newly developed catalystsystem comprises a metallocene component which is activated to a catalytic stateby reaction with an ion exchan;,e compound as described in commonly owned -~
copending U.S. Serial numbers 133,05~; 133,480; 542,236 and 796,729. These
new ionic metallocene catalyst systems are also single-sited ca~alyst which typically
produces polymers of high molecular weight and narrow molecular weight
distribution.
In part then, the set of polymers properties may be "engineered" by the
choice of the catalyst system selected. For production of a hi~h molecular weight
1~ and broad molecular weight distribution polymer, a Ziegler-Natta catalyst may be
selected; for production of a high molecular wei~gllt and narrow molecular weight
distribution polymer, a single-site metallocene type catalyst may be chosen.
Further, in part, the properties of a copolymer may be engineered by selecting aparticular comonomer. For example, an ethylene/ I -octene copoiymer provides a
polymer of greater impact strength and gaugeability than a copolymer produced -~
with a comonomer of a lesser number of carbon atoms, such as l-hexene or 1- --
butene.
Even though it is conceptually possible to engineer the molecular
characteristics of a copolymer to a particular set of properties by selection ofcatalysts and comonomers, the "engineered" polymer must still be practically
- produceable. That is, with the catalyst, comonomer and the polymerization
process conditions selected. the polymer must be producible at a practical rate and
cost of polymer production.
Polyolefins, particularly ethylene-a-olefin copolymers have heretofore been
produced by a wide variety of processes ran~ing from solvent, slurry, high
temperature-pressure, and ~as phase polymerization processes which are carried
out over a wide range of temperature and pressure. In a solvent process,
pû'yme~ization of monomers occurs in the medium of a solvent, typically an inerthydrocarbon, which carries the catalyst into contact with the monomer dissolved
therein and the medium is one in which the product polymer is soluble. The
solvent medium absorbs the heat generated by the polymerization reaction and heat -~
W0 94/03S09 , ~ ; PCr/USg3/0735a`
exchange control of the solvent medium temperature controls the temperature of
the polymerization reaction thereby optimizing produc~ivity or polymer properties
according to the characteristics of the catalyst used. After polymer produc$ion, the
solvent medium and dissolved polymer must be separated by a subsequent
s processing step, such as by evaporation or distillation.
ln slurry processes, monomer polymerization occurs in the medium of a
fluid in which the polymer product is insoluble or poorly soluble and, as polymer is
produced, it precipitates or beads up in the medium while unreacted monomer
remains in fluid forrn. The temperature of the polymerization reaction is controlled
lo by controlling the temperature of the slurry medium. The slurry mediurn must be
separated from the polymer product by a subseguent processing step. Unreacted
monomer is also recovered for recycle in subsequent polymerization reactions.
Any processing step needed after the polymerization reaction to recover
polymer product increases its cost of production and, if practically possible, is
S desirably avoided.
Where possible, polymerization procedures producin~ polyolefin in particle
form are desirable. This consideration ma~es sl~lrry and gas phase procedures
preferred to a solution polymerizalion procedure where the product polyolefin isproduced in dissolved form. Nevertheless, a slurry procedure cannot be used to
20 produce low density ~<0.93 glcc) polymer particles, such as linear low density
polyethylene (LLDPE) and very low density polyethylene (VLDPE). While such
lO~h density polymers are not soluble in the slurry polymerization fluid, they often
become swelled by the fluid n-edium because of their <0.93 ~/cc density. This
unwanted swelling produces a l~elatinous polymer mass in the reactor rather than25 discrete polymer particles. Accordin~ly, such low density polymers are typically
produced by a gas phase polymerization procedure. An additional advantage in a
gas phase procedure is that no fluid medium is used, hence the need to separate the
polyrner product from the fluid, or purify the recovered fluid be~ore reuse, is
avoided. Further, in gas phase procedures, recovery of unreacted monomer for
30 reuse is also simplified.
Although, for reasons noted, gas phase is a preferred technique for
production of LLDPE and other low density types of ethylene polymers, gas phase
polymerization is subject to its own inherent dif~lculties and limita:ions when
producing particulate product. In the ~as phase technique, there is no liquid
35 solvent or fluid diluent utilized which can transfer the heat of the polymerization
reaction away from the reaction site, i.e., the catalyst surface. Gas phase
2141616 ~ ~`
Wo 94/03509 PCr/US93/073S8
- 5 -
polymerization temperature control may be achieved in part by the use of an inert
gas, such as nitro~en, and a fluidized bed of small solid polymer particles as a solid
diluent, for heat transfer.
In gas phase polymerization, polymerization is initiated with an initial bed
5 of polymer granules. Solid supported catalyst particles and monomers are
continuously supplied to the reaction zone of the reactor as the bed is fluidized or
agitated. The fluidization of the bed insures intimate mixino of the catalyst and
monomer as the product polymer is produced in particle form. The temperature of
the polymerization reaction is~ in significant part, controlled by regulation of the
o ~emperature of the gases fed to the reaction zone. A material balance is maintained
in the reactor reaction zone of the reac~or by periodic or continuous removal ofbed polymer particles to maintain the fluidized bed within constant prescribed
weight limits.
Critical to the proper operation of a fluidized bed gas phase reaction .
5 procedure is the ability to continuously remove polymer particles from the bed to
maintain the bed weight within prescribed limits. Hence, production of product
polymer as discrete free-flowing particles is essential. since this is essential to their
removal from the reaction zone.
When localized overheating occurs in a gas phase procedure, the polymer
20 particles which form about the solid supported catalyst particles may melt then
solidify upon cooling to produce adherent a~glomerations of particles, (i.e.,
polymer chunks and sheets), which foul the gas phase reactor. This phenomenon isan obstacle to practical use of a ~as phase procedure. In commercial practice, gas
phase polymerization is conducted in a continuous manner, with a product material
25 stream (polymer~ catalyst, unreacted monomer, etc.) being continuously removed
from the reaction vessel at a rate eguai to that at whicll a reagent material stream
of monomer and fresh catalyst is supplied to the reaction vessel. Formation of
polymer chunks and sheets wilhin the gas phase reactioll vessel interferes with and : .
may block the ability to con~inuously remove a product material stream from the
30 reactor. This would require shutdown of the reactor for defouling treatment. ln
an ideal mode of operation shutdown of the gas phase reactor would never be
required.
To date several methods Or, opolymer production by a fluidized bed gas
phase procedure have been sus~gested. U.S. Patent ~469~855 to Cooper notes that
35 condensation of low volatility comonomer in the reaction zone or in the recycle
circulation gas loop is a particular problem when attempting to produce a
21~1~16
WO 94/03~09 PCl`/US93/073~8
copolymer of low density. As a solution to this problem, Cooper describes the use
of an inert gaseous diluent~ such as N~ or ethane, in the feed gas monomer mixture
tc permit the maintenance of a comonomer partial pressure which is less than that
of ItS saturated vapor pressure at 60C while monomer polymerization is
S conducted over a Ziegler-Natta type catalyst at a polymerization temperature of at
least 60C but less than I 1 0C. Under such constrahlts the quantity of comonomer
which can be incorporated into the polymer is limited to an amount no greater than
about 0.5 mole%, and the copolymer has a relatively broad MWD and a density in
the LLDPE range.
U.S. Patent 4,527~987 to Hogan et al. describes a gas phase procedure
using a specific catalyst composition whereby comonomer is more efficiently
incorporated into the copolymer product, thus allowin~ lower concentrations of
comonomer to be used which in tllrn permits the monomer feed stream to be of
lower entry temperature (i.e., 2j-60C) so the monomer feed stream may be used
1S to control polymerization temperature to a ranoe of between 70-1 20C. Again, a
copolymer produced by this process would be of relatively broad MWD and have a
density like that of LLDPE.
United Kingdom Patent Applic~tion for Cozewith describes gas phase
polymerization with vanadium catalysts for the production of elastomeric
20 copolymers of ethylene and a-olefins up to C 10, but C3 to C5 are preferred
because of practical limitations of temperature and pressure in gas phase.
Likewise, U.S. Patent 5,106,804 to Bailey produces ethylene-butene copolymers ingas phase using zirconium metallocenes with alumoxane activators. U.S. Patent
5,100,979 to Eisinger, et al. discloses the oas phase polymerization of ethylene and
zs octene in gas phase fluidized bed reactor with a Vanadium catalyst and a
hydrocarbyl aluminum co-catalyst~ however the volume of octene that must be
used with the vanadium catalyst to obtain the small amount of incorporated
monomer is too large for practical purposes.
I)espite the suggestions of Cooper, Ho,an et al., Cozewith, Bailey and
30 Eisinger to date and so far as is known, a ~as phase procedure has not been
commercially used for production of a copolymer of ethylene and a comonomer
with 6 or more carbons.
Copolymers of .;;hylene with comonomers havin~ six or more carboil atoms
have various advantageous properties, such as improved impact strength and
35 gaugeability among others, compared to analogues produced with a comonomer oflower carbon number. A method for their practical production by a gas phase
WO 94/03509 2 1 4 1 6 1 6 PCI/US93/û735X
polymerization procedure which would allow one to enjoy the advantages inherent
in gas phase processing has yet to be realized.
SUMMARY OF THE ~NVENTION
This invention relates to the discovery that discrete olefin polymerization
s catalyst systems containing Group 4, 5 or 6 transition metals are capable of
polymerizing ethylene with one or more olefin comonomers, preferably having six
to ten carbon atoms, more preferably seven to ten carbon atoms, even more -~
preferably eight to ten carbon atoms under gas phase reaction conditions with a
high rate of incorporation of the comonomer into the copolymer product.
10 Preferable catalyst systems comprise activated cyclopentadienyl transition metal
catalyst systems. The activating a~ent may be an ahlmoxane or a non-coordinationanion. For a given concentration of a comonomer in the reaction zone a greater
amount of comonomer is incorporated into a narrow molecular weight distribution
copolymer product with the activated cyclopentadienyl catalyst than has heretofore
5 been possible to incorporate under ~as phase conditions with use of other types of
catalysts.
The process comprises contactin~, in a reaction zone, ethylene and one or
more olefin comonomers with an activated cyclopentadienyl transition metal
catalyst composition, under conditions of temperature and pressure which maintain ;
20 the ethylene-comonomer mixture in a ~aseo-ls state to produce an ethylene-a-
olefin copolymer having a density of from about 0. 850 to about 0.940 g/cc.
DETA~LED DESCRIPlON or T~IE PREFERRED EMBODlMENTS
The invention in its preferred embodiments relates to a gas phase process
for polymerizing ethylene in combination \vith olefin monomers such as a-olefins - -
25 and di-olefins, including mono-enes, di-enes, and poly-enes, in the presence of an
activated cyclopentadienyl transition metal catalyst which comprises the reaction
product of a transition metal compound and an ionic e~change composition or
alumoxane.
The polymerization is typically accomplished at a temperature below the
30 temperature at which particles of polymer product may fuse while the
concentration of comonomer is maintained below its de~ point for the temperatureand pressure conditions maintained in the reaction zone. Since the activated
catalysts of this invention incorporate monomer into the growing copolymer .,hair,
in higher amounts, i.e. have a higher reactivity ratio, smaller volumes of the C6 to
35 C10 olefin comonomer are necessary tO make the desired polymer. Thus
copolymers with higl1 comonomer content are a preferred product of this
21~1616
invention. L kewise this invenrion aiso provides a method for ootaining ethylene 7
copolymers that is more efficienr at incorporarinn the desired amount of monomer.
Copolymers havin, a hi~h comonomer content re!ative ~o the concentration of
comonomer and molar ratio or' e~hylene ~o comonomer in rhe reaction zone are
also prererred products or this invenlion.
Comonomer con~ent or'a copolvmer can be con~rolled throu_h the
selection ot ~he transition me~al compound component of the ca~alyst system and
by controllin~ the partial pressure of ~he various monomers. The partial pressure
of the comonomer in the reaction zone may be mainrained up ro an amount which
owould~ at ,~ temperature of I G-C less ~hat ~he ~emDe ature of the monomer mixture
in the re~clion zone. be the sarura~ed vapor pressure of the comonomer to prevent
' condensation of Ihe comonomer Lii~e~ise ~he parrial oressure ot- erhvlene may be
hi~her Inan those previouslv avaiiabie In a prer^erred embodiment ethylene is
present in the reaclion zone a~ a p'artial pressure of ~reater than aoout 40 psi (about
~7S kPa! ( I psi = 6 ~95 I;Pa!, prer`erably abour ! 00 (abour 689 kP~j to about "50
psi (about I 72i kPa). The partiai pressure or the C6 tO C 1 O comonomer is
prererabiv up to abou~ 5 psi (about 3 ~ kPa), even more preferabiv aoout ~ to i
about psi (about 13 kPa to abou~ 3 ~ ,~Pa).
In previousiy i;nown ~as phase poiymeriza~ion ~ecnniques. comonomer
present al the hioh amoun~s ne ded tO produce pol~,mer wilh a densirv of about
O.9I or iess would nave caused the ~ed ~o become iiquid This disadvanraoe is
avoided in ~he insIant invention oecause ~he calalvs; nas such a hit~n reactivitv rario
for the comonomers ~hat the comonomer is copoivmerized before ir can condense
" into a liauid. Furtherrnore. ~he ratio of the oc~ene n10iar concenrra~ion to the
ethylene mo}ar concentration is a use~l means for controlling the polvmenzation
and the final product properties. ln a preferred embodiment. the ratio of the
ethylene molar concen~ration ~o the octene molar concentration is preferably about
up to about 0 05, preîerablv abou~ 0,0~ or iess. e~e:l more preferably abour O.OI to
about 0.02.
The dew point limit has particular limits with hiQher moleeular weioht
comonomers such as octene. The cioser the dew point. the incipient temperature
at which a oas beoins to condensate inlo a liquid. the higher the prooaoility that the
pol~ner parricles in the fluidized bed will beyin ~o srick ~o~ether and cause
fluidization instabiiiries, In ~he ore~'erred embodimenr the rluidiz d bed reactor is
operared at a ~emperature such rhat ~he reacs~r rec- ole aas has a dew poin~ at least
, ~F beio~,v ~hat of ~he reactor bed. more preferaolv a~ leasl 1 0F below rhe reactor
Ai'fiENOFD SHEFI`
WO 94/03509 2 1 ~ 1 6 1 ~i PCI~/US93/0735s
bed temperature. The octene partial pressure in and of itself is not critical as long
as the dew point constraint is not reached. The octene partial pressure contributes
to the overall dew point, but its dew point is not a limitino factor. Rather it is the
total reaction gas dew point which is a controllin~ factor. There is no limit on the
s octene partial pressure except as dictated by the dew point constraint. In general,
the limits become more restrictive with higher comonomer molecular weights.
The polymerizations are preferably run at temperatures greater than the
dew point of the pure monomers. Thus in a preferred embodiment polymenzation
is run at a temperature of l 20F or above (about 48C or above), preferably about
0 130F to about 200F (about 54C to about 94C)~ even more preferably about
160F to about l 80F (abou~ 71 C to about 83C).
A narrow molecular wei~Jht distribution (Mw/Mn < 4, preferably < 3), as
measured by Gel Permeation Chromotography using polyethylene standards, is
produced having a comonomer content of from about 2 to about 3 times greater
than was heretofore possible lo produce under gas phase conditions. ln a preferred ~-
embodiment copolymers having about l O mole % comonomer or less, preferably
ha~ing about 4 to about lO mole% comonomer, are produced. Particularly
preferred polymers havin~g l ,000,000 Mw or above with MWD's of 4 or less are -~
produced using bis(cyclo-pentadienyl)hafnium dimethyl and the tri-substituted
ammonium salt of tetra(pentafiuoropllenyl)boron in the absence of a chain transfer
agent.
Preferred monomers include linear cyclic or branched olefins having from
six to ten carbon atoms, preferably a-olefins or diolefins having six to ten carbon
atoms. Preferred examples of comonorners include, but are not limited to, 1t9-
2~ decadiene, hexene-l, octene-l, 4-methylpentene-l, decene-l, norbornene, 1,4-
hexadiene, 4-methyl- l ,4-hexadiene~ ~-methyl- l ,4-hexadiene. l ,7-octadiene,
ethylidene norbornene, norbornadiene 3,5,S-trimethyl-hexene-l and the like.
These comonomers are contacted with ethylene and a catalyst system
comprising a transition metal compound havin~ a hydrolyzable ligand activated byeither an organoaluminum reagen~ such as methylalumoxane or an ionic exchange
activator composition as described in copendint~ U.S. Patent Application Serial
Nos. 133,052; 133,480; 542,236, 796,729 and ~ l 0~ j5 1, which are incorporated by
referer.cc.
~Activated Catalvst Svstem - Genel ;ll Descril~tioll
ln general, any ligand stabilized hydrolyzable mono, di- or poly-alkyl or
hydride complex of a transition metal may be converted into a reactive
214161~ '
ooraina~iveiv ~nsa~llra~e~ l~;v; or ;l~cir ae A.t!onic om?ie.Y ~v re~crion with an
~ctivator comoosition ?S iesc-:be~ !1e~ a*e The c?rionic ;ransi~ion me-al
_~moie.Y is cALtaivticqiiv Ac:i e `or ?civme ;z..~ion or ~hvie licqilv unsaturated
~onome s. Pre.`erqoiv ;he _a~a!~'S; iS ?re?are i n he-ero-ra leous. iuooorte~ -`orrn i~v
?iac_me~ or ~he atai~s; jv~;t n ~)n ;l iur)L~orl :Is ie~c.:be i in .eia~ed. corJending
. r;.s. Palent .~.ppiica~ion ~e .i ~o ~ i 0. ~ nci irs ;on~inua~ion in ?art ar~piication.
bo~h incorpora~e~ ~ re-are~ n [he r e1rire-v. or bv ?re?aration or`;he cataivst
vstem in particie :`orm.
?re.erred ~taivs;; .`or ~ in tnis inventlon ~re crme- .-`rom ~ transi~ion
0 me-ai ;-~mpouna; n~ainin y .lr .eas. one li~r?.na ~ ich .viik-e~qc: ~itn ~he cq~ion
oortion or`the ionic A?moie~. ?.c ~ cr ?- .e ?.oiv ne ii ~ana s .n ;ne nature or a
:.c.oce.taciie-.vi r-UD. 3S ;LIC.. '1 :~ .or;-nln - ?arl ~r`~ ~oivc.~c:ic i_?na arouo.
:.owe~e . anv ~nc:ik.r. i; ?.no. _..;;alntn 1~ . as; one reac :~.e me~ai-jit-ma i~onci .~n
be e.noiove2. . -ne re-e.!ea :OI)~C : rai!s; ;:nl oe r ?l eserl~e i bv one or -he
~ .oiiowina t~e~.e.~ai .`c~ nulae ' ail ~ enc ~ ;o i-~ro~os beint~ :;-.e ae~,v ~rouo nota~ion
or he ?e~.oaic Tabie e,r` he -. me~ ai des. !i~e~ ~v Che:nicai ana ~ntJ~neo~n~
e ~s -~3(5j ~~. ~85)
~ r(~-~-?)~ i [B ld- ~
~ [(.~-~_D jl~ ' L ~ ~ I r8 ci--
_o
Yl {[B]a }
(JS Z--1--y)
i~
~o wherein:
(A-Cp! i~ either ICpj (Cp ~) or Cp-.~ -Cp*; Co and Cp* are ~he
same or dif~erent cyciooentadi~ l r in - sub~ uted ~.vi~h r`rom ~ero to tlve
substi~ue:m ~.~oups S. ~?.ch s bs~i~uent ( . ouo ~ sei .y inde~e cie -.-lv. a radicai
grouo which is a hvdro-~rbvl. i; bsiitute -hvdr. c?.r ~ i. haiocal l. jubsri~ule -
ii ha~ocari~vi. hvdrocar~ ubs~ t~d or~anollle~ailoi~ aloc?.rbvi-jucstitute
or~nome~ailoid. d.is;:cis;.~ut-3 ~ciron. cijubs~ ea -,r;iC~c,~io.~. i osi;~u~ed
A~ENOED S~IEET
- - :214161~
chalcoge.~l ~r halooe:l radic.~ . or C3 and Cp are cvclopen~adienvl rin~es in which
anv two adiacent S grourJs are joined formin-v a C1 to C,tO ring to r~orm a sanlrated
or unsaturated poivcyciic c~; open~adienyi li~rand:
.~ is a bridt~ing t~rouo~ which vroup mav serve lo restrict rotation of
the Cp and C?~ rintrs or (C~ y-~y~cj and (JS z l-y) groups;
(CsH5 y xS~;) is a c,vcioDen~adienvi rin, substituted wi~h from zero
to five S radicais:
x is from I Ic ~ deno~int~ the de~re~ of substi~ution;
~ 1 isGroup or6 me~AI~
.Y l is a hvdri e radicai. h~drocar3vi radical~ substi~uted-nvdrocar~vl
- . radicaL hvdrocarbvl-subs~i~u~ed ortranometalloid adicai or nalocarbvl-iuostituted
or~anome~ailoid radicai. ~ hi;n adic~ lav op~ionailv be covaientiv Donded to both
or either ~1 and L ~r ail or an~ or ~ .
(JS z I-v) is ?. nelerocl~om ii ~and in wiliCil J is an eiement r;om
15 Group i j or^ ~he P~ iodic T.: ie ol Eie llen~s ~ h a coordina~ion numoer or i or an
element from Grouo 16 wi~n a coordination numi~e or ~: S is a radical t roup
which is a hvarocarbvl subâ:i~uted hvdrocarDyl haiocar~vl. substitut~n nalocart~vi
hvdrocart~yi-substituted or~ anometailoid. or naiocarDvl^jubslituted
or2anome~alloid; and z is the coordination number or Ihe element J;
~o visOor l.
I is an ole-ln dioier;n or arvne iigand. or a neutral L~.vis base: I
can also be a second transi~ion me~ ompouna or' :he same tvpe suc;t Iha~ the l-VO
me~i cente~s l~l and ~ re ~rid ~ed ;b~ Y ~ and .Y wilerein ~l~ has the same
meanin~ 2S M and ~ l hcld ~ - jclme meanin-~ a~ Y i ~here such dimeric
25 compounds wnich are preeu iors ;o lile calionic por;ion or the ca~aivsl are
represen~ed bv Ihe ~ormuia
(C5Hs-y-xsx) (JS ' z-1-y)
(A~)y 1~ (A~)y
(JS z_l_y) (C5H5-y-xSx)
A.~A JDE~ S~Eh
- P~ S ~ ',
RO / U ~ ~ S SEP l9
- 21~1616-
I, ~
~v is ~n inle~ o ~ . ¦
B is a r.ie~nicail~ ~raole. non-nucieophiiic anionic complex havin~ a
molecuiar ~i me-er aoout or ttre~e ~han ~ an-Jsrroms: ~nd
d is an in~e~er ~e?resen~in ~ the char~e or B
The ionic c~.aivsts are ~re?ared bv combinin ~ al le~st ;wo components. In
one pre.e~red me~hod. ;he firs~ ;)mpone!l~ is a ct.ciopentadienyl desiva~ive or a
Group ~ ~ or 6 me~ai compouna con~ainina at le3~1 one iiQand which wiil combine
~i~h ~he second comronenr or ~ le~s~ a portion ~here~r ;ucn as a cation poraion
hereo~ Tne seconQ comoone~r i~ an ion-e.Ychan ~e rompound comprisin~ a cation
0 which wiil irre-~ersioi~ ?.C~ `~'il[il ;11 !e~s~ one ii-~and c~ntaine~ in said me-al
e~mpound ffirst c~mrJonen~ ana a non-coordina~ina anion wilich is ei~her a sin~ie
;ooraination comoieY comprisin~ a pluraii~v or` iinopniiic radicais c~vaie~liy
~orciina~ea to and snieiainy a ~entral tormailv char ~e- e~riny me-ai or metalloid
atoms or an anion c~morisint~ ~. ?iuraiirv or boron a~oms ,uch as polvhedral
boranes. c~rboranes ~nd me~ail~c:1riJoran~
The c~ion por~ion or ~he ~;ond comeponen~ mav comorise Bronsted ac.ds
such as hvdrogen or ?rclonare - L-:vi~ bases or nav comorise re~uci~le Lewis
acids ;UC.l as te.~ic.num. rropyii~lm. triphenvic~r~onium ar si1ver c~eions
.~. Transl~ion ~e!ai Comoonent
The transi~ion me~al compo-lnds pre-èrre~ tor use as first compounds in the
preparation or ~he ionic c~ra~Yst are Pi bonded moie-ies such as cJciopentadienYi
deri~ratives of grouo . S or 6 rransition me-ai com~ounds. pre.re-abiv titanium.zrconiurn and h~rnium. re?rese .led bv ~he ~i10~vint t~eneral formuiae:
C p )!~'~ .
256. (.~-Cp)l~!~L
7 (Cp~)(CpR)~\~lX I
.
~C5~_y-xSx) (I. ' ) w
(~'\ / ~ X2
~vherein: (t~S' z:-l-Y)
(A CDj is ~ ~her ~Cl~) (CP~) cr Cp-~ -Cp~ Co ana Cp~ are he
sarne or di~ere:lt cyc opensadien~ i rin Js suostiruted ~ h rrom ze-o to five
35 ;ubs~i~ue~I ~roups 5. eac'n subsritue~ rouo S ben~. indepe:~aensl~. a ndica~
~roup wnic~ is a hvcroc?.rb~ i. iui~ititute -11! droc a ~ i naioc~rib~ l. iuos;i~u~ed-
AI~ENDED SHEET
r
2141616
halocarbvl. ;~vdrocar~vi~ bstituled ort~anome~ailoid. halocarbyi-iubstituled ' ' - '
organomesalloid, iisubsti~uted boron. disLIbstitured pnictooen, substituted
chalcooen or ha~oaen radical. or C? and Cp~ are c~. clooentadienyi rin_s in wh~ch ', `
any two adjacent S groups are joined rormin(~ a C ~ ;o C~o rint~ to ~ive a sarurated
or unsatura~ed poivcyciic cvciopenradienvi lit~and: -
R is a substiruent on one or' the cyclo~en~adienyl radicals which is '-also bonded to the me~ai alom;
A' is a bridgin~J ~roup. ~ hich ~roup mav ser~e ~o res~rict rotation of
the Cp and Cp* rin~Js or ~C~Hs ~ ;S~;; and Js~(z- 1-~3 ~Jroups;
~1 is ~s de~lned abo~e.
~, yis~Jor l; ' ~
(C~H~.v.y~) is a c-ciopenladienvi ring substituted with rrom zero ' -
tO five S raaicals: -
x is ,'om I lo ~ denolint~ the de~ree or`substirution:
(JS'z l v~ is a hete oalom in ~hich J is an eiement ~rom Group 15
of the P~iodic Tabie of Eiements ~ h a coordina~ion number of ~ or an element
from Group 16 ~,vitn a c~ordin~lion nuMber or ': S' i~ a radical ~roup which is a
hydrocarovl, ,ubstituled hyarocarbyl. I~aiocarbyl. ;ubstituted halocarbvl, ~ -
hvdrocarbvl-;ubstil~led or~non~e~alloid. or halocarDyl-,uDs~ituted
20 organome~alloid; and z is the coordina~ion number or` the eiemen~ J;
L' is an oler;n. diolet;n or ar,~ne ii~Jand. or a neulral Lewis base: L'
can also be a secona ~ransition melai .ompound or ;he same type such that the two
me~al cen~ers M ana ;~1~ are bl ici~ed b~ .~ 1 and .`i' I . ~vherein .~ as ~ne same
- meanin~ as M and .Y'I h~d the ~ame meanin~ 2S .~ ere such dimeric
'~ compounds which ar~ precur;ors to the cationic por;ion or' the cataivst are
represented by the .~'ormuia;
(C5~5-y--xSx) (JS ' z--1--Y~
\ ` ~Xl X ~ /
(A~ / X\ X~ l~M~ ~A~ ) y
(JS ' z-1-y) (C5H5-y-Xsx)
w is an inte~. r'rom ~i to i. a
A,~tENDED SHE~
WO 94/03509 2 1 ~ 1 6 1 6 PCr/US93/0735L
- l 4 -
Xl and X2 are, independently, hydride radicals, hydrocarbyl
radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted
halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloidradicals; or X l and X2 are joined and bound to the metal atom to forrn a
s metallacycle ring containing from about 3 to about 20 carbon atoms; or X1 and X2
together can be an olefin, diolefin or aryne ligand.
Table 1 depicts representative constituent moieties for the metallocene
components of folmulae 6-9. The list is for illustrative purposes only and should
not be construed to be l;miting in any way. A number of final components may be
0 formed by permuting all possible eombinations of the constituent moieties with each other. lllustrative compounds of the formula 6 type are:
bis (cyclopentadienyl)hafnium dimethyl,
bis(tetrahydroindenyl)zirconium dihydride,
bis(pentamethyl)zirconiuM ethyliden~,
3 dimethylsilyl(l-fluorenyl)(cyclopentadienyl)titanium dimethyl and the like.
Illustrative compounds of the formula 7 type are: -
bis(cyclopentadienyl)( l ,3-butadiene)zirconium~
bis(cyclopentadienyl)(2,3-dime~hyl- l ,3-butadiene) zirconium,
bis(penta-methylcyclopentadienyl)(benzyne) zirconium,
bis(pentamethylcyclopentadienyl) titani~lm ethylene and the like.
Illustrative compounds of the formula 8 type are: (pentamethylcyclopentadienyl)
(tetramethylcyclopentadienyl-metllylene)zirconium hydride,
(pentamethylcyclopentadienyl) (tetramethy~vclopentadienyl-methylene)hafnium
benzyl,
(pentamethylcyclo-pentadienyl)(tetramethylcyclopenta-dienylmethylene) zirconium
phenyl andthelike.
Illustrative compounds of the formula 9 type are: -
dimethylsityl(tetramethyl-cyclopentadienyl) (t-butylamido)zirconium dimethyl, ~:
(methylcyclopentadienyl)(phenylamido)titanium dimethyl, :'
methylphenylsilyl(indenyl) (phenyphosphido) hafnium dihydride~ ~-
(pentamethylcyclopentadienyl) (di ~utylamido) hafnium dimethyl and the like
B. The Activator Component
Preferred acti~a~d catalysts can be prap~.red by reactin~, 2 transition metal
compound with some n utral Lewis acids. such as B(C6F5)3, which upon reaction
3s with the hydrolyzable ligand (X) of the transition metal compound forms an anion,
such as ([B(C6F5)3~X)]-), which stabilizes the calionic transition metal species
W0 94/03509 2 1 ~ 1 6 1 6 . PCIIUS93107358
which is generated by the reaction. lonic catal~sts can be, and pre~erably are,
prepared with activator components which are ionic compounds or composi~ions.
Compounds useful as an activator component in the preparation of the .
ionic catalyst system used in the process of this invention comprise a cation, and a
s compatible non-coordinatin~ anion wllicll anioll is relatively large (bulky), capabte
of stabilizing the active catal,~sl species (the Group 4, i or 6 transition metal
cation) which is formed when the tWO compounds are combined and said anion is
sufficiently labile to be displaced by olefinic, diolefinic, and acetylenically
unsaturated substrates or other neutral Lewis bases such as ethers, nitriles and the
lo like. Three classes of compatible non-coordinating anion compositions have been
disclosed in copendin~~ U.S. Patent Application Nos. 133,05~; 133,480 and
796,729 (herein incorporated b~ ret`erence) I ) anionic coordination complexes
comprising~ a plurality of lipophilic r adicals covalently coordinated to and shielding
a central charge-bearin=, metal or metalloid core; 2) anions cornprising a plurality
of boron atoms such as carboranes, metallacarboranes and boranes; and 3)
polyanionic compositions wherein a plurality of either of the above two types ofnon-coordinating anions are covalently bonded tO an atomic, molecular or
polymeric complex or particle ~T) which forms the central core of the polyanionic
composition.
ln general, ~he activa~or compounds conn~linin~ sin~le anionic coordination
complexes which are usef;ll in this inven~ion ma~ be represented by the following
general formula:
10. [[[L'~-HjT]d¦(M~)m+QIQ~ Qn]d~
wherein:
H is a hydro~Ten atom,
[L"-H] is a Bronsted acid;
M' is a metal or metalloid;
Ql to Qn are~ independentlv hydride radicals, bridged or unbridged
dialkylamido radicals, allio~icle and ar~lo:;ide radicals, hydrocarbyl and substituted-
hydrocarbyl radicals, halocarb.~l and substituted-halocarbyl radicals and
hydrocarbyl and halocarbyl-substituted or~anometalloid radicals and any one, butnot more than one, of Q I to Qn may be halide radicals;
m is an inte~ er representingT the formal valence charge of M'; and
n is the total numbel of Q li~ands.
3s As indicated above. anv metal or metalloid capable of forming an anionic
complex which is stable in \~ater ma~ be llsed or conlained in the anion ofthe
WOg4/035~9 2141616 rcr/us93~0'358~ ~
- 1 6 - .
second compound. Suitable rnetals then, includ~, ~ùt are not limited tO, aluminum,
gold, platinum and theilike. Suitable metalloids include, but are not limited to,
boron, phosphorus, silicon and the like. Compounds containing anions which
comprise coordination complexes containing a sin le metal or metalloid atom are,of course, well known and many, paniculal ly suclI compounds containing a singleboron atom in the anion portion~ are available commercially. In light of this, sal~s
containing anions comprising a coordination complex containing a single bor~n
atom are preferred.
The preferred activator compounds comprising boron may be represented
0 by the following general formula:
11 . [L"-H]+[BArl Ar~X3X4]-
wherein:
[L"-H] is as defined above;
B is boron in a valence state of 3~
Arl and Ar~ are the same or dif~erent aromatic or
substituted-aromatic hydrocarbon radicals containins~ from about 6 to about 20
carbon atoms and may be linl;ed tO each other throu(~h a stable bridging group; and
X3 and X4 are. independently, hydride radicals, hydrocarbyl
and substituted-hydrocarbyl radicals, halocarb~l and s~lbstituted-halocarbyl
radicals, hydrocarbyl and halocarbyl- sllbstitllted oroanometalloid radicals,
disubstituted pnictogen radicals. substi~uted chalcooen radicals and halide radicals,
with the proviso that X3 and X4 will not be halide at the same time. -~-
In general, Arl and Ar~ may, independently, be any aromatic or
substituted-aromatic hydrocarbon radical. suitable aromatic radicals include, but `
are not limited to, phenyl, naphthyl and anthracenyl radicals. Suitable substituents
no the substituted-aromatic hydrocarbon radicals, include, but are not necessarily
Iimited to, hydrocarbyl radicals, include. but are not necessarily limited to,
hydrocarbyl radicals, or~ano metalloid radicals, alko~y and arylo~y radicals,
alkylamido radicals, fluorocarbyl and fluorohydrocarby!l radicals and the like such
as those usefui as X3 and X4. The substituent may be ortho, meta or para, relative
to the carbon atoms bonded to the boron atom. When either or both X3 and X4 ::
z.~e a hydroca.by! radical, each may be the same or a dif~erent aromatic or
substituted-aromatic radical as the Arl and Ar~. or the same may be a straight or
branched alkyl, alkenyl or alkynyl radical, a c~clic hydrocArbon radical or an alkyl-
substituted cyclic hydrocarbon radical X~. and X4 may also. independently be
W094/03~09 21 416 16 ~ PCr/US93/0735B
- 17-
alkoxy of diallcylamido radicals ~herein the all~yl portion of said alkoxy and
dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and thelike. As indicated above, Arl and Ar2 could be linked tO either X3 or X4. Finally,
X3 and X4 may also be linked to each other through a suitable bridging group. 5
s The most preferred activator compounds comprising boron may be
represented by the following g~eneral formula:
12. [L"-H]+[B(C6F5)3Q]- q
wherein~
F is fluorine, C is carbon and [L"-H], B, and Q are defined above.
o Illustrative, but not limiting, examples of most preferred activator compounds
comprising boron which may be used in the preparation of the improved catalysts
of this invention include N,N-dialkylanilinium salts, e.g., L" = N,N-dialkylaniline,
where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or
where Q is a polymeric hydrocarbyl of indefinite chain length such as polystyrene,
polyisoprene, or poly-paramethylstyrene. Polymeric Q substituents on the most
preferred anion offer the advantage of providino a solid phase catalyst system
which may be used as such in gas phase proceessng, without the need for a separate
catalyst support material.
Activator components based on anions which contain a plurality of boron
atoms may be represented by the following general formulae:
13. [L''-H]c[(CX)a(BX')m~''b]C- or
14. [L''-H~d~[[(CX6)a~(BX7)n1~(X~)b~]c~]2Mlln+]
wherein:
[L"-H] is either H~ or a Bronsted acid derived from the protonation
of a neutral Lewis base;
X, X', X", X6, X7 and Xg are, independently, hydride radicals,
halide radicals, hydrocarbyl radicals. substituted-hydrocarbyl radicals, halocarbyl
radicals, substituted-halocarbyl radicals, or hydrocarbyl or halocarbyl-substituted
organometalloid radicals;
M" is a transition metal;
a and b are integers > 0; c is an integer ~ l; a + b + c = an even
numbered integer from 2 to about ~; and m is an imeger ranging from 5 to about
22;
a' and b' are the same or a different integer; c' is an integer ~ 2; a' +
b' + c' = an even-numbered integer from 4 to about 8; m' is an integer from 6 toabout 12; n' is an integer swch that 2c' = n' = d'; and d' is an inte_er ~ 1.
21~161G
WO94/03~09 PCI/US93/07358 f J''
- lS -
Preferred anions comprisin~ a plurality of boron atoms are
(1) A trisubstituted ammonium salt ~ bornane or carborane anion
satisf~ing the general formula
1 5 [(CH)ax(BH~bx]Cx~
s wherein;
ax is either 0 or l; cx is either l or 2; ax + x = 2; and bx is an
integer ranging from about l O to 12;
('~) A trisubstituted ammonium salt of a borane or carborane or a
neutral borane or carborane compound satisfying the general formulae
16 [(CH)ay(BH)my(H)by]CY~
wherein
ay is an inte~er from 0 to 2; by is an inte ~er from 0 to 3; cy is an
integer from 0 to 3; ay + by + cy = ~. and my is an inle~er from about 9 to about
18; or
(3) A trisubstituted ammonium salt of a metallaborane of
metallacarborane anion satisfying the followin~ eneral formula
17 [~[(cH)az(BH)mz(H)bz]cz-]2Mllnz+]d
wherein
az is an integer from 0 to 2; bz is an integer from 0 to 2; cz is either -
2 or 3; mz is an integer from about 9 to l l; az + bz + cz = 4; and nz and dz are,
respectively, 2 and 2 or 3 and l: M" is as defined abo~ e
The activator composition most preferred for formin;, the ionic catalyst
used in this process are those containing a tetrapentafluorophenyl boron anion or ~-
two or more tripentafluorophenyl boron anion groups covalently bound to a central
-atomic, molecular or polymeric complex or particle Other examples of activator
specific compositions which may be used to form an anionic catalyst usefill in this ~-
invention are idçntified and more fully described in European Patent applications 0
277 003 and 0 277 004 which are hereby incorporated by reference
The catalyst used above may also be activated with alumoxanes Preferred
alumoxanes are those alumoxanes represented by the following general formulae
1 8 (R3-Al-O)p
19 ~D~4(RS Al O)p-AlR62
20 (M~)n+Q~m
An alumoxane is generally a mixture of both the linear and cyclic compounds In
the general alumoxane formula~ R3, R4~ R~ and R6 are~ independently a Cl-C6
WO 94/03509 2 1 ~ 1 6 1 6 PCr/US93/07358
1 9
alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "p" is aninteger from I to about 50 Most preferably, R3, R4, R5 and R6 are, each methyl
and "p" is a least 4. When an alkyl aluminum halide is employed in the preparation
ofthe alumoxane, one or more R3-6 t~roups may be halide. M' and M are as
described previously and Q' is a partially or fully fluorinated hydrocarbyl.
As is now well known, alumoxanes can be prepared by v~rious procedures.
For example, a trialkyl aluminum may be reacted with water, in the form of a moist
inert organic solvent; or the trialkyl aluminum may be contacted with a hydratedsalt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield
an alumoxane. Generally, however prepared, the reaction of a trialkyl aluminum
with a limited amount of water yields a mixture of both linear and cyclic species of
alumoxane.
The Alumoxane activated transition metal compounds of this invention may
be placed on a support as disclosed in U.S. patetnt 4,808,561 which is herein
incorporated by reference as if fully set forth.
C. The Catalvst Support
Typically, the support can be any of the l;nown solid catalyst supports,
particularly porous supports, such as talc, silica, inorganic oxides, and resinous
- support materials such as polyolefins. Preferably~ the support material is silica or
an inorganic oxide in finely divided form.
Suitable inorganic oxide materials which are desirably employed in
accordance with this invention include Group 2, 4, 13 or 14 metal oxides. The
most preferred catalyst suppon materials include silica, alumina, and silica-alumina
and mixtures thereof. Other inorganic oxides that may be employed either alone or
in combination with the silica, alumina or silica-alumina are magnesia, titania,zirconia, and the like. A preferred support is magnesium chloride as disclosed in
US Patent ~,106,804 to Bailey, which is incorporated by reference herein. Other
suitable support materials, howe~er. can be employed, for example, finely divided
polyolefins such as finely divided polyethylene.
The metal oxide support used in the preparation of the catalyst may be any
particulate oxide or mixed oxide such that it is substantially free of adsorbed
moisture. Generally, the metal oxides contain acidic surface hydroxyl groups
wh~ch may react with and deaclivate the ionic metallocene catalyst when the
catalyst is added to the slurried metal oxide support. Therefore, if a catalyst
support material which contains surface hydroxyl ~roups is employed, it is
preferred that the support be treated prior to use, e.g., subjected to a thermal or
Wo 94~03509 21 ~ 1 6 1~ PCI/US93/073_ ~
- ~0
chemical treatment, in order to remove water ar!d réduce the concentration of the
surface hydroxyl groups. The treatment may bë carried out in vacuum or while
purging with a dry inert gas such as nitrogen at a temperature of about 100C toabout I000~C, and preferably, from about 3û0C to about ~00C. The duration of
the thermal treatment can be from about I to about 24 hours. Shorter or longer
times can be employed provided equilibrium is established with the surface
hydroxyl groups.
As an alternative method of dehydration of the metal oxide support
material, chemical dehydration can be advantaoeously employed. Chemical
10dehydration converts all water and hydroxyl groups on the oxide surface to inert
species. Useful chemical agents are for example, chlorosilanes, such as ~-
trimethylchlorosilane, dimethylaminotrimethylsilane and the like. The chemical
dehydration is accomplished by slurryin~ the inoroanic particulate material, such ~ ~
as, for example, silica in an inert low boiling hydrocarbon, such as, for example, . `
1~hexane. During the chemical dehydration reaction, the silica should be maintained :
in a moisture and oxygen-free atmosphere. To the silica slurry is then added a low :
boiling inert hydrocarbon solution of the chemical dehydrating agent, such as, for ~ .
example, dichlorodimethyls ,ane. The solution is added slowly to the slurry. Thetemperature ranges during chemical dehydration reaction can be fram about 25C ~;
20to about 120C, however, higher and lower temperatures can be employed.
Preferably, the temperature will be about 50C to about 70C. The chemical
dehydration procedure should be allowed to proceed until cessation of gas ~-evolution. Generally at this point all the moisture is removed from the particulate
support material. Normally, Ihe chemical del-ydration reaction will be allowed tO
25proceed from about 30 minutes to about 16 hours, preferably I to 5 hours. Upon ~:
c ompletion ofthe chemical dehydration, the solid particulate material is filtered
under a nitrogen atmosphere and washed one or more times with a dry, oxygen-
free inert hydrocarbon solvent. The wash SG. ~nts, as well as the diluents
employed to form the slurry and the solution of chemical dehydratin~ agent, can be --
30any suitable inert hydrocarbon. Illustrative of such hydrocarbons are heptane, hexane, toluene, isopentane and the lil;e.
Once treatment to minimize or reduce, the surface hydroxyl groups is
complete, it is preferred to further treat the s-:,,p^r~. media with an aluminum alkyl
solution, preferably about 3 mmol of I M hexane solution per gram of support
35isolated. This treatment ~enerally leads to an increase in catalytic activity and
prolonged shelf life of the supported catalyst system. It has been found that when
:
~ - 2141616. . . ~. . WO ~41035~9 PCrJUS93107358
~ 1
employing the supported ionic catalyst of the subject invention in conjunction with
an organoadditive, such as a Group 13 additive, during polymerization, increasedcatalytic efficiency and reduced reactor fouling is observed. If a support media is t
employed where dehydration to remove surface hydroxyl ~roups is not necessary,
s one may optionally proceed to treat the support with the aluminurn alkyl to obtain
the benefits disclosed. A further optional step to employ is to prepolymeri2e the
supported catalyst system with an olefinic monomer in order to strengthen particle
size of the polymer product formed.
The specific particle size, surface area, pore vol~lme, and number of surface
hydroxyl groups characteristic of the inorganic oxide determine the amount of
inorganic oxide that it is desirable to employ in preparing the catalyst
compositions, as well as affecting the properties of polymers formed with the aid
ofthe catalyst compositions, these characteristics must freguently be taken intoconsideration in choosing an oxide for use in a particular aspect of the invention.
For example, since the catalyst composition is to be used in a gas-phase
polymerization process - a type of process in which it is known that the polymerparticle size can be varied by varying the particle size of the support - the inorganic
oxide used in preparing the catalyst composition should be one having a particlesize that is suitable for the production of a polymer having the desired particle size.
In general, optimum results are usually obtained by the use of inorganic oxides
- having an averaoe particle size in the range of about 30 to 600 microns, preferably
about 30 to l O0 microns; a surface area of about 50 to 1,000 square meters per
gram, preferably about 100 to 400 scluare melers per gram; and a pore volume of
about 0.5 to 3.5 cc per gram; preterably abo-lt 0.5 to ~ cc per gram.
D. Catalvst Preparation and Use
The supported ionic mesallocene catalyst used in this invention may be
prepared by combining the me~allocene component, the activator component and
the support. Typically this combination occurs in a suitable solvent in one or more
steps. lt is preferred that the metallocene and activator components be combinedin the presence of a suitable solvent or diluen~ as a first step and therea~er the
metallocene-activator product be contacted with the support. Suitable solvents
include, but are not necessarily limited to~ straight and branched-chain
hydroca.bons such aS isGbutane, butane, pentane, hexane, isohexane, heptane,
octane and the like; cyclic and alicyclic hydrocarbons such âS cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane and the like; and aromatic
21~1611i
Wo 94/03~09 PCr/US93/073~8
and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the
like. The aromatic and alkyl-substituted aromatic sol~nts are preferred.
While the supported ionic metallocene cata!ysts do not contain pyrophoric
species, it is nevertheless preferred that the catalyst components ~e handled in an
S inert, moisture-free, oxygen-free environment such as ar~on, nitrogen or helium
because of the sensitivity of the catalyst components to moisture and oxygen.
In a preferred method, the metallocene and activator components are ~ ~
combined in a first step in an aromatic solvent to produce a catalytic solution. This . .
reaction may be carried out in the temperature Mnge offrom -100 to about 300 -~
0 C, preferably about 0 to about l 00C. Holding times to allow for the completion
ofthe reaction may range from about 10 seconds to about 60 minutes depending ~
upon variables such as reaction temperature and choice of reactants. ~ ~.
The catalytic solution produced by combinino the metallocene and activator : .
components is then contacted with the support. The method of contact may vary, .; ~-
but it is preferred that the catalytic solution be added to a rapidly stirred slurry of :
the catalyst support in a hydrocarbon solvent, preferably an aliphatic solvent.
Contact temperatures may ran~e from about 0~ to about l 00C depending upon
the solvents used. Contact times may vary from about 10 seconds to about 60
minutes, longer contact times than 60 minutes not providino any significant
additional benefits. In a pref'erred embodiment the activated catalys~ is placed in .
slurry ofthe dried support material in an aliphatic solvent for a contacting peniod
offrom about 10 seconds to about 60 minutes. .
The activated cataiyst is contacted with an alumina, silica or silica-alumina
support to produce the most preferred activated catalyst. ~
In the preparation of the supported catalyst, the rea~ents should be :
combined to provide a catalyst concentration (metallocene and activator) on the
support offrom about O.Ol wt.% to about 20 wt.%, preferably about 1 wt.% to :~:
- about S wt.% based upon the weight of the support.
An alternative embodiment of this invention is to place the activator
component on a support employiny the steps disclosed above. The supported
activator may be stored as is, under inert conditions, to be combined at a later time
with a metallocene component. A further alternative is to place the metallocene
component orl a support and store as is, to be later activated by ar. activator
component. In another preferred embodirnent of the invention the activated
3S catalyst is placed on a support according to the method disclosed in copending
United States Application Number USSN 7/885,170 filed 5-18-92.
r - 2 1 ~ 1 6 1 6
WO94/03509 PCIIUS93/07358
~ .
-23-
In a most preferred embodiment of the present invention, the catalyst
system is forrned with a bis(cyclopentadienyl) titanium or zirconium compound,
I;ke those of formulae number 5-7. Examples of preferred compounds and
activators include but are not limited to bis(cyclopentadienyl)zirconium dimethyl or
s bis(cyclopentadienyl)hafnium dimethyl reacted with N,N-dimethylanilinium ~3
tetra(pentafluorophenyl)boron (DMAH) or methylalumoxane.
Employing a mixed metallocene catalyst system can achieve molecular P
weight distributions within the ran~e of about I . 5 to about I S. The substituents of
the cyclopentadienyl radicals, however, can exert a profound influence on polymer
o molecular weights and degree of comonomer incorporation.
A particularly surprisin~ feature of some of the supported catalysts of~this
invention, particularly those based on hafnocenes in combination with an activator -
component comprising perfluorinated tetraphenylborate anions, is that when the
catalysts of this invention are used to copolymerize ethylene and a-olefins alone or
in combination with diolefins, the amount of higher molecular weight olefin or
diolefin incorporated into the copolymer is significantly increased when compared
to copolymers prepared with the more conventional Ziegler-Natta type catalysts,
vanadium catalysts and bis(cyclopentadienyl)zirconium catalysts. The relative rates
of reaction of ethylene and hi~her a-olefins with the aforementioned hafnium-
based catalysts are much closer than with conventional Ziegler-Natta type catalysts
ofthe Group 4 metals. The comonomer distribution in copolymers prepared with
- the catalysts will range from about near perfectly alternating to statistically
random. Consequently, the hafnocene based ionic metallocene supported catalysts
are particularly preferred.
ln other embodiments of the invention wherein the catalyst system is
formed with a cyclopentadienyl transition metal compound like that of formula
number 8, titanium is the preferred transition metal. In this case a titanium species
ofthe catalyst generally exhibit higher catalyst activities and permit production of
polymers of greater molecular weight and greater amounts of incorporated
comonomer than do analogous species of zirconium or haffiium.
The Polvmerizsltion Process
The polymerization of ethylene and comonomer is effected using an
activated catalyst system as describcd, preferably the catalyst is supported as
described. The polymerization is carried ou~ in a continious gas phase, preferably
~S in a fluidized bed reactor. Polymerization is initiated with an initial bed of polymer
granules, preferably the polymer of the initial bed is of like kind to the copolymer
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WOg4/03509 PCI~/US93/073~8 t~
- 24 -
to be produced as product polymer. Solid supported~talyst particles and I --
monomers are continuously supplied to the rea~i'on zone of the gas phase reactor ¦ -:
while the bed is fluidized or agitated. Preferabiy the gas mixture comprising the , :
monomers is utilized to fluidize the bed. As the polymerization reaction proceeds ~,
S a material bal~nce is maintained in the gas phase reaction zone by periodic orcontinuous removal of bed particles to maintain the bed within prescribed desired
limits. In general it is desirable to l;eep the bed level at its maximum height to --.
maintain a high production rate.
Temperature control is ef~ected by control of the temperature of gas
mixture feed to the reaction zone, the concentration of monomers within the gas `
mixture feed to the réaction zone, the concentration of catalyst feed to the reaction - `
zone, or by evaporation of a hydrocarbon spray supplied to the reactian zone, or ~ : -
by a combination of two or more of these means for control. Preferably the
temperature of the reaction zone is controlled to be between about 130 to 1 90FlS (54 to 88C) to minimize the chance of reactor fouling by fusion of polymer :
particles within the reaction bed or along the walls of the reaction zone. -~
Bed temperature is preferably controlled by ~a combined control of inlet
feed gas mixture temperaturej recirculating gas temperature and concentration of -
catalyst supplied to the reaction zone. Generally, it is preferred to supply the feed
~ gas to the reaction zone at a temperature in the range of from about 0 to about 50 ~ `
;C and to supply~a monomer concentration and catalyst concentration to the zone
sufficient to produce a~ heat of reactlon from the polymerization reaction that will :
maintain a~gas ternpat~ure in the zone ~which is 5 to:50C higher than the
temperature ofthe~feed ~gas. ~ ~
The~feed gas supplied to the reaction zone in part comprises ethylene, the
- balance being the~ selected olefin comonomers alone or a combination of
comonomer with an inert diluent`~as~such as ni~rogen or ethane. When a diluent
gas is used, it is preferably nitro~,en. To prevent condensation of comonomer
within the reaction zone to a liquid phase thal could disrupt fluidization of the bed,
the concentration within the feed~ gas must be limited to be below that amount
which, at~the condition of pressure and reaction ~as temperature maintained within ' .
the zone, causes the comonomer to exceed its saturated vapor pressure. Thus the
partial pressure of thc comonomer must be carefiully observed and controlled. For
the condition of pressure existin~ in the reaction zone, the amount of comonomer: 3S supplied thereto should provide a partial pressure of the comonomer which is less
than the saturated vapor pressure of the comonomer at that temperature which is ;
;~
WO 94/03509 2 1 4 1 6 1 6 PCr/USg3/073~8 ~ :
~, }
less than the reaction zone temperal~lre. and preferably ~C less than the reaction
zone temperature. ln a preferred embodiment a polymerization temperature of .
about 80C plus or minus ten de ,rees C will be maintained in the reaction zone and .
the inlet gas will be maintained at or below a parlial pressure equal to the saturated
s vapor pressure of the comonomer feed at the reactor temperature. The inlet gas is
preferably 5C or more below the reactor temperature, more preferably 10C or
more below the reactor temperature.
With respect to the amount of comonomer supplied to the reaction zone,
the amount of ethylene supplied may then be selected to provide a copolymer
10 product having the desired mole% of incorporated comonomer -- which is
dependent upon the particulars of the ionic catalyst system used. Accordingly,
under some conditions of ~gas phase operation. depending upon the desired content
of comonomer to be incorporated into the copolymer product, the feed gas may be
ethylene and comonomer alone. Under other conditions it may be necessary to use
5 an inert diluent gas as a component in the feed gas either to produce a copolymer
ofthe desired comonomer contenl or to aid in temperature control in the reactionzone or both. In any event~ b)~ reason of the catalys~ system with which the gasphase reaction is carried out~ it is possible ~o mhlimize the amount of diluent gas
which may be needed, which in lurn ma~;imizes the productivity of the gas phase
20 reactor.
This is a particular advantage wherein a comonomer having seven or more
carbon atoms is used. Since ethylene- l -octene copolymers have greater impact
strength and gaugeability than similar mole % comonomer content copolymers of
ethylene with l-hexene or 1 -b~ltene, the process of this invention is of particular
25 advantage in the production of an ethylene- I -octene copolymer. Thus, even when
a relatively low mole % content of l-octene is desired in the copolymer product,the ethylene and l-octene monomers for its production may be supplied to the
reaction zone in concentrations based upon the maxin1um permissible l-octene
concentration~ which, by comparison ~o prior gas phase processes, means a greater
30 concentration of ethylene and a lesser concentration or even no inert diluent gas is
needed, and this maximizes Ihe producti~it~ of ll~e reactor. Likewise, where prior
gas phase processes were incapable of producing, at economically feasible
production rasc~. a copolymer havingl a content of l-octene of greater than about
0.5 mole %, this invention produces copol!~mers of ethylene having contents of 0.8
35 mole % octene and greater at economicall~ teasible production rates.
21~1616 ;~
WO94/03509 PCrJUS93/0735~
~..
- ~6 - ,
As noted, the particulars of the.p~e'ssures and temperatures selected for
maintenance within the reaction zone of the reactor will dictate the rnaximum ~:
permissible amount of the selected comonomer which may be supplied thereto; thisin turn will dictate the amounts of ethylene and/or inert diluent gas that must be ~ ;
supplied to the reaction zone in order to produce with the particular ionic catalyst .. `.
used a polymer of the desired amount of incorporated comonomer. Typically, the .: .
gas phase reaction may be carried out at pressures ranging from about 50 psi ~ ~ .
(about 344 kPa) to about 500 psi (about 3500 kPa); and preferably from about 200 ;~.
psi (about 1379 kPa) to about 350 psi (about ~100 kPa). With respect to the
o partial pressure selected for the reaction, the amo~lnt of catalyst to be supplied is
that amount which will maintain a rate of reaction of monomers within the zone : .
sufficient for the cooling systern to remove the heat of reaction that will maintain
the desired gas temperature within the reaction zone. :~:
CODOIVmer PrOdllCtS Or tl1e Metl10d :::
I5 The copolymers prodLlced by this invention are higher in comonomer
content resulting in products of lower density and have higher molecular weight
than conventional copolymers. The hit~her comonomer content of these polymers ~:
gives higher tear strengtll. and allow thinner films to be produced with equivalent
tear strengths to films formed from conventional polymers. The copolymers of this
invention also produce fi1ms of gre~ter clarity.
The copolymer of this inventi~n can be t`ormed into ~rticles, films, adhesives,
lubricants, molded articlesmtlelt blown articles. fibers. fabrics. sheets, spun bond
fibers or spun bond fabrics by methods well l;nown in the art.
EXAMPLES
All Molecular weight are weigllt average molecular weight unless
otherwise noted. Molecular weigThts (Mw and Mn) were measured by standard
Gel Permeation Chromotography techniques known in the art. Melt Index (MI)
was measured according to ASTM-D 1~38, condition E. Density was measured
according to ASTM D -1501. Comonomer content was measured by proton N~
using standard techniques known in the art. Melt Index Ratio is the ratio of I
over I2. I2 1 is measured by ASTM-D I ~38-F. 1~ is measured by ASTM-D 1238-
E (and is also known as Melt Index). ~vlelt index is inversely proportional to
~olecular weight and Melt Inde.~; Ration is directl~ proportional tc molecu!..,
weight. Bulk density was measured by the followhlg method: The resin is poured
3s via a 7t8" diameter ~Innel into a fi:~ed \~olume cylinder of 400 cc. The bulk density
is measured as the wei~ht of the resin divided by 400 cc to give values in g/cc.
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WO 94/03509 PCr~US93/07358
Panicle size was measured by de~erlllinin6 the wei~ht of the material collected in a
series of U.S. Standard sieves and determininc~ the ~veight average particle size .
based on the sieve series used.
Catalyst system may be produced using the followin~, procedure. First, a .
5 silica support is dehydrated at 200C for 4 hours in a fluidized bed dehydrator. We
used Davison 948 silica manufactured by the Davison Chemical Division of W. R.
Grace Corporation. Those skilled in the art will appreciate that other supports
could be substituted. 800 ~rams of this dehydrated silica is placed in a clean, dry,
nitrogen sparged mixer reactor at 24C. To this, ~.00 Iiters of toluene and 1.06o liter of 30% MAO in toluene are rapidly added while stirrino. The temperature of
the reactor is increased to 68C and held at this temperature for four hours while
continuing mixinn. Ne!;t, ~3 ~rams of bis( I -metll~yl. 3-n-butvl cyclopentadienyl)
zirconium dichloride dissol~ed in .50 iiters of tolllene are rapidly added whilecontinuing to stir. Synthesis and pllrit'ication of this metallocene is performed
15 using techniques known to those sl;illed in the art. The mixer is maintained at
68C for one hour followin~ the addition of the metallocene. Vacuum is
maintained on the reactor until the slurry dries to a free flowing solid with volatiles
of 10% or less. Mixing is continued throughout dryin~n This process yields about1.0 kg of the completed catalyst s~stem. Those skilled in the art will appreciate
20 that the process can be scaled Llp to produce the catal~st system in commercial
quantities.
In an alternative embodiment. a shnilal catalyst s~stem is produced uSin
the same bis( I -methyl, 3-n-b~llyl :yclopentadienyl) zirc~nium dichloride
metallocene ln this method, however, the MAO is formed in situ. 4.82 liters of a25 15% trimethyl aluminum in heptane sol-ltion is added to a clean~ dry, nitrogen
sparged mixer. The reactor is cooled to -4C. To this solution 700g of hydrated
silica with a loss on ignition (OH content) ~alue of 1~.5% is slowly added,
maintaining a temperat~lre witllin th~ ran!~e of -~C to 1 0C. The silica addition
should occur at a continuous slow rate over a I to ~ hour period. Those sliilled in
30 the art will appreciate that the reaction of trimethyl alumin-lm with the moisture
contained in the si5ica is hihly e~othermic and must be carefi~lly controlled to
a~oid temperature transients and other process problems. The silica used is
Davison 948 manufactured by the Davisor. Chc..,ical Divisio.. of W. R. Grace
Corporation. Followino completion of silica addition. the temperature is
maintained at 10C and 15.75~, ofthe metallocene dissolved in heptane is added.
The reactor temperat~lre is then increased to 68C over l hour, and then is
21~161G. I;
W094/03509 PCr/US93/073~8
~,~, ,.,~
maintained at 68C for one hollr while mixin~ lixin`l~ is then ceased and the ~ ~:
solids are permitted to settle for 30 minutes as the temperature is dropped to 38C. , ~ :
The liquid phase is decanted and the r emainin~, sl-lrry is dried at 68C under ;- ~
vacuum for about 4 hours~ until the residue becomes a free-flowing solid with a ; .
s volatiles level of 10% or less. This process yields about 0.9 I;g ofthe completed
catalyst system. ~:
As described above, bis(l-methyl, 3-n-b~ltyl cyclopentadienyl) zirconium :
dichloride supported on silica with a MA0 activator produced in accordance with ~ ::
one of the methods described above is a preferred catalyst system and yields good -
10 results. However, those sliilled in the art will appreciate that a suitable silica
supported catalyst system employinl!~. this metallocene and an MA0 co-catalyst can ¦
be produced in a variety of other manners. For e~ample, the absolute and relative
amounts of the metallocene and co-catalyst can be varied as necessary to optimize
the catalyst system. The support can also be altered.
Further, we have found tht~ other metallocenes can be substituted for that
described above. For e.Yample, we ha~e achieved ~enerall!, satisfactory results
with other metallocen~s, sucll ~is bi~(n-bulyl-~ clopenladienyl) zirconium dichloride
and bis(i-propyl-cyclopentadienyl) zirconium dichlol ide. Each different
metallocene will yield a uni~lue composition distribution. As with the preferred20 metallocene, we have found that thes~ alternati~es, when used in supported form in
a sontinuous gas-phase polymerization process, yield resins with a somewhat
broader composition distribution and a somewhat hi~her l~lz/Mw than is obtained
when using the same metallocene in its unsupported form. This is very~ significant
because the slight broadening~ of the composition distribution and the slight
25 increase in Mz/Mw yield improvements in processability of the resins and also in
certain important properties of products incorporatin~ the resins. While we have ,,
only tested a relatively small n-lmber of metallocenes in the process of this ~ :
invention, we contemplate that a si(~nificant number, including~ substituted andunsubstituted mono-, bis and tris cyclopentadienyl metallocenes, could be
30 successfiully employed. Similal Iy it i~ conlelllplated that co-catalysts other than
MA0 could be used. It will also be desirable to used mixed metallocene catalyst
systems in some applicalions L!si~ a mi.~e(l mctallocene sys~em will typically
yield a broader molecu'ar wei~llt disilibulioll than a sino~le metallocene system.
ln the preferred embodiment, the resin is produced using a continuous gas-
3s phase fluidized - bed polymerization process. Such continuous, gas-phase,
flui~siized bed polymerization processes are well known to those skilled in the art.
~.` . 2141616
WO 94/03~09 PCr/US93/07358
I
~9 1:
Certain parameters of the ,as-phase process must be adjusted somewhat where a
supported metallocene is used. For e~;ample, the rate of comonomer incorporationby a metallocene catalyst is higher than that for a conventional coordination
catalyst. Accordingly, to achieve a given density the comonomer should be
5 maintained at a lower concentration in the reactor than would be the case were a
Ziegler-Natta catalyst employed. While, we used an 18" (41 cm) gas phase pilot ~.
plant, those skilled in the art will appreciate that for other reactor configurations
certain of these conditions will vary. J
EXAMPLE 1
0 Catalvst Prep~r~tion
To a clean, dry mi~er under a blanke~ of nitro~en were added 800 grams of
silica dehydrated at 200 C with an LOI (loss on ignition~ water content of
approximately 3 weight percenn To thi~ was added ~000 ml of toluene to suspend
the silica. To this, ~.00 liters of toluene and 1.06 liter of 30% MAO in tolueneS were rapidly added while stirrin~n 1 he jacket temperature was increased to
produce an internal temperal~lle oJ` I ~jF ( 6SC). The temperature was held for
four hours with continious mi~in~n Ne~t, ~3 grams of bis( l-methyl, 3-n-butyl
cyclopentadienyl) zirconium dichloride dissolved in .50 liters oftoluene was rapidly
added while continuing to stir. This was allowed to react at 155 F ~68C) for
20 another hour with mixing. The catalyst solids were dried with nitrogen under
vacuum at 155F (68C) until the catalyst was dl~ and free flowing The catalyst
had a volatiles content of 10 weight percent or less.
Polvmeriz:ltioll
An eighteen inch continio~ls gas phase fluidized bed reactor having a bed of
25 ethylene/ I-octene ~ranules wai ~Ised. The gdseous feed streams of ethylene,
hydrogen and liquid octene were mi~ed to~ether in a mixing tee arrangement and
introduced ~elow the reactor bed into the recycle ~as line. Tri-ethylaluminum
(TEAL) was also mixed with this stream as a 1% by weig~ht solution in isopentanecarrier solvent. The individual flow r ates of ethylene~ hydrogen and octene were
30 controlled too maintain fi~;ed composition targets. The ethylene concentration was
controlled to maintain a constant ethylelle partial pressure of 157 psia (1083 kPa).
Equivalently the ethylene concentration was contl olled at 50 mole percent. The
hydrogen was controlled to maintain a constant hvdros~en to ethylene mole ra~iv.Octene flow rates were controlled at a fi~ned flow ratio to ethylene. The
35 concentration of octene was also measured by an of~-line gas chromato~,raph to
ensure relatively constant octene composition in ~he recvcle ~gas stream. The 1-
WO 94/03S09 2 1 ~ 1 6 i 6 P~JUS93/07358 ~
...
. ,.~
- '.0- 1
octene was purified before use by pur~ g with nitro,,en and treatment in a fixedbed of molecular sieves. The solid catalyst (bis ( I -methyl, 3-n-butyl ¦ ~ -
cyclopentadienyl) zirconium dichtoride activated wi~h~nethyl alumoxane) was ~ -
injected directly into the fluidized bed using purifie~ nitrogen as the carrier. Its
S rate was adjusted to maintain a constant production rate. The reacting bed of
- ~owing polymer particles was maintAined in a fluidized state by continuous flow
ofthe make up feed and recycle ~as through the reaction zone. A superficial gas ¦
velocity of 1.7 ~/sec was used to achieve this. The reactor was operated at a total
pressure of 300 psig (2069 kPa). To maintain constant reactor temperature, the
temperature of the recycle gas was continuously adjusted up or down to
accommodate any changes in the rate of heat generation due to the polymerization.
The fluidized bed was ~maintained at a constant height by withdrawing a portion of
the bed at a rate equal to the formation of particulate product The product was
removed semi-continlously ViA a series of vatves into~a fixed volume chamber, -~-
which was simultaneously~vented back lo the reactor. This provided for highly
efflcient removal of the product, while at the same time recycling a large portion of
the unreacted gases back to the reacton The producl, an ethylene-octene
copolymer, was then pur ,ed to remove entrained ~hydrocarbons and treated with a ~ -
~; ~ small steam of humidified nitroyen to deacti\~ate any trace quantities of residual
cata!yst.~ Other parameters and data are summarized in the table~below. ~ -
'~
' ~ i ' .
~ ~ ''':
.
2141~1G
WO 94/03509 PCI /US93/07358
, . .
Reactor I 'roperties
Melt Index (d~lmin) 1 05
Density (glcc) 0 91 S0
Melt Index Ratio 18.1 _ _
Physical I 'roperties
Bulk Density (lb/~_/k~lm3) _9.1 / 466.~
Avg. Particle Size (inch I cm)_ 0.Q308 / .078
Fines (%) through 120 mesh 0.S8
Ash (ppm) 186 _ _
Reactor Co lcentrations
Ethylene (mole %) 50.~ -
Octene (mole %) 0.45'~ _
Hydrogen (mole%) 101 _
Nitrogen (mole%) 47.8
Octenelethylene mole ratio 0 0090
Hydrogenlethylene mole ratio 0.000~0 _
TEAL (wt. ppm) 7g
_ Reaclor C `onditions
Production Rate (lblhr 11 I;~fhr) ~7 0 /J ~5 86
Reactor Temp (F/ C) _ 174 1 / 78.94
CatalystProd (Ib/lb) 3630
Bed Weight (lbl kg~) '~37 / 107.5
Reactor Res. Time (hr) 4.1
Gas Velocity (ftJsec 11 m/sec) 1. 7 11 0. 518
Pressure (psig / kPa) 3001 ~068. 5
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