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USOO748241 OB2

(12) United States Patent (10) Patent No.: US 7482.410 B2


Fischbuch (45) Date of Patent: Jan. 27, 2009
(54) PROCESSES FOR PRODUCING HIGH 5,066,736 A 1 1/1991 Dumain et al.
DENSITY POLYETHYLENE 5,137,994 A 8, 1992 Goode et al.
5,352,749 A 10/1994 DeChellis et al.
(75) Inventor: D. Brett Fischbuch, Kingwood, TX
(US)
(73) Assignees: ExxonMobil Chemical Patents Inc., (Continued)
Houston, TX (US); Saudi Basic FOREIGN PATENT DOCUMENTS
Industries Corporation, Riyadh (SA);
Saudi Yanbu Petrochemical Company, EP O 359444 3, 1990
Yanbu Al Sinalyah (SA)
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 (Continued)
U.S.C. 154(b) by 36 days. Primary Examiner Fred MTeskin

(22) Filed: Mar 22, 2006


O O Processes for reducing the ultra high molecular weight poly
(65) Prior Publication Data meric material content of a high density polyethylene pro
US 2006/0223958A1 Oct. 5, 2006 duced with a bis-triarylsilyl chromate catalyst system are
provided. Processes for reducing the gel content of articles
Related U.S. Application Data produced from high density polyethylene are also provided.
(60) Provisional application No. 60/666,982, filed on Mar The gel content of the articles is reduced by using the high
31, 2005 s- Y-1's density polyethylene with reduced ultra high molecular
s weight polymeric material content to produce the articles.
(51) Int. Cl The processes described reduce the content of ultra high
cosF 2M34 (2006.01) molecular weight polymeric material in comparison to con
COSFIO/O2 (2006.015 ventional high density polyethylene by introducing at least
one catalyst deactivator into a recycle gas line containing a
(52) U.S. Cl. "535, si 36. s 5. recycle gas stream associated with the fluidized bed reactor.
s s s f The at least one catalyst deactivator has a boiling point lower
(58) Field of Classification sts, 84.67. 68. than the maximum temperature within the recycle gas line. In
lication file f 1 s so is hhi s s certain embodiments, the at least one catalyst deactivator is
See application file for complete search history. introduced in the portion of the recycle gas line upstream of a
(56) References Cited recycle gas cooler at a ratio of 0.0075 mole of the at least one
catalyst deactivator per 1 million moles of make-up ethylene
U.S. PATENT DOCUMENTS to about 0.12 mole of the at least one catalyst deactivator per
3,324,095 A 6, 1967 Carricket al. 1 million moles of make-up ethylene in the reaction system.
3,324,101 A 6, 1967 Baker et al. In certain embodiments, the at least one catalyst deactivatoris
3,704,287 A 11, 1972 Johnson OXygen.
4,003,712 A 1, 1977 Miller
4,803,251 A 2f1989 Goode et al. 53 Claims, 4 Drawing Sheets
US 7482.410 B2
Page 2

U.S. PATENT DOCUMENTS FOREIGN PATENT DOCUMENTS


5,462.999 A 10, 1995 Griffin et al. EP O 449 519 10, 1991
5,625,012 A 4/1997 Hussein et al. WO WO 99/O9075 2, 1999
6,022.933 A 2/2000 Wright et al. WO WO 03/042253 5, 2003
6,878,454 B1 * 4/2005 Shannon et al. ............. 428,523
2004/0236040 A1 11/2004 Mihan et al. * cited by examiner
U.S. Patent Jan. 27, 2009 Sheet 1 of 4 US 7482.410 B2

Fig. 1

-Ziegler-Natta Catalyzed Polyethylene H 'Bis-triarysily Chromate Catalyzed Polyethylene

Carbon Number
U.S. Patent Jan. 27, 2009 Sheet 2 of 4 US 7482.410 B2

Fig. 2
U.S. Patent Jan. 27, 2009 Sheet 3 of 4 US 7482.410 B2

£
25,

(Wudd) use ulueuoo oleu/iod MNH?


U.S. Patent Jan. 27, 2009 Sheet 4 of 4 US 7482.410 B2

(zuysef) ulu unopies)


US 7482.410 B2
1. 2
PROCESSES FOR PRODUCING HIGH reaction.” The Application also indicates that the fine dust
DENSITY POLYETHYLENE wetted by the catalyst poison that is not removed in the
cyclone serves to avoid undesirable polymerization and
CROSS-REFERENCE TO RELATED deposit formation in the circulating gas. The Application
APPLICATIONS discloses that the catalyst poison must have a boiling point
above the maximum temperature within the recycle stream.
This application claims the benefit of U.S. Provisional U.S. Pat. No. 5,066,736 to Dumain, et al., discloses the
Application 60/666,982, filed Mar. 31, 2005, which is fully addition of an activity retarder into a reaction system for
incorporated herein by reference. polymerization of alpha-olefins, particularly linear low den
10 sity polyethylene. The activity retarder may be a polymeriza
FIELD OF THE DISCLOSURE tion inhibitor. The retarder is added to the polymerization
system to control the temperature within the polymerization
This disclosure relates to processes for producing high reactor. The retarder may be added directly to the reactor; to
density polyethylene with reduced ultra high molecular a monomer feed line; to a recycle separator device Such a
weight polymeric material content Suitable for producing 15 cyclone separator, to a recycle line from the cyclone separa
articles having reduced gel content. tor, or to a reaction mixture recycle line located downstream
BACKGROUND OF THE DISCLOSURE
of a heat exchanger used to cool the reaction mixture recycle
Stream.

Numerous systems and processes for polymerizing olefins BRIEF DESCRIPTION OF THE INVENTION
are known. Introduction of various compounds into polymer
ization reactors to control polymer product properties is also This invention relates to processes for reducing the con
known. For example, U.S. Pat. No. 6,022.933 to Wright, et al., centration of ultra high molecular weight (“UHMW) poly
discloses the addition of a “catalyst poison'. Such as oxygen, meric material when producing high density polyethylene
to a fluidized bed reactor used to produce high density poly 25 with bis-triarylsilyl chromate catalyst systems in fluidized
ethylene using bis-triarylsilyl chromate catalyst systems. The bed reactors and processes for producing articles from the
catalyst poison is added directly to the reactor or in a gas high density polyethylene. The processes are useful for pro
recycle line at a location downstream of the associated ducing high density polyethylene Suitable for conversion into
recycle gas cooler. The 933 patent discloses that the catalyst films and other articles having reduced gel contents. In addi
poison is to be introduced into the reactor in the range of about 30 tion to films, the high density polyethylene is suitable for
0.005 to about 0.5 part by volume per million parts by volume production of a variety of articles having reduced gel content
of ethylene feed to the reactor. The catalyst poison is added in such as pipes, geomembranes, and molded articles.
this manner to increase environmental stress crack resistance
of articles made with the polymer produced. The 933 patent The gel content in the films and articles is reduced by the
refers to the addition of oxygen as "oxygen addback. 35
reduction of the concentration of UHMW polymeric material
in the polyethylene produced by the processes described
Another effect attributed to the "oxygen addback” is lowering herein. The processes described herein reduce the content of
the molecular weight of the high density polyethylene pro UHMW polymeric material in comparison to conventional
duced.
high density polyethylene production processes by introduc
U.S. Pat. No. 4,803,251 to Goode, et al., discloses a process ing at least one catalyst deactivator into a recycle gas stream
for the reduction of sheeting during polymerization of alpha 40
at a location selected from (i) upstream of a recycle gas cooler
olefins by the introduction of positive charge generating addi associated with the fluidized bed reactor, (ii) into the recycle
tives or negative charge generating additives into the poly gas cooler, (iii) 2 meters or less downstream of the outlet of
merization reactor to neutralize the static charge in the the recycle gas cooler, (iv) 1 meter or less downstream of the
reactor. The polymerization processes disclosed are for use outlet of the recycle gas cooler, and (V) combinations thereof.
with titanium or vanadium catalysts with aluminum cocata 45
The at least one catalyst deactivator has a boiling point lower
lysts. Positive charge generating additives are identified as than the maximum temperature within the recycle gas line.
alcohols containing up to 7 carbonatoms, oxygen, and nitric In certain embodiments, the at least one catalyst deactiva
acid. Methanol is described as the preferred positive charge tor is introduced at a ratio of 0.0075 mole of the at least one
generating additive. Negative charge generating additives are catalyst deactivator per 1 million moles of make-up ethylene
identified as ketones containing up to 7 carbon atoms such as 50
feed to about 0.12 mole of the at least one catalyst deactivator
acetone and methyl isobutyl ketone. The 251 patent per 1 million moles of make-up ethylene feed. In certain
describes that the additives are to be added to the reactor.
Introduction of the additives to the recycle stream just embodiments, the at least one catalyst deactivator is oxygen.
upstream of the inlet to the bottom of the reactor vessel' is BRIEF DESCRIPTION OF THE DRAWINGS
described and exemplified. This location is downstream of the 55
recycle stream compressor and cooler.
Addition of compounds to the recycle gas stream in olefin FIG. 1 is a graphical representation of oligomer content of
polymerization systems is known. For example, Published polyethylene resins produced with bis-triarylsilyl chromate
U.S. Patent Application 2004/0236040 to Mihan, et al., dis catalyst systems compared to the oligomer content of poly
closes the introduction of a liquid catalyst poison upstream of 60 ethylene resins produced with Ziegler-Natta catalyst systems.
a cyclone separator positioned in the recycle stream. The FIG. 2 is a schematic diagram of an exemplary reactor
liquid catalyst poison serves to “wet fine dust particles to system for producing high density polyethylene having a
facilitate removal of the particles from the recycle gas in the reduced concentration of UHMW polymeric materials in
cyclone. Another effect attributed to the catalyst poison wet accordance with the processes described herein.
ting the dust particles is that the catalyst poison is removed 65 FIG. 3 is a graphical representation of UHMW polymeric
from the circulating gas to prevent it from reaching the reactor material content over time for high density polyethylene that
where it “can have an adverse effect on the polymerization may be produced according to the processes described herein
US 7482.410 B2
3 4
and high density polyethylene that may be produced accord embodiments, the level of incorporation of the at least one
ing to conventional processes. comonomer is from about 0.1 wt.% to about 2 wt.%.
FIG. 4 is a graphical representation of gel counts over time In certain embodiments, the molar ratio of the at least one
for films that may be produced according to the processes comonomer to ethylene in the fluidized bed reactor is about
described herein and for films that may be produced accord 0.001:1 to about 0.015:1. In additional embodiments, the
ing to conventional processes. molar ratio of the at least one comonomer to ethylene in the
fluidized bed reactor is about 0.002:1 to about 0.008:1. In still
DETAILED DESCRIPTION OF THE INVENTION other embodiments, the molar ratio of the at least one
comonomer to ethylene in the fluidized bed reactor is about
A variety of advantages are obtained by production of high 10 0.003:1 to about 0.006:1. The molar ratio of the at least one
density polyethylene using bis-triarylsilyl chromate catalyst comonomer to ethylene in the reactor, of course, corresponds
systems. However, it is observed that such catalyst systems to the molar ratio of monomers incorporated into the high
frequently impart increased gel content in films and other density polyethylene.
articles produced from Such high density polyethylene. The fluidized bed of the reaction systems used in the pro
Gels in films and other articles result, at least in part, from 15 cesses described herein may also contain hydrogen, typically
the presence of UHMW polymeric material in the high den to control the melt index of the high density polyethylene
sity polyethylene used to produce the films and other articles. produced. In certain embodiments, hydrogen is introduced
This disclosure relates to processes for producing high den into the fluidized bed reactorata concentration of in the range
sity polyethylene using bis-triarylsilyl chromate catalyst sys of about 0.005 mole to about 0.08 mole of hydrogen per mole
tems. This disclosure also relates to processes for reducing of ethylene. In other embodiments, hydrogen is introduced
the concentration of UHMW polymeric material in such high into the fluidized bed reactorata concentration of in the range
density polyethylene resins. Additionally, this disclosure of about 0.0075 mole to about 0.05 mole of hydrogen per
relates to processes for reducing gels in films and other mole of ethylene. In still other embodiments, hydrogen is
articles produced from high density polyethylene resins. introduced into the fluidized bed reactorata concentration of
For purposes of this disclosure, the term “high density 25 in the range of about 0.01 mole to about 0.04 mole of hydro
polyethylene' refers to polymers incorporating at least 90 wt. gen per mole of ethylene.
% of polymeric units derived from ethylene monomers and The processes described herein are useful for producing
having a density of about 0.94 g/cm to about 0.965 g/cm. In high density polyethylene suitable for conversion into films
certain embodiments, high density polyethylene produced by and other articles having reduced gel contents. The processes
the processes described herein has a density of about 0.94 30 described herein are particularly suitable for producing poly
g/cm to about 0.96 g/cm. In other embodiments, high den ethylene polymerized with bis-triarylsilyl chromate catalyst
sity polyethylene produced by the processes described herein systems in fluidized bed reactors.
has a density of about 0.948 g/cm to about 0.958 g/cm. Gels are unmelted polymer particles or streaks in the poly
High density polyethylene, as described herein, is pro meric material matrix forming an article. With respect to
duced by polymerizing ethylene alone, or optionally, in the 35 films, gels generally have a thickness greater than the gauge
presence of at least one comonomer. The ethylene and the of the film matrix. The gels are also typically more opaque
optional at least one comonomer should be present at certain than the film matrix. The dominant gel type observed in films
concentrations in the reactor for a given catalyst to produce a produced from high density polyethylene resins catalyzed
polyethylene of a certain density and melt index. The density with bis-triarylsilyl chromate catalyst Systems is a round
and melt index of the polyethylene generally depend on how 40 semi-opaque gel with a melting point that is 0°C. to 5° C.
well a catalyst incorporates the at least one comonomer. Suit above the melting point of the film matrix. Even if the gels
able comonomers include olefins having from 3 to 20 carbon have the same melting point as the as the polymeric material
atoms in one embodiment and 3 to 12 carbon atoms in other Surrounding the gel, the gel may not melt upon melting of the
embodiments. Exemplary comonomers include propylene, polymeric material because the thickness or other geometric
butene, pentene, 4-methylpentene, hexene, octene, decene, 45 dimensions of the gels may prevent them from heating to the
and cyclic olefins such as styrene. Other monomers can melting point. Excessive gel levels result in poor visual
include polar vinyl, dienes, norborene, acetylene and alde appearance of extruded films and other articles and may lead
hyde monomers. to breakage or failure during production or use of the film or
In certain embodiments, the at least one optional comono article. Generally, when gel levels exceed a certain threshold
mer is selected from the group of C to Cs alpha-olefins, and 50 level, a film or article is rendered substandard and must be
mixtures thereof. In other embodiments, the at least one disposed of or sold at a reduced cost.
comonomer is selected from the group of butene, pentene, It is believed that one factor contributing to the formation
hexene, octene, and mixtures thereof. In still other embodi of gels is the presence of UHMW polymeric material in the
ments, the at least one comonomer is selected from the group high density polyethylene used to produce the films and
ofbutene, hexene, octene, and mixtures thereof. In additional 55 articles exhibiting gels. It is believed that gels become larger
embodiments, the at least one comonomer is selected from and occur at greater concentrations as UHMW materials
the group of butene, hexene, and mixtures thereof and the accumulate in the recycle gas system particularly in the lower
high density polyethylene has a density of about 0.948 g/cm temperature regions that exist from the recycle-gas-line
to about 0.958 g/cm. cooler to the reactor distributor plate. It is believed that poly
The ratio of the at least one comonomer to the ethylene, 60 meric particles exiting the recycle line cooler may adhere to
when present, in the high density polyethylene may vary over downstream Surfaces and continue to polymerize to produce
a range. Typical concentration ranges of the at least one UHMW materials in the lower temperature regions of the of
comonomer in the high density polyethylene range up to 10 the recycle system.
wt.%. In certain embodiments, the concentration of the at It is believed that polymeric particles have a greater pro
least one comonomer may range up to 5 wt.%. In other 65 pensity to adhere to Surfaces in the lower temperature regions
embodiments, the concentration of the at least one comono of reaction systems employing bis-triarylsilyl chromate cata
mer is from about 0.1 wt.% to about 5 wt.%. In still other lyst systems than in reaction systems utilizing other catalyst
US 7482.410 B2
5 6
systems because of the higher oligomer concentrations typi embodiments, the boiling point of the at least one catalyst
cally present in bis-triarylsilyl chromate catalyzed material. deactivator is determined at the highest pressure within the
FIG. 1 is a graphical representation of C to C. oligomer recycle line. In other embodiments, the boiling point is deter
concentrations measured in granular resin Samples using two mined at Standard pressure, 1 atmosphere (101.3 kPag).
methods: 1) short-path thermal desorption gas chromatogra In certain embodiments of the processes described herein,
phy using a mass spectroscopic detector, and 2) gas chroma the maximum temperature within the recycle gas line is about
tography of liquid extracts from the granular resins. High 120° C., the minimum temperature within the recycle line is
density polyethylene produced with a bis-triarylsilyl chro about 25°C., and the maximum pressure within the recycle
mate catalyst System and a high density polyethylene cata gas line is about 2,000 kPag to about 2,600 kPag. In other
lyzed with a Ziegler-Natta catalyst were analyzed. The oligo 10 embodiments of the processes described herein, the maxi
mer concentrations are reported as ppm by weight of the mum temperature within the recycle gas line is about 115°C.,
oligomer per 1 million parts by weight polyethylene. It is seen the minimum temperature within the recycle line is about 30°
that in the Co to Coligomer range, the bis-triarylsilyl chro C., and the maximum pressure within the recycle gas line is
mate catalyst system produces dramatically higher concen about 2,000 kPag to about 2,600 kPag. In additional embodi
trations of oligomers. These oligomers are present in the cycle 15 ments, of the processes described herein, the maximum tem
gas in Sufficient concentrations to condense on Surfaces in the perature within the recycle gas line is about 110° C., the
lower temperature regions of the reaction system. It is minimum temperature within the recycle line is about 35°C.,
believed that the condensed oligomers provide a sticky Sur and the maximum pressure within the recycle gas line is about
face to which polymeric particles adhere. Bis-triarylsilyl 2,000 kPag to about 2,600 kPag.
chromate catalyst Systems have greater longevity and more Introduction of the at least one catalyst deactivator inhibits
activity than Ziegler-Natta catalysts in the lower temperature the catalytic activity of bis-triarylsilyl chromate catalyst sys
regions from the cooler to the distributor plate. Thus, the tem particles entrained in the recycle gas, particularly in the
chromate catalyst systems are still active and will continue to lower temperature regions of the recycle system within and
polymerize polymeric particles into UHMW polymeric mate downstream of the recycle line cooler. Due to the inhibited
rial at the Sticky Surface created by the oligomeric material. 25
catalytic activity, continued polymerization of the polymeric
It is thought that after the adhered particles polymerize into particles that are trapped by condensed oligomers and
UHMW polymeric materials, some of the UHMW materials adhered to the metal Surfaces, and other polymeric particles,
periodically break off from the surfaces to which they are is inhibited. Therefore, reduction in the creation of UHMW
adhered and are carried into the fluidized bed where they are polymeric material that serves as gel precursors in high den
mixed with the desirable lower molecular weight high density 30
sity polyethylene and gels in films and other articles produced
polyethylene product. The UHMW polymeric material serves therefrom is reduced.
as a precursor to gels in films and articles produced from the At least one other mechanism, in addition to the mecha
high density polyethylene.
For purposes of this disclosure, the term “UHMW poly nism described above, may promote generation of gel precur
meric material” refers to polymeric material having a weight 35
sors in high density polyethylene catalyzed by bis-triarylsilyl
average molecular weight (M) of greater than 500,000. (The chromate catalyst systems. It is believed that the processes
weight average molecular weight can actually be much described herein also disrupt these other potential gel-forma
higher, in the range of 1-2,000,000, or even higher.) High tion mechanisms, thereby contributing to further reduction of
density polyethylene resins produced with bis-triarylsilyl gel precursors. Although this mechanism is not fully under
chromate catalyst systems typically have a weight average 40 stood, an initial and immediate reduction in gel concentra
molecular weight of about 75,000 to about 350,000. tions in films and articles produced from high density poly
The processes described herein are thought to reduce the ethylene produced by the processes described herein would
formation of UHMW polymeric materials in the lower tem confirm disruption of the mechanism.
perature regions of reaction systems employing bis-triarylsi Based upon a reduction in the formation and growth of
lyl chromate catalyst systems. The reduction in the formation 45 UHMW polymeric materials as described above, a reduction
of these UHMW polymeric materials thereby reduces the of gels in the later stages of a polymerization run are
concentration of gel precursors in the high density polyeth explained. However, a reduction ingels in the initial stages of
ylene and correspondingly provides a reduction in gels in a polymerization run are unexplained by a reduction in the
films and other articles produced from the high density poly formation UHMW materials over time. Therefore, it is
ethylene. The processes described herein reduce the forma 50 thought that another mechanism contributes to formation of
tion of UHMW polymeric materials by the introduction of at gel precursors in the early stages of a polymerization run, and
least one catalyst deactivator in the reaction system recycle likely the later stages as well, is disrupted by the processes
line at a location selected from (i) upstream of a recycle gas described herein.
cooler associated with the fluidized bed reactor, (ii) into the As used herein, the term “bis-triarylsilyl chromate catalyst
recycle gas cooler, (iii) 2 meters or less downstream of the 55 system” refers to the supported reaction product of at least
outlet of the recycle gas cooler, (iv) 1 meter or less down one bis-hydrocarbylsilyl chromate and at least one compound
stream of the outlet of the recycle gas cooler and (v) combi selected from the group consisting of hydrocarbylaluminum
nations thereof. compounds and hydrocarbylboron compounds. Exemplary
The at least one catalyst deactivator has a boiling point catalyst systems are described in U.S. Pat. No. 5,137,994.
lower than the maximum temperature within the recycle gas 60 Bis-tryarylsilyl chromates and methods of their preparation
line. For purposes of determining the maximum temperature are described in U.S. Pat. Nos. 3,324,095; 3,324,101; and
and pressure within the recycle line, various equipment 3,704,287. Exemplary bis-triarylsilyl chromates are bis
through which the recycle gas stream is routed Such as com triphenylsilyl chromate; bis-tritolylsilyl chromate; bis-trixy
pressors and recycle coolers are considered to be part of the lylsilyl chromate; bis-trinaphthylsilyl chromate; bis-trieth
recycle gas line. In certain embodiments, the at least one 65 ylphenylsilyl chromate; bis-trimethylnaphthylsilyl
catalyst deactivator has a boiling point lower than the mini chromate; and bis-adamantyl chromate. The hydrocarbylalu
mum temperature within the recycle gas line. In certain minum compound may be described as a co-catalyst, as a
US 7482.410 B2
7 8
promoter, or as a reducing agent when it is reacted with the to about 100 microns; a surface area of about 100 to about 750
chromate prior to carrying out the copolymerization. square meters per gram and preferably about 240 to about 550
Exemplary hydrocarbylaluminum compounds include tri square meters per gram; and a pore size of about 80 Ang
hydrocarbylaluminum compounds, hydrocarbylaluminum stroms to about 300 Angstroms and preferably about 120 to
halides, hydrocarbylaluminum hydrocarbyloxides, and about 250 Angstroms.
hydrocarbylaluminum hydrides. In these compounds, the The catalyst systems can be prepared by reacting the bis
hydrocarbyl group can contain from 1 to about 14 carbon triarylsilyl chromate, the hydrocarbylaluminum compound
atoms, and the halogen may be chlorine, bromine, fluorine, or or hydrocarbyl boron compound, and a dehydrated Support
iodine. The hydrocarbyl group can be an alkyl, aralkyl, aryl, material together. The bis-triarylsilyl chromate reacts with
alkaryl, alicyclic, or bicyclic group. Examples of the hydro 10 hydroxyl groups, which are present on the Surface of the
carbylaluminum compounds are trimethylaluminum, triethy Support. Thus, the chromate is for the most part chemically
laluminum, tributylaluminum, tridecylaluminum, tridodecy adsorbed on the surface of the support. Any part of the chro
laluminum, diethylaluminum chloride, dibutylaluminum mate, which is not chemically adsorbed, is physically
chloride, dibutylaluminum bromide, dibutylaluminum adsorbed on the surface of the support. Usually, about 50 to
iodide, dibutylaluminum fluoride, dihexylaluminum chlo 15 about 100 percent of the chromate is chemically adsorbed. It
ride, methylaluminum dichloride, ethylaluminum dibromide, should be noted, however, that the chromate retains one or
butylaluminum dichloride, pentylaluminum dichloride, more reactive groups, which react with the hydrocarbyl alu
diethylaluminum hydride, dibutylaluminum hydride, dihexy minum or boron compound. The amount of Support used is
laluminum hydride, methylaluminum dihydride, ethylalumi generally that which will provide about 0.01 to about 0.3
num dihydride, butylaluminum dihydride, and pentylalumi millimole of chromium per gram of Support and preferably
num dihydride. They can be generically classified as about 0.03 to about 0.1 millimole of chromium per gram of
compounds having the formula RAIX, wherein R is a Support.
hydrocarbyl group as defined above, X is a halogen, a hydro In certain embodiments, the molar ratio of aluminum to
carbyloxide, or a hydrogen and n is an integer from 1 to 3. chromium in the catalyst systems described above is from
The hydrocarbylboron compounds that may be incorpo 25 about 0.6:1 to about 6:1. In other embodiments, the molar
rated into the catalyst systems have the general formula: ratio of aluminum to chromium in the catalyst systems
described above is from about 1:1 to about 5:1. In still other
BR embodiments, the molar ratio of aluminum to chromium in
wherein R is a hydrocarbyl group having 1 to 14 carbon the catalyst systems described above is from about 1.5:1 to
30 about 4:1.
atoms. Exemplary groups are trimethylborane, triethylbo The processes described herein may be carried out over a
rane, triisobutylborane, and tributylborane. In one embodi range of catalyst concentrations in the fluidized bed. In cer
ment, triethylborane is selected. The hydrocarbylaluminum tain embodiments, the concentration of the catalyst system in
hydrocarbyloxides, which are commonly termed “alkylalu the fluidized bed reactor is from about 0.1 parts by weight to
minum alkoxides', are compounds of the general formula: 35 about 0.5 parts by weight, based upon 1000 parts by weight of
RAl(OR), the polyethylene in the fluidized bed. In additional embodi
ments, the concentration of the catalyst system in the fluid
wherein n is an integer from 1 to 2, and R is a hydrocarbyl ized bed reactor is from about 0.15 parts by weight to about
group having 1 to 14 carbonatoms. In one embodiment, Rhas 0.4 parts by weight, based upon 1000 parts by weight of the
1 to 8 carbon atoms. The hydrocarbyl group can be alkyl, 40 polyethylene in the fluidized bed. In still other embodiments,
aralkyl, aryl, alkaryl, alicyclic, or bicyclic. Exemplary com the concentration of the catalyst system in the fluidized bed
pounds are methyl, ethyl, propyl, iso-propyl. n-butyl, iso reactor is from about 0.2 parts by weight to about 0.3 parts by
butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, cyclohexyl, 2-me weight, based upon 1000 parts by weight of the polyethylene
thy-pentyl, heptyl, octyl, 2-ethylhexyl, cyclohexylmethyl, in the fluidized bed.
nonyl, decyl undecyl, dodecyl, tridecyl, tetradecyl, benzyl, 45 Catalyst productivity may vary considerably in the pro
pinyl, pinylmethyl, phenethyl p-methybenzyl, phenyl, tolyl, cesses described herein. In certain embodiments, the catalyst
Xylyl, naphthyl, ethylphenyl, methynaphthyl, dimethylnaph productivity may range from about 1,500 kg to about 8,000 kg
thyl, norborynyl, and norbornyl methyl. In certain embodi of high density polyethylene for each kg of catalyst. In other
ments, the hydrocarbylaluminum hydrocarbyloxide com embodiments, the catalyst productivity may range from about
pound is diethylaluminumethoxide. 50 2,000 kg to about 5,000 kg of high density polyethylene for
In all of the above embodiments, the hydrocarbyl groups, each kg of catalyst. In additional embodiments, the catalyst
the halide groups, and the hydride groups are independently productivity may range from about 2,500 kg to about 4,000 kg
selected, i.e., these groups can be the same or different. of high density polyethylene for each kg of catalyst.
As discussed above, the reaction product of the chromate The at least one catalyst deactivator may be selected from
and the hydrocarbylaluminum compound or hydrocarbyl 55 as any compound or chemical species or combination of
boron compound is supported. While silica is the preferred compounds and/or chemical species that serve to deactivate a
Support, other inorganic oxides can be used. Exemplary Sup bis-triarylsilyl chromate catalyst system when in contact with
port materials are aluminum phosphate, alumina, silica and the catalyst system and that have boiling points, as deter
alumina mixtures, silica modified with a hydrocarbylalumi mined at the pressures described above, lower than the maxi
num compound Such as triethylaluminum, silica modified 60 mum temperature within the recycle gas line of the processes
with diethylzinc, silica modified with a titanium tetrahydro described herein. In certain embodiments, the at least one
carbyloxide compound Such as titanium tetraisopropoxide, catalyst deactivator is selected from oxygen; certain oxygen
silica/titania cogels, titanias and a mixture of silica and cal bearing compounds such as alcohols having 1 to 4 carbon
cium carbonate. A typical Support is a dehydrated, solid, atoms; including methanol, ethanol, and propanol; acetone;
particulate porous material essentially inert to the polymer 65 phosphorus; certain Sulfur-bearing compounds such as Sulfur
ization. It is used as a dry powder having an average particle dioxide and carbonyl sulfide; arsenic; halogen-bearing com
size of about 2 to about 150 microns and preferably about 10 pounds; certain nitrogen-bearing compounds Such as nitro
US 7482.410 B2
9 10
gen dioxide, nitric oxide, ammonia, nitrous oxide; carbon introduced into the recycle gas line at a ratio of 0.02 mole of
monoxide, methanal; diethanolamine; and combinations the at least one catalyst deactivator per 1 million moles of
thereof. In certain embodiments, theat least one deactivatoris make-up ethylene to about 0.06 mole of the at the least one
selected from oxygen, methanol, and mixtures thereof. In catalyst deactivator per 1 million moles of make-up ethylene
other embodiments, the at least one catalyst deactivator is 5 in the reaction system.
OXygen. FIG. 2 provides a schematic representation of an exem
In certain embodiments, the at least one catalyst deactiva plary reaction system for producing high density polyethyl
tor has a boiling point, as determined at the pressures ene in accordance with the processes described herein. Addi
described above, lower than the minimum temperature within tional information regarding polyethylene polymerization
the recycle gas line. Oxygen, carbon monoxide, nitric oxide, 10 systems is provided in U.S. Pat. No. 5,352,749 to DeChellis,
nitrous oxide, diethanolamine, and mixtures thereof are et al. With reference to FIG. 2, a reactor 10 contains a fluid
exemplary catalyst deactivators having Such boiling points in ized bed of polymer particles in a reaction Zone 12. A catalyst
typical recycle systems. supply 20 is injected into the reactor near the base of the
The at least one catalyst deactivator may be introduced into reaction Zone 12 at location 34 to Sustain an ongoing poly
the recycle gas line over a range of concentrations. As dis- 15 merization in the reaction Zone. Fluidizing gas enters the
cussed above the at least one catalyst deactivator may be reaction Zone through perforations in the distributor plate 18,
introduced into a recycle gas stream at a location selected at a superficial gas velocity sufficient to fluidize the bed. A
from (i) upstream of a recycle gas cooler associated with the typical gas velocity of from about 0.6 m/s to about 0.9 m/s.
fluidized bed reactor, (ii) into the recycle gas cooler, (iii) 2 The fluidizing gas also removes at least a portion of the heat
meters or less downstream of the outlet of the recycle gas 20 of polymerization reaction. The reactor temperature setpoint
cooler, (iv) 1 meter or less downstream of the outlet of the is generally in the range of about 80° C. to about 115°C. In
recycle gas cooler, and (V) combinations thereof. Although it certain embodiments, the reactor temperature setpoint is from
is within the contemplation of this disclosure to introduce the about 85° C. to about 110° C. In other embodiments, the
at least one catalyst deactivator directly into a recycle gas reactor temperature setpoint is from about 90° C. to about
cooler, from a practical viewpoint, because of the multiple- 25 105°C. The operating pressure of the reactor is generally in
tube or multiple-chamber structure of typical recycle gas the range of about 2000 kPag to about 2500 kPag. In certain
coolers, it is generally impractical or inefficient to introduce embodiments, the operating pressure of the reactor is gener
the at least one catalyst deactivator directly into the body of a ally from about 2000 kPag to about 2200 kPag. In other
recycle gas cooler. It is generally more practical and efficient embodiments, the operating pressure of the reactor is gener
to introduce the at least one catalyst deactivator into the 30 ally from about 2200 kPag to about 2450 kPag.
recycle gas cooler by introducing the at least one deactivator Once polymerization is underway, polymer stream 42 is
into the inlet of the recycle gas cooler. For purposes of this periodically removed from the reactor through a product dis
disclosure, the term “upstream of the recycle gas cooler charge system 36. As the fluidizing gas rises through the
refers to the inlet area of a recycle gas cooler, the recycle line, reaction Zone, ethylene and at least one comonomer are con
and associated components in communication with and 35 sumed by the polymerization reaction. Gases exit the fluid
upstream of the recycle gas cooler. ized bed in the velocity reduction or freeboard Zone 14.
In certain embodiments, the at least one catalyst deactiva Entrained polymer and/or catalyst particles are largely disen
tor is introduced into the recycle gas line at a location gaged from the rising gas in the freeboard Zone and fall back
upstream of a recycle gas cooler. In other embodiments, the at to the bed. However, some of these particles remain entrained
least one catalyst deactivatoris introduced into the recycle gas 40 in the fluidized gas and circulate through the recycle system.
line at a location 2 meters or less downstream of the outlet of Gases exit the reactor into the recycle line 16. The recycle gas
a recycle gas cooler. In additional embodiments, the at least is circulated through the reactor loop using a compressor 28.
one catalyst deactivator is introduced into the recycle gas line A Small slipstream of gas is removed from the recycle line
at a location 1 meter or less downstream of the outlet of a downstream of the compressor and routed to a series of ana
recycle gas cooler. In still other embodiments, the at least one 45 lyZers 24. These analyzers 24 are used to measure the com
catalyst deactivator is introduced into the recycle gas line at a position of all gaseous components in the recycle stream. The
location into the recycle gas cooler. In other additional composition of the gas stream withdrawn from the recycle
embodiments, the at least one catalyst deactivator is intro line downstream of the compressor is essentially the same as
duced into the recycle gas line at a location upstream of a the composition in the freeboard Zone 14. Typically, pressures
recycle gas cooler and at a location 2 meters or less down- 50 within the recycle gas line are maintained in a range of about
stream of the outlet of a recycle gas cooler. In further embodi 2,000 kPag to about 2,600 kPag.
ments, the at least one catalyst deactivator is introduced into The compressed recycle gas enters a cooler 26 that
the recycle gas line at a location upstream of a recycle gas removes heat from the recycle gas stream via sensible or
cooler and at a location 1 meters or less downstream of the sensible and latent cooling. As described in U.S. Pat. No.
outlet of a recycle gas cooler. 55 5,462.999 to Griffin, et al., the cooler may discharge up to half
In certain embodiments, the at least one catalyst deactiva (50 wt.%) of the recycle stream as a liquid. Typically, the
tor is introduced into the recycle gas line at a ratio of 0.0075 recycle gas cooler is maintained at a pressure of about 2000
mole of the at least one catalyst deactivator per 1 million kPa to about 2600 kPa. In certain embodiments, the recycle
moles of make-up ethylene to about 0.12 mole of the at least gas cooler is maintained at a pressure of about 2200 kPa to
one catalyst deactivator per 1 million moles of make-up eth- 60 about 2500 kPa. In other embodiments, the recycle gas cooler
ylene in the reaction system. In other embodiments, the at is maintained at a pressure of about 2300 kPa to about 2400
least one catalyst deactivatoris introduced into the recycle gas kPa.
line at a ratio of 0.01 mole of the at least one catalyst deacti An inert condensing agent may optionally be provided to
vator per 1 million moles of make-up ethylene to about 0.08 the recycle stream at any location but, if provided at all, is
mole of the at least one catalyst deactivator per 1 million 65 typically provided downstream of the cooler 26. The molar
moles of make-up ethylene in the reaction system. In addi concentration of the inert condensing agent is generally in the
tional embodiments, the at least one catalyst deactivator is range of 1% to 30% of the recycle stream. In certain embodi
US 7482.410 B2
11 12
ments, the molar concentration of the inert condensing agent bed. In other embodiments, it is necessary to introduce the at
is from about 5% to 25% of the recycle stream. In other least one catalyst deactivator into the recycle line within 1
embodiments, the molar concentration of the inert condens meter downstream of the outlet of the recycle cooler to ben
ing agent is from about 8% to 20% of the recycle stream. eficially reduce UHMW material content and to avoid impair
A co-catalyst or catalyst activator 32 may be injected into ing catalyst activity in the fluidized bed.
the recycle line to enhance performance of the polymeriza The at least one catalyst deactivator may be introduced into
tion catalyst. Makeup feeds 22, recovered liquids 40, and, if the recycle line over a wide temperature range. In certain
needed, recovered gases 38 are injected into the recycle line. embodiments, the at least one catalyst deactivator is intro
Generally, the makeup feeds maintain an ethylene molar con duced at ambient temperature. The at least one catalyst deac
centration in the reaction Zone of about 40% to about 90%. In 10
certain embodiments, the ethylene molar concentration in the tivator may be introduced into the recycle stream over a wide
reaction Zone is from about 45% to about 75%. In other pressure range as well. Generally, the at least one catalyst
embodiments, the ethylene molar concentration in the reac deactivator may be introduced into the recycle stream at any
tion Zone is from about 50% to about 70%. pressure above the pressure of the recycle stream.
The recycle stream enters the bottom of the reactor 10 and 15 In the embodiment depicted, the injection point for the at
passes through and around a deflector plate 30 designed to least one catalyst deactivator is upstream of the compressor
keep solids from accumulating under the distributor plate 18. 28. However, in accordance with certain embodiments of the
Introduction of the at least one catalyst deactivator into the processes described herein, the at least one catalyst deactiva
recycle line is depicted as being provided by an at least one tor may be delivered to the recycle stream at location down
catalyst deactivator source 44 in communication with the stream of the compressor but upstream of the recycle stream
recycle line. The at least one catalyst deactivator Source may cooler 26. In accordance with other embodiments of the pro
be any container or Supply source capable of providing a cesses described herein the injection point may be a location
stream of the at least one catalyst deactivator. The at least one selected from locations upstream of the recycle gas cooler 26,
catalyst deactivator may be provided in pure form. However, into the recycle gas cooler 26, a location 2 meters or less
in certain embodiments, the at least one catalyst deactivator 25 downstream of the outlet of the recycle gas cooler 26, a
may be diluted in an inert gas such as nitrogen for better location 1 meter or less downstream of the outlet of the
control of the volume of the at least one catalyst deactivator recycle gas cooler 26, and combinations thereof.
delivered to the recycle stream. If diluted in an inert stream, As discussed above, introduction of the at least one catalyst
the at least one catalyst deactivator may be diluted over a deactivator in the recycle line at a location upstream of the
range. In certain embodiments, the at least one catalyst deac 30 recycle stream cooler 26 inhibits polymerization into UHMW
tivator may be diluted by mixing with an inert at a concentra polymeric materials in the lower temperature regions of the
tion of about 1 mole % to about 10 mole % of the at least one reaction system within and downstream of the recycle line
catalyst deactivator in the inert. In certain embodiments, the cooler 26. In particular, these lower temperature regions exist
at least one catalyst deactivator is oxygen and the oxygen is from the cooler 26 to the distributor plate 18.
introduced into the recycle line at a molar concentration of 35
Experimental Evaluation
about 1 mole % oxygen to about 10 mole % oxygen in a
nitrogen stream. FIG. 3 is a graphical representation of UHMW polymeric
Precise control of the concentration of the at least one material content over time for high density polyethylene that
catalyst deactivator delivered to the recycle stream is desir may be produced according to the processes described herein
able since introduction of the at least one catalyst deactivator 40 and high density polyethylene that may be produced accord
at concentrations below about 0.0075 mole of catalyst deac ing to conventional processes. The UHMW polymeric mate
tivator per 1 million moles of make-up ethylene may have a rial content in the high density polyethylene may increase as
negligible impact on the content of the UHMW polymeric the time period after the reaction system is cleaned and Ser
material in the high density polyethylene while introduction Viced increases. In conventional processes, the increase in the
of the at least one catalyst deactivator at concentrations 45 UHMW polymeric material content is expected to be fairly
greater than about 0.1 mole of the at least one catalyst deac rapid and somewhat sinusoidal in nature with the overall
tivator per 1 million moles of make-up ethylene may result in curve increasing overtime, as shown by the collection of data
an reduction of polymerization activity in the fluidized reac points designated by triangles in the graph. However, the
torbed since all of the at least one catalyst deactivator may not UHMW polymeric material content of the high density poly
be consumed in the recycle line. Generally, it is desirable to 50 ethylene produced by the processes described herein in which
control the introduction of the at least one catalyst deactivator the at least one catalyst deactivator is added to the recycle
in the recycle stream at a level that minimizes polymerization stream would be expected to increase more slowly as shown
in the lower temperature regions within and downstream of by the collection of data points designated by Squares in the
the cooler but not in the fluidized reactor bed. graph.
In certain embodiments in which the at least one catalyst 55 FIG. 4 is a graphical representation of gel counts over time
deactivator is added to the recycle stream at a location in the for films that may be produced according to the processes
recycle line downstream of the recycle cooler, the benefit of described hereinversus films that may be produced according
reducing the UHMW polymeric material content in the high to conventional processes. The gel content of the high density
density polyethylene is achieved by introducing the at least polyethylene films and articles may increase as the time
one catalyst deactivator into the recycle line within 2 meters 60 period after the reaction system is cleaned and serviced
downstream of the outlet of the recycle cooler. The beneficial increases. In conventional processes, this increase is expected
reduction of the UHMW material is attenuated the further to be somewhat sinusoidal in nature with the overall curve
downstream the at least one catalyst deactivatoris introduced. increasing relatively sharply over time, as shown with the
Introducing the at least one catalyst deactivator into the collection of data points designated by triangles in the graph.
recycle line more than 2 meters downstream of the outlet of 65 On the other hand, the gel content of a film produced with
the recycle cooler provides no beneficial reduction in UHMW resin produced by the processes of the current invention in
material content and impairs catalyst activity in the fluidized which the at least one catalyst deactivator is added to the
US 7482.410 B2
13 14
recycle stream would be expected to increase more slowly as 6. The process of claim 1, wherein the at least one catalyst
shown by the collection of data points designated by squares deactivator is selected from the group consisting of oxygen,
in the graph. methanol, carbon monoxide, and mixtures thereof.
The high density polyethylene produced by the processes 7. The process of claim 1, wherein the catalyst concentra
described herein may be used to produce a variety of different tion in the fluidized bed is from about 0.1 parts by weight to
types of products exhibiting reduced gel content. Among the about 0.5 parts by weight, based upon 1000 parts by weight of
products that may be produced using the high density poly the polyethylene in the fluidized bed.
ethylene are films, geomembranes, sheets, molded objects, 8. The process of claim 1, wherein the at least one catalyst
extruded forms, and thermoformed objects. These various deactivator is oxygen.
products exhibiting reduced gel contents may be produced by 10 9. The process of claim 1, wherein the at least one catalyst
any suitable production techniques for producing Such prod deactivator is provided to the recycle gas line at a ratio of 0.01
ucts from high density polyethylene. mole of the at least one catalyst deactivator per 1 million
With respect to the various ranges set forth herein, any moles of make-up ethylene to about 0.08 mole of the at least
upper limit recited may, of course, be combined with any one catalyst per 1 million moles of make-up ethylene in the
lower limit for selected sub-ranges. 15 reaction system.
All patents and publications, including priority documents 10. The process of claim 1, wherein the molar ratio of
and testing procedures, referred to herein are hereby incor aluminum to chromium in the catalyst system is from about
porated by reference in their entireties. 1:1 to about 5:1.
Although the present invention and its advantages have 11. The process of claim 1, wherein the reactor is at a
been described in detail, it should be understood that various temperature of about 85°C. to about 105° C. and a pressure of
changes, Substitutions, and alterations could be made without about 2000 kPag to about 2500 kPag.
departing from the spirit and scope of the invention as defined 12. The process of claim 1, wherein the catalyst concen
by the following claims. tration in the fluidized bed reactor is from about 0.15 parts by
What is claimed is: weight to about 0.4 parts by weight, based upon 1000 parts by
1. A process for reducing ultra high molecular weight 25
weight of the polyethylene in the fluidized bed.
polymeric material in a polyethylene resin comprising: 13. The process of claim 4, wherein the at least one
(i) contacting a mixture comprising ethylene with a cata comonomer is selected from the group consisting ofbutene,
lyst system comprising the Supported reaction product pentene, hexene, octene, and mixtures thereof.
of at least one bis-hydrocarbylsilyl chromate and at least 14. The process of claim 1, wherein the fluidized bed is at
one compound selected from the group consisting of 30
a pressure from about 2000 kPag to about 2200 kPag.
hydrocarbylaluminum compounds and hydrocarbylbo
ron compound in a fluidized bed reactor to provide a 15. The process of claim 1, wherein the fluidized bed is at
polyethylene resin having a density of about 0.94 g/cm a pressure from about 2200 kPag to about 2500 kPag.
to about 0.965 g/cm; 16. The process of claim 1, wherein the molar concentra
(ii) providing a recycle gas stream to the fluidized bed 35 tion of ethylene in the fluidized bed reactor is from about 40%
to about 90%.
reactor through a recycle gas line having a recycle gas
cooler in fluid communication therewith; and 17. The process of claim 1, wherein the at least one catalyst
(iii) providing a stream comprising make-up ethylene to deactivator is provided to the recycle gas line at a ratio of 0.02
the fluidized bed reactor, wherein at least one catalyst mole of the at least one catalyst deactivator per 1 million
deactivator having a boiling point, as determined at 40 moles of make-up ethylene to about 0.06 mole of the at least
101.3 kPag, lower than the maximum temperature one catalyst deactivator per 1 million moles of make-up eth
within the recycle gas line is provided to the recycle gas ylene in the reaction system.
line not more than 2 meters from the recycle gas cooler 18. The process of claim 1, wherein the molar ratio of
outlet or upstream thereof to reduce the concentration of aluminum to chromium in the catalyst system is from about
1.5:1 to about 4:1.
ultra high molecular weight polymeric material in the 45
polyethylene resin. 19. The process of claim 3, wherein the recycle gas cooler
2. The process of claim 1, wherein the at least one catalyst is at a pressure of about 2100 kPa to about 2600 kPa.
deactivator is provided to the recycle gas line at a ratio of 20. The process of claim 4, wherein the molar ratio of the at
0.0075 mole of the at least one catalyst deactivator per 1 least one comonomer to ethylene in the fluidized bed reactor
million moles of make-up ethylene to about 0.12 mole of the 50 is about 0.001:1 to about 0.15:1.
at least one catalyst deactivator per 1 million moles of make 21. The process of claim 1, wherein hydrogen is introduced
up ethylene in the reaction system. into the fluidized bed reactorata concentration in the range of
3. The process of claim 1, wherein the recycle gas line about 0.005 to about 0.08 mole of hydrogen per mole of
comprises an upstream portion of the recycle gas line and a ethylene.
downstream portion of the recycle gas line wherein the 55 22. The process of claim 1, wherein the fluidized bed
upstream portion of the recycle gas line is provided upstream reactor is maintained at a temperature of about 90° C. to about
of the recycle gas coolerand wherein the downstream portion 1000 C.
of the recycle gas line is provided downstream of the recycle 23. The process of claim 1, wherein the molar concentra
gas cooler, and wherein the at least one catalyst deactivator is tion of ethylene in the fluidized bed reactor is from about 45%
provided to the recycle gas line at a location upstream of the 60 to about 75%.
recycle gas cooler, into the recycle gas cooler, or 1 meter or 24. The process of claim 1, wherein the at least one catalyst
less downstream of the outlet of the recycle gas cooler. deactivator has a boiling point, as determined at 101.3 kPag,
4. The process of claim 1, wherein the mixture comprising lower than the minimum temperature within the recycle gas
ethylene comprises at least one comonomer. line.
5. The process of claim 3, wherein the at least one catalyst 65 25. A process for reducing the concentration of ultra high
deactivator is provided to the upstream portion of the recycle molecular weight polymeric material in a polyethylene resin
gas line. having a density of about 0.94 g/cm to about 0.965 g/cm
US 7482.410 B2
15 16
produced in a gas phase reaction system with a bis-triarylsilyl mum temperature within the recycle gas line is provided
chromate catalyst system comprising: to the recycle gas line, the maximum temperature within
contacting a mixture comprising ethylene with a catalyst the recycle gas line is about 110°C., and the maximum
system comprising the Supported reaction product of at pressure within the recycle gas line is about 2,000 kPag
least one bis-hydrocarbylsilyl chromate and at least one to about 2,600 kPag.
compound selected from the group consisting of hydro 30. The process of claim 29, wherein the at least one
carbylaluminum compounds and hydrocarbylboron catalyst deactivatoris provided to the recycle gas lineata ratio
compound in a fluidized bed reactor; of 0.0075 mole of the at least one catalyst deactivator per 1
providing a recycle gas stream to the fluidized bed reactor million moles of make-up ethylene to about 0.12 mole of the
through a recycle gas line having a recycle gas cooler in 10 at least one catalyst deactivator per 1 million moles of make
fluid communication therewith, the recycle gas cooler up ethylene in the reaction system.
having an outlet; and 31. The process of claim 29, wherein the at least one
providing a stream comprising make-up ethylene to the catalyst deactivatoris provided to the recycle gas lineata ratio
reaction system, of 0.01 mole of the at least one catalyst deactivator per 1
wherein at least one catalyst deactivator having a boiling 15 million moles of make-up ethylene to about 0.08 mole of the
point, as determined at the highest pressure within the at least one catalyst per 1 million moles of make-up ethylene
recycle gas line, lower than the maximum temperature in the reaction system.
within the recycle gas line is provided to the recycle gas 32. The process of claim 29, wherein the at least one
line not more than 2 meters from the recycle gas cooler catalyst deactivatoris provided to the recycle gas lineata ratio
outlet or upstream thereof to reduce the concentration of of 0.02 mole of the at least one catalyst deactivator per 1
ultra high molecular weight polymeric material in the million moles of make-up ethylene to about 0.06 mole of the
polyethylene resin. at least one catalyst deactivator per 1 million moles of make
26. A process for reducing the gel content in an article up ethylene in the reaction system.
produced from high density polyethylene comprising produc 33. The process of claim 29, wherein the recycle gas line
ing the article from a high density polyethylene produced in 25 comprises an upstream portion of the recycle gas line and a
accordance with the process of: downstream portion of the recycle gas line wherein the
(i) contacting a mixture comprising ethylene with a cata upstream portion of the recycle gas line is provided upstream
lyst system comprising the Supported reaction product ofa recycle gas coolerand wherein the downstream portion of
of at least one bis-hydrocarbylsilyl chromate and at least the recycle gas line is provided downstream of the recycle gas
one compound selected from the group consisting of 30
cooler, and wherein the at least one catalyst deactivator is
hydrocarbylaluminum compounds and hydrocarbylbo provided to the recycle gas line at a location selected from the
ron compound in a fluidized bed reactor to provide a group consisting of (i) upstream of the recycle gas cooler, (ii)
polyethylene resin having a density of about 0.94 g/cm into the recycle gas cooler, (iii) 2 meters or less downstream
to about 0.965 g/cm; of an outlet of the recycle gas cooler, (iv) 1 meter or less
(ii) providing a recycle gas stream to the fluidized bed 35
downstream of the outlet of the recycle gas cooler, and (v)
reactor through a recycle gas line having a recycle gas combinations thereof.
cooler in fluid communication therewith; and 34. The process of claim 33, wherein the at least one
(iii) providing a stream comprising make-up ethylene to catalyst deactivator is provided to the upstream portion of the
the fluidized bed reactor, recycle gas line.
wherein at least one catalyst deactivator having a boiling 40
35. The process of claim 29, wherein the at least one
point, as determined at 101.3 kPag, lower than the maxi catalyst deactivator is selected from the group consisting of
mum temperature within the recycle gas line is provided oxygen, methanol, carbon monoxide, and mixtures thereof.
to the recycle gas line not more than 2 meters from the 36. The process of claim 29, wherein the at least one
recycle gas cooler outlet or upstream thereof to reduce catalyst deactivator is oxygen.
the concentration of ultra high molecular weight poly 45
37. The process of claim 29, wherein the at least one
meric material in the polyethylene resin. catalyst deactivator has a boiling point, as determined at
27. The process according to claim 26, wherein the article 101.3 kPag, lower than the minimum temperature within the
is a film. recycle gas line.
28. The process of claim 26, wherein the article is a molded 38. The process of claim 29, wherein the catalyst concen
article. 50
29. A process for reducing the concentration of ultra high tration in the fluidized bed is from about 0.1 parts by weight
molecular weight polymeric material in a polyethylene resin to about 0.5 parts by weight, based upon 1000 parts by weight
having a density of about 0.94 g/cm to about 0.965 g/cm of the polyethylene in the fluidized bed.
produced in a gas phase reaction system with a bis-triarylsilyl 39. The process of claim 29, wherein the catalyst concen
chromate catalyst system comprising: 55 tration in the fluidized bed reactor is from about 0.15 parts by
contacting a mixture comprising ethylene with a catalyst weight to about 0.4 parts by weight, based upon 1000 parts by
system comprising the Supported reaction product of at weight of the polyethylene in the fluidized bed.
least one bis-hydrocarbylsilyl chromate and at least one 40. The process of claim 29, wherein the molar ratio of
compound selected from the group consisting of hydro aluminum to chromium in the catalyst system is from about
carbylaluminum compounds and hydrocarbylboron 60 1:1 to about 5:1.
compound in a fluidized bed reactor; 41. The process of claim 29, wherein the reactor is at a
providing a recycle gas stream to the fluidized bed reactor temperature of about 85°C. to about 105° C. and a pressure of
through a recycle gas line; and about 2000 kPag to about 2500 kPag.
providing a stream comprising make-up ethylene to the 42. The process of claim 29, wherein the fluidized bed is at
reaction system, 65 a pressure from about 2000 kPag to about 2200 kPag.
wherein at least one catalyst deactivator having a boiling 43. The process of claim 29, wherein the fluidized bed is at
point, as determined at 101.3 kPag, lower than the maxi a pressure from about 2200 kPag to about 2500 kPag.
US 7482.410 B2
17 18
44. The process of claim 29, wherein the fluidized bed is 53. A process for reducing the concentration of ultra high
maintained at a temperature of about 90° C. to about 100° C. molecular weight polymeric material in a polyethylene resin
45. The process of claim 29, wherein the mixture compris having a density of about 0.94 g/cm to about 0.965 g/cm
ing ethylene comprises at least one comonomer. produced in a gas phase reaction system with a bis-triarylsilyl
46. The process of claim 45, wherein the at least one 5 chromate catalyst system comprising:
comonomer is selected from the group consisting ofbutene, contacting a mixture comprising ethylene with a catalyst
pentene, hexene, octene, and mixtures thereof. system comprising the Supported reaction product of at
47. The process of claim 45, wherein the molar ratio of the least one bis-hydrocarbylsilyl chromate and at least one
at least one comonomer to ethylene in the fluidized bed reac compound selected from the group consisting of hydro
tor is about 0.001:1 to about 0.15:1. 10 carbylaluminum compounds and hydrocarbylboron
48. The process of claim 29, wherein the molar concentra compound in a fluidized bed reactor;
tion of ethylene in the fluidized bed reactor is from about 40% providing a recycle gas stream to the fluidized bed reactor
to about 90%. through a recycle gas line; and
49. The process of claim 29, wherein the molar ratio of providing a stream comprising make-up ethylene to the
aluminum to chromium in the catalyst system is from about 15 reaction system,
1.5:1 to about 4:1. wherein:
50. The process of claim33, wherein the recycle gas cooler at least one catalyst deactivator having a boiling point, as
is at a pressure of about 2100 kPa to about 2600 kPa. determined at 101.3 kPag, lower than the maximum
51. The process of claim 29, wherein hydrogen is intro temperature within the recycle gas line is provided to the
duced into the fluidized bed reactor at a concentration in the recycle gas line;
range of about 0.005 to about 0.08 mole of hydrogen per mole the recycle gas line comprises an upstream portion of the
of ethylene. recycle gas line and a downstream portion of the recycle
52. The process of claim 29, wherein the molar concentra gas line.
tion of ethylene in the fluidized bed reactor is from about 45%
to about 75%.