Title of Invention

AN OLEFIN POLYMERIZATION CATALYST

Abstract An olefin polymerization catalyst comprising a porous metal oxide, a transition metal catalyst system and an antistatic additive, wherein said antistatic additive comprises a polysulfone and a solvent for said polysulfone and wherein said catalyst is further characterized in that said antistatic additive is added to said porous metal oxide in an amount of from 5,000 to 50,000 parts per million by weight based on the weight of said porous metal oxide and have a pore volume of from 0.1 to 5 mL/g.
Full Text SUPPORTED ANTISTATIC POLYMERIZATION CATALYST
BACKGROUND ART
The polymerization of olefins using supported catalyst systems is
well known. It will also be recognized by those skilled in the art that the
use of such supported catalysts is often associated with the development
of static charges within the polymerization reactor and subsequent reactor
fouling, particularly in gas phase or slurry polymerization reactors. Severe
reactor fouling may cause such problems as poor heat transfer; the
formation of polymer agglomerates or sheets which adhere to the reactor
walls; plugging of the polymer discharge system; and in severe cases, the
development of large "chunks" which can force a reactor shut down.
Efforts to mitigate reactor fouling problems are widely reported in
the patent literature.
The use of a salt of a carboxylic acids, especially aluminum
stearate, as an antifouling additive to olefin polymerization catalyst
compositions is disclosed in United States Patent (USP) numbers
6,271,325 (McConville et al.; to Univation); and 6,281,306 (Oskam et al.;
to Univation).
The preparation of supported catalysts using an amine antistatic
agent, such as the fatty amine sold under the trademark KEMANINE AS-
990, is disclosed in USP 6,140,432 (Agapiou et al.; to Exxon) and
6,117,955 (Agapiou et al.; to Exxon).
Antistatic agents are commonly added to aviation fuels to prevent
the buildup of static changes when the fuels are pumped at high flow
rates. The use of these antistatic agents in olefin polymerizations is also
known.
For example, an aviation fuel antistatic agent sold under the
trademark STADIS™ composition (which contains a "polysulfone"
copolymer, a polymeric polyamine and an oil soluble sulfonic acid) was
originally disclosed for use as an antistatic agent in olefin polymerizations
in USP 4,182,810 (Wilcox, to Phillips Petroleum). The examples of the

Wilcox '810 patent illustrate the addition of the "polysulfone" antistatic
agent to the isobutane diluent in a commercial slurry polymerization
process. This is somewhat different from the teachings of the earlier
referenced patents - in the sense that the carboxylic acid salts or amine
antistats of the other patents were added to the catalyst, instead of being
added to a process stream.
The use of "polysulfone" antistatic composition in olefin
polymerizations is also subsequently disclosed in:
1) chromium catalyzed gas phase olefin polymerizations, in
USP 6,639,028 (Heslop et al.; assigned to BP Chemicals Ltd.);
2) Ziegler Natta catalyzed gas phase olefin polymerizations, in
USP 6,646,074 (Herzog et al.; assigned to BP Chemicals Ltd.); and
3) metallocene catalyzed olefin polymerizations, in USP
6,562,924 (Benazouzz et al.; assigned to BP Chemicals Ltd.).
The Benazouzz et al. patent does teach the addition of STADIS™
antistat agent to the polymerization catalyst in small amounts (about 150
ppm by weight).
However, in each of the Heslop et al. '028, Herzog et al. '074 and
Benazouzz et al. '924 patents listed above, it is expressly taught that it is
preferred to add the STADIS™ antistat directly to the polymerization zone
(i.e. as opposed to being an admixture with the catalyst).
We have discovered that supported olefin polymerization catalysts
prepared with large amounts of a polysulfone-containing antistat provide
surprisingly good polymerization activity and excellent antistatic
performance.
DISCLOSURE OF INVENTION
The present invention provides an olefin polymerization catalyst
comprising a porous metal oxide, a transition metal catalyst system and an
antistatic additive, wherein said antistatic additive comprises a polysulfone
and a solvent for said polysulfone and wherein said catalyst is further
characterized in that said antistatic additive is added to said porous metal

oxide in an amount of from 5,000 to 50,000 parts per million by weight
based on the weight of said porous metal oxide.
BEST MODE FOR CARRYING OUT THE INVENTION
Part A: Catalyst System
As used herein, the phrase "catalyst system" includes at least one
"transition metal catalyst" (also referred to herein as a "catalyst
compound") and may also include a cocatalyst or activator.
As used herein, the phrase "catalyst compound" includes any
compound that, once appropriately activated, is capable of catalyzing the
polymerization or oligomerization of olefins. The catalyst compound
comprises at least one Group 3 to Group 15 metal atom (preferably a
Group 4 to 12 transition metal, most preferably titanium, zirconium or
hafnium) or lanthanide or actinide atom.
Thus, the catalyst compound may include for example, the well-
known "chromium" polymerization catalysts (which are typically prepared
by depositing a chromium species on a metal oxide support the group
consisting of silica and alumina.
"Ziegler Natta" polymerization catalysts may also be employed.
These catalysts typically comprise a group 4 or group 5 metal - especially
titanium or vanadium - in combination with hydrocarbyl aluminum activator
of the general formula:

where Ra1 is a hydrocarbyl group having from 1 to 10 carbon atoms; ORb1
is an alkoxy or aryloxy group where ORb1 is a hydrocarbyl fragment having
from 1 to 10 carbon atoms and being bonded to oxygen; X is chloride or
bromide and a+b+c = 3, with the proviso that a is greater than 0.
Examples of the hydrocarbyl aluminum activator in widespread use include
trimethyl aluminum, trimethyl aluminum and tributyl aluminum.
However, it is preferred to use a well characterized organometallic
compound as the catalyst compound in the process of this invention.
These catalyst compounds typically comprise a metal atom, at least one
"functional" ligand and at least one leaving group. Further details follow.

As used herein, the phrase "leaving group" generally refers to one
or more chemical moieties bound to the metal center of the catalyst
compound that can be abstracted from the catalyst compound, thus
producing a species active towards olefin polymerization or
oligomerization.
As used herein, in reference to Periodic Table "Groups" of
Elements, the "new" numbering scheme for the Periodic Table Groups are
used as in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David
R. Lide ed., CRC Press 81st ed. 2000).
As used herein, a "hydrocarbyl" includes aliphatic, cyclic, olefinic,
acetylenic and aromatic radicals (i.e. hydrocarbon radicals) comprising
hydrogen and carbon that are deficient by one hydrogen. A
"hydrocarbylene" is deficient by two hydrogens.
As used herein, an "alkyl" includes linear, branched and cyclic
paraffin radicals that are deficient by one hydrogen. Thus, for example, a
-CH3 group ("methyl") and a CH3CH2- group ("ethyl") are examples of
alkyls.
As used herein, an "alkenyl" includes linear, branched and cyclic
olefin radicals that are deficient by one hydrogen; alkynyl radicals include
linear, branched and cyclic acetylene radicals deficient by one hydrogen
radical.
As used herein, "aryl" groups includes phenyl, naphthyl, pyridyl and
other radicals whose molecules have the ring structure characteristic of
benzene, naphthylene, phenanthrene, anthracene, etc. For example, a
C6H5" aromatic structure is an "phenyl", a C6H42- aromatic structure is an
"phenylene". An "arylalkyl" group is an alkyl group having an aryl group
pendant therefrom, examples of which include benzyl, phenethyl,
tolylmethyl and the like; an "alkylaryl" is an aryl group having one or more
alkyl groups pendant therefrom, examples of which include tolyl, xylyl,
mesityl, cumyl and the like.
As used herein, an "alkylene" includes linear, branched and cyclic
hydrocarbon radicals deficient by two hydrogens. Thus, -CH2-

("methylene") and --CH2CH2-- ("ethylene") are examples of alkylene
groups. Other groups deficient by two hydrogen radicals include "arylene"
and "alkenylene".
As used herein, the phrase "heteroatom" includes any atom other
than carbon and hydrogen that can be bound to carbon. A "heteroatom-
containing group" is a hydrocarbon radical that contains a heteroatom and
may contain one or more of the same or different heteroatoms. In one
embodiment, a heteroatom-containing group is a hydrocarbyl group
containing from 1 to 3 atoms selected from the group consisting of boron,
aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.
Non-limiting examples of heteroatom-containing groups include radicals of
imines, amines, oxides, phosphines, ethers, ketones, oxoazolines
heterocyclics, oxazolines, thioethers, and the like.
As used herein, "heterocyclic" refers to ring systems having a
carbon backbone that comprise from 1 to 3 atoms selected from the group
consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorous,
oxygen and sulfur, unless the heteroatom (non-carbon atom) is described.
As used herein, an "alkylcarboxylate", "arylcarboxylate", and
"alkylarylcarboxylate" is an alkyl, aryl, and alkylaryl, respectively, that
possesses a carboxyl group in any position. Examples include
C6H5CH2C(O)O-, CH3C(O)O, etc.
As used herein, "non-interfering" means that the ligand (or cation)
being referred to does not interfere with olefin polymerization (i.e. that it
does not reduce the activity of olefin polymerization by more than 50% in
comparison to a polymerization conducted in the absence of the ligand or
cation).
As used herein, the term "substituted" means that the group
following that term possesses at least one moiety in place of one or more
hydrogens in any position, the moieties selected from such groups as
halogen radicals (esp., CI, F, Br), hydroxyl groups, carbonyl groups,
carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl
groups, naphthyl groups, C1 to C10 alkyl groups, C2 to C10 alkenyl groups,

and combinations thereof. Examples of substituted alkyls and aryls includes, but are not limited
to, acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,
dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyol radicals, carbomoyl radicals,
alkyl-and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals,
and combinations thereof.
As used herein, structural formulas are employed as is commonly understood in the
chemical arts; lines ("--") used to represent associations between a metal atom ("M", Group 3 to
Group 15 atoms) and a ligand or ligand atom (e.g. cyclopentadienyl, nitrogen, oxygen, halogen
ions, alkyl, etc.) as well as the phrases "associated with", "bonded to" and "bonding", are not
limited to representing a certain type of chemical bond, as these lines and phrases are meant to
represent a "chemical bond", a "chemical bond" defined as an attractive force between atoms
that is strong enough to permit the combined aggregate to function as a unit, or "compound".
Unless stated otherwise, no embodiment of the preset invention is herein limited to the
oxidation state of the metal atom "M" as defined below in the individual descriptions and
examples that follow. The ligation of the metal atom "M" is such that the compounds described
herein are neutral, unless otherwise indicated.
Part B: Transition Metal Catalyst (Or Catalyst compound
In general, any transition metal catalyst compound which is activated by an aluminum
alkyl or methyl aluminoxane (MAO), or an "ionic activator" (discussed in Part C, below) is
potentially suitable for use in the present invention. An extensive discussion of such catalysts is
provided in USP 6,720,396 (Bell et al. ; assigned to Univation Technologies) and the references
cited therein. A general (non-limited) overview of such catalyst compounds follows. Such
catlalysts typically contain a "bulky" functional ligand. Preferred catalyst compounds are group
4 metal complexes (especially titanium or zirconium) which contain one cyclopentadienyl

ligand ("homocyclopentadienyl complexes") or two cyclopentadienyl
ligands ("biscyclopentadienyl complexes").
The bulky ligands are generally represented by one or more open,
acyclic, or fused ring(s) or ring system(s) or a combination thereof. The
ring(s) or ring system(s) of these bulky ligands are typically composed of
atoms selected from Groups 13 to 16 atoms of the Periodic Table of
Elements. Preferably the atoms are selected from the group consisting of
carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron
and aluminum or a combination thereof. Most preferably the ring(s) or ring
system(s) are composed of carbon atoms such as but not limited to those
cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or
other similar functioning ligand structure such as a pentadiene, a
cyclooctatetraendiyl or an imide ligand. The metal atom is preferably
selected from Groups 3 through 15 and the lanthanide or actinide series of
the Periodic Table of Elements. Preferably the metal is a transition metal
from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most
preferably the transition metal is from Group 4.
In one embodiment, catalyst compounds are represented by the
formula:

where M is a metal atom from the Periodic Table of the Elements and may
be a Group 3 to 12 metal or from the lanthanide or actinide series of the
Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition
metal, more preferably M is zirconium, hafnium or titanium. The bulky
ligands, LA and LB, are open, acyclic or fused ring(s) or ring system(s) and
are any ancillary ligand system, including unsubstituted or substituted,
cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom
substituted and/or heteroatom containing cyclopentadienyl-type ligands.
Non-limiting examples of bulky ligands include cyclopentadienyl ligands,
cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands,
fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,
cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,

pentalene ligands, phosphoyl ligands, phosphinimine, pyrrolyl ligands,
pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like,
including hydrogenated versions thereof, for example tetrahydroindenyl
ligands. In one embodiment, LA and LB may be any other ligand structure
capable of .eta.5-bonding to M, preferably .eta.3-bonding to M and most
preferably .eta.5-bonding. In another embodiment, LA and LB may
comprise one or more heteroatoms, for example, nitrogen, silicon, boron,
germanium, sulfur and phosphorous, in combination with carbon atoms to
form an open, acyclic, or preferably a fused, ring or ring system, for
example, a hetero-cyclopentadienyl ancillary ligand. Other LA and LB bulky
ligands include but are not limited to bulky amides, phosphides, alkoxides,
aryloxides, phosphinimides, imides, carbolides, borollides, porphyrins,
phthalocyanines, corrins and other polyazomacrocycles. Independently,
each LA and LB may be the same or different type of bulky ligand that is
bonded to M. In one embodiment of formula (I) only one of either LA or LB
is present.
Independently, each LA and LB may be unsubstituted or substituted
with a combination of substituent groups R. Non-limiting examples of
substituent groups R include one or more from the group selected from
hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl
radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals,
alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals,
alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,
alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals,
aroylamino radicals, straight, branched or cyclic, alkylene radicals, or
combination thereof. In a preferred embodiment, substituent groups R
have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that
can also be substituted with halogens or heteroatoms or the like. Non-
limiting examples of alkyl substituents R include methyl, ethyl, propyl,
butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and
the like, including all their isomers, for example tertiary butyl, isopropyl,
and the like. Other hydrocarbyl radicals include fluoromethyl, fluroethyl,

difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted
organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-
bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and
disubstituted boron radicals including dimethylboron for example; and
disubstituted heteroatom radicals including dimethylamine,
dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen
radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and
ethylsulfide. Non-hydrogen substituents R include the atoms carbon,
silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,
germanium and the like, including olefins such as but not limited to
olefinically unsaturated substituents including vinyl-terminated ligands, for
example but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least
two R groups, preferably two adjacent R groups, are joined to form a ring
structure having from 3 to 30 atoms selected from carbon, nitrogen,
oxygen, phosphorous, silicon, germanium, aluminum, boron or a
combination thereof. Also, a substituent group R group such as 1-butanyl
may form a carbon sigma bond to the metal M.
Other ligands may be bonded to the metal M, such as at least one
leaving group Q. As used herein the term "leaving group" is any ligand
that can be abstracted from a bulky ligand catalyst compound to form a
bulky ligand catalyst species capable of polymerizing one or more
olefin(s). In one embodiment, Q is a monoanionic labile ligand having a
sigma-bond to M. Depending on the oxidation state of the metal, the value
for n is 0, 1 or 2 such that formula (I) above represents a neutral bulky
ligand catalyst compound.
Non-limiting examples of Q ligands include weak bases such as
amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals
having from 1 to 20 carbon atoms, hydrides or halogens and the like or a
combination thereof. In another embodiment, two or more Q's form a part
of a fused ring or ring system. Other examples of Q ligands include those

substituents for R as described above and including cyclobutyl, cyclohexyl,
heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene,
methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide),
dimethylamide, dimethylphosphide radicals and the like.
In another embodiment, the catalyst compound is represented by
the following formula:

These compounds represented by formula (II) are known as
bridged, ligand catalyst compounds. LA, LB, M, Q and n are as defined
above. Non-limiting examples of bridging group A include bridging groups
containing at least one Group 13 to 16 atom, often referred to as a divalent
moiety such as but not limited to at least one of a carbon, oxygen,
nitrogen, silicon, aluminum, boron, germanium and tin atom or a
combination thereof. Preferably bridging group A contains a carbon,
silicon or germanium atom, most preferably A contains at least one silicon
atom or at least one carbon atom. The bridging group A may also contain
substituent groups R as defined above including halogens and iron. Non-
limiting examples of bridging group A may be represented by R2C, R'2Si,
R'2Si R2Si, R2Ge, R'P, where R' is independently, a radical group which is
hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-
substituted organometalloid, disubstituted boron, substituted chalcogen, or
halogen or two or more R' may be joined to form a ring or ring system. In
one embodiment, the bridged, ligand catalyst compounds of formula (II)
have two or more bridging groups A.
In one embodiment, the catalyst compounds are those where the R
substituents on the bulky ligands LA and LB of formulas (I) and (II) are
substituted with the same or different number of substituents on each of
the bulky ligands. In another embodiment, the bulky ligands LA and LB of
formulas (I) and (II) are different from each other.
In a most preferred embodiment, catalyst compounds useful in the
invention include bridged heteroatom, mono-bulky ligand compounds.

More specifically, these highly preferred catalysts are group 4 metal
(especially titanium) complexes characterized by having a bridged,
bidentate cyclopentadienyl-amine ligand, as disclosed in the
aforementioned USP 5,04A475. Preferred bridging groups are dialkyl
silyls - especially dimethyl silyl. The amine portion of the ligand preferably
has an alkyl substituent on the nitrogen atom (especially tertiary butyl) with
the remaining nitrogen bands bonding to the transition metal (preferably
titanium) and the silicon atome of the preferred dimethyl silyl bridging
group. The cyclopentadienyl ligand is pi-bonded to the transition metal
and covalently bonded to the bridging group. The cyclopentadienyl group
is preferably substituted, especially tetra methyl cyclopentadienyl.
Preferred catalyst compounds include dimethylsilyltetramnethyl
cyclopentadienyl-tertiary butyl amido titanium di chloride (and the alkyl
analogues - i.e. with the two chloride ligands being replaced by simple
alkyls, especially methyl) and the catalyst compounds illustrated in the
present examples. U.S. Patents 5,057,475 and 5,064,802 (are also
illustrated in the present Examples).
In another embodiment, the catalyst compound is represented by
the formula:

where M is a Group 3 to 16 metal atom or a metal selected from the Group
of actinides and lanthanides of the Periodic Table of Elements, preferably
M is a Group 4 to 12 transition metal, and more preferably M is a Group 4,
5 or 6 transition metal, and most preferably M is a Group 4 transition metal
in any oxidation state, especially titanium; Lc is a substituted or
unsubstituted bulky ligand bonded to M; J is bonded to M; A is bonded to
M and J; J is a heteroatom ancillary ligand; and A is a bridging group; Q is
a univalent anionic ligand; and n is the integer 0, 1 or 2. In formula (III)
above, Lc, A and J may form a fused ring system. In an embodiment, Lc
of formula (III) is as defined above for LA in formula (I) and A, M and Q of
formula (III) are as defined above in formula (I).

In formula (III) J is a heteroatom containing ligand in which J is an
element with a coordination number of three from Group 15 or an element
with a coordination number of two from Group 16 of the Periodic Table of
Elements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfur
atom with nitrogen being most preferred.
In another embodiment, catalyst compound is a complex of a metal,
preferably a transition metal, a bulky ligand, preferably a substituted or
unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such
as those described in U.S. Patent 5,527,752.
In another embodiment, the catalyst compounds are represented by
the formula:

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition
metal, and most preferably a Group 4, 5 or 6 transition metal; LD is a bulky
ligand that is bonded to M; each Q is independently bonded to M and
Q2(YZ) forms a unicharged polydentate ligand; A or Q is a univalent
anionic ligand also bonded to M; X is a univalent anionic group when n is 2
or X is a divalent anionic group when n is 1; n is 1 or 2.
In formula (IV), L and M are as defined above for formula (I). Q is
as defined above for formula (I), preferably Q is selected from the group
consisting of --O-, -NR-, -CR2- and -S-. Y is either C or S. Z is
selected from the group consisting of-OR, -NR2) -CR3, -SR, -SiR3, -
PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that
when Q is --NR-- then Z is selected from one of the group consisting of
-OR, -NR2, -SR, -SiR3, -PR2 and -H; R is selected from a group
containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably
where R is a hydrocarbon group containing from 1 to 20 carbon atoms,
most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer from 1
to 4, preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a
divalent anionic group when n is 1; preferably X is a carbamate,
carboxylate, or other heteroallyl moiety described by the Q, Y and Z
combination.

In another embodiment of the invention, the catalyst compounds
are heterocyclic ligand complexes where the bulky ligands, the ring(s) or
ring system(s), include one or more heteroatoms or a combination thereof.
Non-limiting examples of heteroatoms include a Group 13 to 16 element,
preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous
and tin. Examples of these bulky ligand catalyst compounds are described
in U.S. Patent 5,637,660.
In one embodiment, the catalyst compounds are represented by the
formula:

where M is a metal selected from Group 3 to 13 or lanthanide and actinide
series of the Periodic Table of Elements; Q is bonded to M and each Q is
a monovalent, bivalent, or trivalent anion; X and Y are bonded to M; one or
more of X and Y are heteroatoms, preferably both X and Y are
heteroatoms; Y is contained in a heterocyclic ring J, where J comprises
from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is
bonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1
to 50 carbon atoms, preferably Z is a cyclic group containing 3 to 50
atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a
bridging group joined to at least one of X, Y or J, preferably X and J; q is 1
or 2; n is an integer from 1 to 4 depending on the oxidation state of M. In
one embodiment, where X is oxygen or sulfur then Z is optional. In
another embodiment, where X is nitrogen or phosphorous then Z is
present. In an embodiment, Z is preferably an aryl group, more preferably
a substituted aryl group.
It is also within the scope of this invention, in one embodiment, that
the catalyst compounds include complexes of Ni2+ and Pd2+ described in
U.S. Patent 5,852,145. These complexes can be either dialkyl ether
adducts, or alkylated reaction products of the described dihalide
complexes that can be activated to a cationic state by the activators or
cocatalysts are described below.

Also included as catalyst compounds are those diimine based ligands of Group 8 to 10
metal compounds.
Other suitable catalyst compounds are those Group 5 and 6 metal imido complexes
described in U.S. Patent 5,851,945. In addition, bulky ligand catalyst compounds include bridged
bis(arylamido) Group 4 compounds, bridged bis(amido) catalyst compounds and catalysts having
bis(hydroxy aromatic nitrogen ligands).
It is also contemplated that in one embodiment, the catalyst compounds of the invention
described above include their structural or optical or enantiomeric isomers (meso and racemic
isomers) and mixtures thereof.
Other catalyst compounds useful in this invention are disclosed in the aforementioned U.S.
Patent 6,720,396
Part C: Activation
The above described transition metal catalysts are utilized for olefin polymerization in the
presence of a cocatalyst of activator.
Aluminoxanes, especially methyl aluminoxane, are well known cocatalyst for
organometallic catalyst compounds. Methyl aluminoxane, and near variants thereof (which
typically contain small levels of higher alkyl groups) are commercially available products.
Although the exact structure of these aluminoxanes is still somewhat uncertain, it is generally
agreed that they are oligomeric species that contain repeating units of the general formula:

Where R is (predominantly) methl.
It is alos well known to employ so-called "ionic activators" (also referred to herein as activator
compounds) with organometallic catalyst

compounds, as described in USP 5,198,401. In general, these activators
comprise a cation and a substantially non-coordinating anion.
More specifically, preferred activator compounds contain a
compatible anion having up to 100, and preferably up to 50 non-hydrogen
atoms and having at least one substituent comprising an active hydrogen
moiety. Preferred substituents comprising an active hydrogen moiety
correspond to the formula:

wherein G is a polyvalent hydrocarbon radical, T is O, S, NR, or PR,
wherein R is a hydrocarbyl radical, a trihydrocarbyl silyl radical, a
trihydrocarbyl germyl radical, or hydrogen, H is hydrogen, q is 0 or 1, and
preferably 1, and r is an integer from 1 to 3, preferably 1. Polyvalent
hydrocarbon radical G has r+1 valencies, one valency being with a metal
or metalloid of the Groups 5-15 of the Periodic Table of the Elements in
the compatible anion, the other valency or valencies of G being attached
to r groups T-H. Preferred examples of G include divalent hydrocarbon
radicals such as: alkylene, arylene, aralkylene, or alkarylene radicals
containing from 1 to 20 carbon atoms, more preferably from 2 to 12 carbon
atoms. Suitable examples of G include phenylene, biphenylene,
naphthylene, methylene, ethylene, 1,3-propylene, 1,4-butylene,
phenylmethylene (-C6H4-CH2-). The polyvalent hydrocarbyl portion G
may be further substituted with radicals that do not interfere with the
coupling function of the active hydrogen moiety. Preferred examples of
such noninterfering substituents are alkyl, aryl, alkyl- or aryl-substituted
silyl and germyl radicals, and fluoro substituents.
The group T-H in the previous formula thus may be an -OH, --SH,
--NRH, or --PRH group, wherein R preferably is a C1-18, preferably a C1-10
hydrocarbyl radical or hydrogen, and H is hydrogen. Preferred R groups
are alkyls, cycloalkyls, aryls, arylalkyls, or alkylaryls of 1 to 18 carbon
atoms, more preferably those of 1 to 12 carbon atoms. The -OH, -SH,
-NRH, or -PRH groups may be part of a larger functionality such as, for
example, C(O)--OH, C(S)--SH, C(O)--NRH, and C(O)-PRH. Most

preferably, the group T--H is a hydroxy group, -OH, or an amino group,
-NRH.
Very preferred substituents Gq(T-H)r comprising an active
hydrogen moiety include hydroxy- and amino-substituted aryl, aralkyl,
alkaryl or alkyl groups, and most preferred are the hydroxyphenyls,
especially the 3- and 4-hydroxyphenyl groups, hydroxytolyls, hydroxy
benzyls (hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyls,
hydroxycyclohexyls, hydroxymethyls, and hydroxypropyls, and the
corresponding amino-substituted groups, especially those substituted with
-NRH wherein R is an alkyl or aryl radical having from 1 to 10 carbon
atoms, such as for example methyl, ethyl, propyl, i-propyl, n-, i-, or t-butyl,
pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl, benzyl, tolyl, xylyl,
naphthyl, and biphenyl.
The compatible anion containing the substituent which contains an
active hydrogen moiety, may further comprise a single Group 5-15
element or a plurality of Group 5-15 elements, but is preferably a single
coordination complex comprising a charge-bearing metal or metalloid core,
which anion is bulky. A compatible anion specifically refers to an anion
which when functioning as a charge balancing anion in the catalyst system
of this invention, does not transfer an anionic substituent or fragment
thereof to the transition metal cation thereby forming a neutral transition
metal compound and a neutral metal by-product. "Compatible anions" are
anions that are not degraded to neutrality when the initially formed
complex decomposes and are noninterfering with desired subsequent
polymerizations. Preferred anions are those containing a single
coordination complex comprising a charge-bearing metal or metalloid core
carrying a substituent containing an active hydrogen moiety which anion is
relatively large (bulky), capable of stabilizing the active catalyst species
(the transition metal cation) which is formed when the activator compound
and transition metal compound are combined and said anion will be
sufficiently labile to be displaced by olefinic, diolefinic and acetylenically
unsaturated compounds or other neutral Lewis bases such as ethers,

nitrites and the like. Suitable metals for the anions of activator compounds
include, but are not limited to, aluminum, gold, platinum and the like.
Suitable metalloids include, but are not limited to, boron, phosphorus,
silicon and the like. Activator compounds which contain anions comprising
a coordination complex containing a single boron atom and a substituent
comprising an active hydrogen moiety are preferred.
Preferably, compatible anions containing a substituent comprising
an active hydrogen moiety may be represented by the following general
Formula (I):

wherein M' is a metal or metalloid selected from Groups 5-15 of the
Periodic Table of the Elements; Q independently in each occurrence is
selected from the group consisting of hydride, dihydrocarbylamido,
preferably dialkylamido, halide, hydrocarbyloxide, preferably alkoxide and
aryloxide, hydrocarbyl, and substituted-hydrocarbyl radicals, including
halo-substituted hydrocarbyl radicals, and hydrocarbyl- and
halohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbyl
portion having from 1 to 20 carbons with the proviso that in not more than
one occurrence is Q halide; G is a polyvalent, having r+1 valencies and
preferably divalent hydrocarbon radical bonded to M' and T; T is O, S, NR,
or PR, wherein R is a hydrocarbon radicals a trihydrocarbyl silyl radical, a
trihydrocarbyl germyl radical, or hydrogen; m is an integer from 1 to 7,
preferably 3; n is an integer from 0 to 7, preferably 3; q is an integer 0 or 1,
preferably 1; r is an integer from 1 to 3, preferably 1; z is an integer from 1
to 8, preferably 1; d is an integer from 1 to 7, preferably 1; and n+z-m=d.
Preferred boron-containing anions that are particularly useful in this
invention may be represented by the following general Formula (II):

wherein B is boron in a valence state of 3; z' is an integer from 1-4,
preferably 1; d is 1; and Q, G, T, H, q, and r are as defined for Formula (I).
Preferably, z' is 1, q is 1, and r is 1.

Illustrative, but not limiting, examples of anions of activator
compounds to be used in the present invention are boron-containing
anions such as triphenyl(hydroxyphenyl)borate, diphenyl-
di(hydroxyphenyl)borate, triphenyl(2,4-dihydroxyphenyl)borate, tri(p-
tolyl)(hydroxyphenyl)borate, tris-
(pentafluorophenyl)(hydroxyphenyl)borate, tris-(2,4-
dimethylphenyl)(hydroxyphenyl)borate, tris-(3,5-
dimethylphenyl)(hydroxyphenyl)borate, tris-(3,5-di-
trifluoromethylphenyl)(hydroxyphenyl)borate, tris(pentafluorophenyl)(2-
hydroxyethyl)borate, tris(pentafluorophenyl)(4-hydroxybutyl)borate,
tris(pentafluorophenyl)(4-hydroxycyclohexyl)borate,
tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate,
tris(pentafluorophenyl)(6hydroxy-2-naphthyl)borate, and the like. A highly
preferred activator complex is tris(pentafluorophenyl)(4-
hydroxyphenyl)borate. Other preferred anions of activator compounds are
those above mentioned borates wherein the hydroxy functionality is
replaced by an amino NHR functionality wherein R preferably is methyl,
ethyl, or t-butyl.
The cationic portion b.1) of the activator compound to be used in
association with the compatible anion b.2) can be any cation which is
capable of reacting with the transition metal compound to form a
catalytically active transition metal complex, especially a cationic transition
metal complex. The cations b.1) and the anions b.2) are used in such
ratios as to give a neutral activator compound. Preferably the cation is
selected from the group consisting of Bronsted acidic cations, carbonium
cations, silylium cations, and cationic oxidizing agents.
Bronsted acidic-cations may be represented by the following
general formula:

wherein L is a neutral Lewis base, preferably a nitrogen, phosphorus, or
sulfur containing Lewis base; and (L--H)+ is a Bronsted acid. The
Bronsted acidic cations are believed to react with the transition metal

compound by transfer of a proton of said cation, which proton combines
with one of the ligands on the transition metal compound to release a
neutral compound.
Illustrative, but not limiting, examples of Bronsted acidic cations of
activator compounds to be used in the present invention are trialkyl-
substituted ammonium cations such as triethylammonium,
tripropylammonium, tri(n-butyl)ammonium, trimethylammonium,
tributylammonium, and tri(n-octyl)ammonium. Also suitable are N,N-
dialkyl anilinium cations such as N,N-dimethylanilinium, N,N-
diethylanilinium, N,N-2,4,6-pentamethylanilinium, N,N-
dimethylbenzylammonium and the like; dialkylammonium cations such as
di-(i-propyl)ammonium, dicyclohexylammonium and the like; and
triarylphosphonium cations such as triphenylphosphonium,
tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium,
dimethylsulphonium, diethylsulphonium, and diphenylsulphonium.
Particularly suitable are those cations having longer alkyl chains
such as dihexydecylmethylammonium, dioctadecylmethylammonium,
ditetradecylmethylammonium, bis (hydrogenated tallow alkyl)
methylammonium and similar.
Particular preferred activators of this type are alkylammonium tris
(pentaflurorphenyl) 4-(hydroxyphenyl) borates. A particularly preferred
activator is bis (hydrogenated tallow alkyl) methyl ammonium tris
(pentafluorophenyl) (4-hydroxyphenyl) borate.
A second type of suitable cations corresponds to the formula: Cwherein C+ is a stable carbonium or silylium ion containing up to 30
nonhydrogen atoms, the cation being capable of reacting with a
substituent of the transition metal compound and converting it into a
catalytically active transition metal complex, especially a cationic transition
metal complex. Suitable examples of cations include tropyllium,
triphenylmethylium, benzene(diazonium). Silylium salts have been
previously generically disclosed in J. Chem. Soc. Chem. Comm., 1993,
383-384, as well as Lambert, J. B., et al., Organometallics, 1994,13,

2430-2443. Preferred silylium cations are triethylsilylium, and
trimethylsilylium and ether substituted adducts thereof.
Another suitable type of cation comprises a cationic oxidizing agent
represented by the formula:

wherein Oxe+ is a cationic oxidizing agent having a charge of e+, and e is
an integer from 1 to 3.
Examples of cationic oxidizing agents include: ferrocenium,
hydrocarbyl-substituted ferrocenium, Ag+ and Pb2+.
The quantity of activator compound in the supported catalyst
component and the supported catalyst is not critical, but typically ranges
from 0.1, preferably from 1 to 2,000 micromoles of activator compound per
gram of treated support material. Preferably, the supported catalyst or
component contains from 10 to 1,000 micromoles of activator compound
per gram of treated support material.
The supported catalyst component of the present invention as such
or slurried in a diluent can be stored or shipped under inert conditions, or
can be used to generate the supported catalyst of the present invention.
With respect to this type of activator, a particularly preferred
compound is the reaction product of an alkylammonium tris
(pentafluorophenyl)-4-(hydroxyphenyl) borate and an organometallic
compound, for example trimethylaluminum.
Part D: Particulate Metal Oxide Support
The catalyst of this invention must be prepared with a particulate
metal oxide support.
The use of metal oxide supports in the preparation of olefin
polymerization catalysts is known to those skilled in the art. An exemplary
list of suitable metal oxides includes oxides of aluminum, silicon,
zirconium, zinc and titanium. Alumina, silica and silica-alumina are metal
oxides that are well known for use in olefin polymerization catalysts and
are preferred for reasons of cost and convenience. Silica is particularly
preferred.

It is preferred that the metal oxide have a particle size of from about
1 to about 200 microns. It is especially preferred that the particle size be
between about 30 and 100 microns if the catalyst is to be used in a gas
phase or slurry polymerization process and that a smaller particle size
(less than 10 microns) be used if the catalyst is used in a solution
polymerization.
Conventional porous metal oxides that have comparatively high
surface areas (greater than 1 m2/g, particularly greater than 100 m2/g,
more particularly greater than 200 m2/g) are preferred to non-porous metal
oxides.
Highly preferred silica is further characterized by having a pore
volume of from 0.1 to 5 mL/g (especially 0.5 to 3 mL/g). Average pore
sizes of 50 to 500 Angstroms (A) (especially 75 to 400 A) are also
preferred.
While not wishing to be bound by theory, it is believed that the high
surface area of the preferred supports facilitates the incorporation of the
high levels of antistatic agent (which are required by this invention) onto
the support.
The support material may be subjected to a heat treatment and/or
chemical treatment to reduce the water content or the hydroxyl content of
the support material.
Typically chemical dehydration agents are reactive metal hydrides,
aluminum alkyls and halides. Prior to its use the support material may be
subjected to treatment at 100°C to 1000°C and preferably at 200 to 850°C
in an inert atmosphere under reduced pressure.
The support material may be further combined with an
organoaluminum compound and most preferably a trialkylaluminum
compound in a dilute solvent.
The support material is preferably pretreated with the
trialkylaluminum compound at a temperature of 20°C to 150°C and
preferably at 20°C to 100°C.

The molar ration of transition metal in the catalyst compound (which
transition metal is preferably titanium or zirconium) to ionic activator
employed in the method of the present invention may be in the range
1:10000 to 100:1. A preferred range is from 1:5000 to 10:1 and most
preferred from 1:10 to 10:1.
Part E: Antistatic "Polysulfone" Additive
The antistatic polysulfone additive comprises at least one of the
components selected from:
(1) a polysulfone copolymer;
(2) a polymeric polyamine; and
(3) an oil-soluble sulfonic acid, and, in addition, a solvent for the
polysulfone copolymer.
Preferably, the antistatic additive comprises at least two
components selected from above components (1), (2) and (3). More
preferably, the antistatic additive comprises a mixture of (1), (2) and (3).
According to the present invention, the polysulfone copolymer
component of the antistatic additive (often designated as olefin-sulfur
dioxide copolymer, olefin polysulfones, or poly(olefin sulfone)) is a
polymer, preferably a linear polymer, wherein the structure is considered
to be that of alternating copolymers of the olefins and sulfur dioxide,
having a one-to-one molar ratio of the comonomers with the olefins in
head to tail arrangement. Preferably, the polysulfone copolymer consists
essentially of about 50 mole percent of units of sulfur dioxide, about 40 to
50 mole percent of units derived from one or more 1-alkenes each having
from about 6 to 24 carbon atoms, and from about 0 to 10 mole percent of
units derived from an olefinic compound having the formula ACH=CHB
where A is a group having the formula —(Cx H2x)—COOH wherein x is
from 0 to about 17, and B is hydrogen or carboxyl, with the proviso that
when B is carboxyl, x is 0, and wherein A and B together can be a
dicarboxylic anhydride group.
Preferably, the polysulfone copolymer employed in the present
invention has a weight average molecular weight in the range 10,000 to

1,500,000, preferably in the range 50,000 to 900,000. The units derived
from the one of more 1-alkenes are preferably derived from straight chain
alkenes having 6-18 carbon atoms, for example 1-hexene, 1-heptene, 1-
octene, 1-decene, 1-dodecene, 1-hexadecene and 1-octadecene.
Examples of units derived from the one or more compounds having the
formula ACH=HB are units derived from maleic acid, acrylic acid, 5-
hexenoic acid.
A preferred polysulfone copolymer is 1-decene polysulfone having
an inherent viscosity (measured as a 0.5 weight percent solution in toluene
at 30°C) ranging from about 0.04 dl/g to 1.6 dl/g.
The polymeric polyamines that can be suitably employed in the
process of the present invention are described in U.S. Patent 3,917,466, in
particular at column 6 line 42 to column 9 line 29.
The polymeric polyamine may be prepared for example by heating
an aliphatic primary monoamine or N-aliphatic hydrocarbyl alkylene
diamine with epichlorohydrin in the molar proportion of from 1:1 to 1:1.5 at
a temperature of 50°C to 100°C in the presence of a solvent, e.g. a
mixture of xylene and isopropanol, adding a strong base, e.g. sodium
hydroxide and continuing the heating at 50 to 100°C for about 2 hours.
The product containing the polymeric polyamine may then be separated by
decanting and then flashing off the solvent.
The polymeric polyamine is preferably the product of reacting an N-
aliphatic hydrocarbyl alkylene diamine or an aliphatic primary amine
containing at least 8 carbon atoms and preferably at least 12 carbon
atoms with epichlorohydrin. Examples of such aliphatic primary amines
are those derived from tall oil, tallow, soy bean oil, coconut oil and cotton
seed oil. The polymeric polyamine derived from the reaction of
tallowamine with epichlorohydrin is preferred. A method of preparing such
a polyamine is disclosed in U.S. Patent 3,917,466, column 12, preparation
B.1.0

The above-described reactions of epichlorohydrin with amines to
form polymeric products are well known and find extensive use in epoxide
resin technology.
A preferred polymeric polyamine is a 1:1.5 mole ratio reaction
product of N-tallow-1,3-diaminopropane with epichlorohydrin. One such
reaction product is "Polyflo™ 130" sold by Universal Oil Company.
According to the present invention, the oil-soluble sulfonic acid
component of the process aid additive is preferably any oil-soluble sulfonic
acid such as an alkanesulfonic acid or an alkylarylsulfonic acid. A useful
sulfonic acid is petroleum sulfonic acid resulting from treating oils with
sulfuric acid.
Preferred oil-soluble sulfonic acids are dodecylbenzenesulfonic acid
and dinonylnaphthylsulfonic acid.
The antistatic additive preferably comprises 1 to 25 weight % of the
polysulfone copolymer, 1 to 25 weight % of the polymeric polyamine, 1 to
25 weight % of the oil-soluble sulfonic acid and 25 to 95 weight % of a
solvent. Neglecting the solvent, the antistatic additive preferably
comprises about 5 to 70 weight % polysulfone copolymer, 5 to 70 weight
% polymeric polyamine, and 5 to 70 weight % oil-soluble sulfonic acid and
the total of these three components is preferably 100%.
Suitable solvents include aromatic, paraffin and cycloparaffin
compounds. The solvents are preferably selected from among benzene,
toluene, xylene, cyclohexane, fuel oil, isobutane, kerosene and mixtures
thereof for instance.
According to a preferred embodiment of the present invention, the
total weight of components (1), (2), (3) and the solvent represents
essentially 100% of the weight of the antistatic additive.
One useful composition, for example, consists of 13.3 weight % 1:1
copolymer of 1-decene and sulfur dioxide having an inherent viscosity of
0.05 determined as above, 13.3 weight % of "Polyflo™ 130" (1:1.5 mole
ratio reaction product of N-tallow-1,3-diaminopropane with
epichlorohydrin), 7.4 weight % of either dodecylbenzylsulfonic acid or

dinonylnaphthylsulfonic acid, and 66 weight % of an aromatic solvent
which is preferably toluene or kerosene.
Another useful composition, for example, consists of 2 to 7 weight
% 1:1 copolymer of 1-decene and sulfur dioxide having an inherent
viscosity of 0.05 determined as above, 2 to 7 weight % of "Polyflo™ 130"
(1:1.5 mole ratio reaction product of N-tallow-1,3-diaminopropane with
epichlorohydrin), 2 to 8 weight % of either dodecylbenzylsulfonic acid or
dinonylnaphthylsulfonic acid, and 78 to 94 weight % of an aromatic solvent
which is preferably a mixture of 10 to 20 weight % toluene and 62 to 77
weight % kerosene.
According to a preferred embodiment of the present invention, the
process aid additive is a material sold by Octel under the trade name
STADIS™, preferably STADIS™ 450, more preferably STADIS™ 425.
The polysulfone additive composition is used in large quantity in the
process of this invention. It is essential to use at least 5,000 parts per
million of the additive composition (note: this weight is the total of all
components, including the polysulfone copolymer, any polyamine, any oil
soluble sulfonic acid and solvent).
It is preferred to use from 10,000 to 30,000 ppm of the mixed
polymer antistatic composition sold under the trade name STADIS™.
PartF: Polymerization Process
Polymerization processes suitable for this include gas phase, slurry
phase process; a high pressure process or a combination thereof.
In one embodiment, the process of this invention is directed toward
a high pressure, slurry or gas phase polymerization process of one or
more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to
12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention
is particularly well suited to the polymerization of two or more olefin
monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-
1, hexene-1, octene-1 and decene-1.
Other monomers useful in the polymerization process of the
invention include ethylenically unsaturated monomers, diolefins having 4

to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers and cyclic
olefins. Non-limiting monomers useful in the invention may include norbornene, norbomadiene,
isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene
norbornene, dicyclopentadiene and cyclopentene.
In the most preferred embodiment of the process of the invention, a copolymer of ethylene
is produced, where with ethylene, a comonomer having at least one alpha-olefin having from 4 to
15 carbon atoms, preferably from 4 to .12 carbon atoms, and most preferably from 4 to 8 carbon
atoms, is polymerized in a solution polymerization process.
In another embodiment of the process of the invention, ethylene or propylene is polymerized
with at least two different comonomers, optionally one of which may be a diene, to form a
terpolymer.
In one embodiment, the invention is directed to a polymerization process for polymerizing
propylene alone or with one or more other monomers including ethylene, and/or other olefins
having from 4 to 12 carbon atoms. Polypropylene polymers may also be produced.
Typically in a gas phase polymerization process a continuous cycle is employed where in
one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle
stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is
removed from the recycle composition in another part of the cycle by a cooling system external
to the reactor. Generally, in a gas fluidized bed process for producing polymers, a gaseous stream
containing one or more monomers is continuously cycled through a fluidized bed in the presence
of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed
and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the
reactor and fresh monomer is added to replace the polymerized monomer. (See for example U.S.
Patent 4,543,399)
The reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500
psig (3,448kPa), preferably in the range

of from about 200 psig (1,379 kPa) to about 400 psig (2,759 kPa), more
preferably in the range of from about 250 psig (1,724 kPa) to about 350
psig (2,414 kPa).
The reactor temperature in a gas phase process may vary from
about 30°C to about 120°C, preferably from about 60°C to about 115°C,
more preferably in the range of from about 70°C to 110°C, and most
preferably in the range of from about 70°C to about 95°C.
Other gas phase processes contemplated by the process of the
invention include series or multistage polymerization processes.
In a preferred embodiment, the reactor utilized in the present
invention is capable and the process of the invention is producing greater
than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 Ibs/hr
(90,900 Kg/hr) or higher of polymer, preferably greater than 1,000 Ibs/hr
(455 Kg/hr), more preferably greater than 10,000 Ibs/hr (4,540 Kg/hr),
even more preferably greater than 25,000 Ibs/hr (11,300 Kg/hr), still more
preferably greater than 35,000 Ibs/hr (15,900 Kg/hr), still even more
preferably greater than 50,000 Ibs/hr (22,700 Kg/hr) and most preferably
greater than 65,000 Ibs/hr (29,000 Kg/hr) to greater than 100,000 Ibs/hr
(45,500 Kg/hr).
A slurry polymerization process generally uses pressures in the
range of from about 1 to about 50 atmospheres and even greater and
temperatures in the range of 0°C to about 120°C. In a slurry
polymerization, a suspension of solid, particulate polymer is formed in a
liquid polymerization diluent medium to which ethylene and comonomers
and often hydrogen along with catalyst are added. The suspension
including diluent is intermittently or continuously removed from the reactor
where the volatile components are separated from the polymer and
recycled, optionally after a distillation, to the reactor. The liquid diluent
employed in the polymerization medium is typically an alkane having from
3 to 7 carbon atoms, preferably a branched alkane. The medium
employed should be liquid under the conditions of polymerization and
relatively inert. When a propane medium is used the process must be

Operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an
isobutane medium is employed.
A preferred polymerization technique of the invention is referred to as particle form
polymerization, or a slurry process where the temperature is kept below the temperature at which
the polymer goes into solution. Such technique is well know in the art, and described in for
instance U.S. Patent 3,248,179. Other slurry processes include those employing a loop reactor
and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-
limiting examples of slurry processes include continuous loop or stirred tank processes. Also,
other examples of slurry processes are described in U.S. Patent 4,613,484.
In an embodiment the reactor used in the slurry process of the invention is capable of
and the process of the invention is producing greater than 2,000 lbs of polymer per hour (907
Kg/hr), more preferably greater than 5,000 lbs/hr (2,268 Kg/hr), and most preferably greater than
10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor used in the process of the
invention is producing greater than 15,000 lbs of polymer per hour (6,804 Kg/hr), preferably
greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
Further details are illustrated in the following non-limiting examples
EXAMPLES
Part A- Catalyst Synthesis
Catalysts
Grace-Davison sylopol 948 silica was calcined dehydrated at 250°C under a nitrogen
atmosphere for 5 hours, prior to use in the preparation of a "passified" silica (i.e. silica treated
with triethyl aluminum, "TEAL") described in the following section.

(A.1) TEAL-Treated Silica (SiO2/TEAL)
650 mL of dry, degassed heptane were added to a 1 L flask,
followed by 11.25 mL of a 0.29 weight % solution of polysulfone/solvent
antistatic additive sold under the trademark STADIS™ 425 (purchased from
Octel Starrion L.L.C.) in heptane, and 150 g of calcined Sylopol 948 silica.
The flask was placed on the rotating arm of a rotary evaporator and turned
slowly for 15 minutes. 100 mL of a 25 weight (wt) % TEAL in hexane
solution was added to the flask and then swirled by hand (Note: there is
some heat evolution). 75 mL of 25 weight % TEAL in hexane was then
added. The flask was then placed on the rotating arm of a rotary
evaporator and turned slowly for 1 hour. The slurry was filtered. The filter
cake was transferred back to the flask, reslurried in 350 mL of heptane
and rotated for an additional 30 minutes. The slurry was filtered. The filter
cake was transferred back to the flask, reslurried in 350 mL of heptane
and rotated for an additional 30 minutes. The slurry was filtered a third
time. The filter cake was transferred back to the flask, reslurried in 350 mL
of heptane along with 11.25 mL of the 0.29 weight % solution of STADIS™
425 in heptane. The flask was placed on the rotating arm of a rotary
evaporator and turned slowly for 15 minutes. The solvent was then
removed under vacuum while heating to 60°C to reach a final vacuum of
300 millitorr.
(A.2) Preparation of Supported Catalyst (Method A - "Sequential"
STADIS™ Addition)
Working in a glovebox under inert atmospheric conditions, 1.43 mL
of a 9.58 weight % toluene solution of an activator (described in Part C of
the preferred embodiments), namely
[(C18H37)2CH3NH]{(C6F5)3B(C6H4OH)}) and 0.42 mL of 0.25 molar TEAL in
toluene were mixed in a 100 mL round-bottomed flask and allowed to sit
for 5 minutes. 1.61 g of SiO2/TEAL (from A.1) was then added and the
mixture was shaken on a Lab-Line Mistral Multi-Mixer at high speed for 1
hour. 1.08 mL of 8 weight % of a transition metal catalyst (or catalyst
compound, as described in Part B of the preferred embodiments), namely

(N-(tert-butyl)-l, 1 -di-p-tolyl-1 -((1,2,3,3a,7a-Ti)-3-(1,3-dihydro-2H-isoindol-2-
yl)1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium catalyst molecule in
heptane was premixed with the 0.3 mL of hexene. The catalyst
molecule/hexene solution was then added to the round bottom flask
containing the support/activator material. The flask was then shaken for 1
hour. A (calculated) amount of a 0.29 weight % solution of STADIS™ 425
in heptane to achieve the targeted total antistatic agent concentration in
the final product (as shown in Tables 1 and 2) was then added to the
mixture followed by an additional 15 minutes of mixing. The flask was
then placed under vacuum and dried to a residual pressure of 300 millitorr.
(A.3) Preparation of Supported Catalyst (Method B - "Simultaneous"
STADIS" Addition)
Working in a glovebox under inert atmospheric conditions, 1.43 mL
of a 9.58 weight % toluene solution of
[(C18H37)2CH3NH]{(C6F5)3B(C6H4OH)} and 0.42 mL of 0.25 molar TEAL in
toluene were mixed in a 100 mL round-bottomed flask and allowed to sit
for 5 minutes. 1.61 g of SiC^/TEAL was then added and the mixture was
shaken on a Lab-Line Mistral Multi-Mixer at high speed for 1 hour. 1.08
mL of 8 weight % (N-(tert-butyl)-1 ,1-di-p-tolyl-1-((1,2,3,3a,7a-n)-3-(1,3-
dihydro-2H-isoindol-2-yl)1H-inden-1-yl)silanaminato-(2-)-N-
)dimethyltitanium catalyst molecule in heptane was premixed with the 0.3
mL of hexene. A (calculated) amount of STADIS™ 425 to achieve the
targeted total agent concentration in the final product was then added to
the mixture (see Tables 1 and 2). The catalyst molecule/hexene/STADIS™
solution was then added to the round bottom flask containing the
support/activator material. The flask was then shaken for 1 hour. The
flask was then placed under vacuum and dried to a residual pressure of
300 millitorr.
Part B - Batch Polymerization
Ethylene polymerization experiments in Bench Scale Reactor were
conducted on a 2 L, stirred, autoclave reactor in gas phase operation.

Ethylene polymerizations were run at 80°C for 60 minutes with a total
operating pressure of 300 pounds per square inch gauge (psig) under
homopolymerization conditions. Ethylene partial pressure was 120 psig
and nitrogen constituted the remainder of the gas phase mixture
(approximately 60 mole %). During reactor conditioning and setup, 0.4 mL
of a 25 weight percent solution of tri-isobutylaluminum (TiBAL) was used
as an impurity scavenger to assist with purification of reactor internals and
the seedbed (150 g of high density polyethylene). Catalyst (See Table 1)
was loaded into an injection tube under anaerobic conditions in a glovebox
and was then connected to the reactor. A portion of the nitrogen used to
make up the reactor gas composition was used to push the catalyst into
the reactor at the start of polymerization.





Part C - TSR Polymerization
Continuous, ethylene-hexene gas phase copolymerization
experiments were conducted in a larger 70L Technical Scale Reactor
(TSR) in continuous gas phase operation. Ethylene polymerizations were
run at 80°C with a total operating pressure of 300 pounds per square inch
gauge (psig). Gas phase compositions for ethylene and hexene were
controlled via closed-loop process control to values of 50.0 and 0.22 mole
percent, respectively. Hydrogen was metered into the reactor in a molar
feed ratio of 0.00215 relative to ethylene feed during polymerization.
Nitrogen constituted the remainder of the gas phase mixture
(approximately 49 mole %). Typical production rate for these conditions is
2 to 2.5 of polyethylene per hour.
The catalyst metering device used for administering catalyst to the
reactor is equipped with a probe that measures electrostatic charge
carried by the solid material passing through a monitored tube leading
catalyst to the reactor.

Two catalysts were tested on the catalyst metering system of the
Technical Scale Reactor (corresponding to catalyst 1 and catalyst 3 from
Table 1).
The probe did not detect electrostatic charge (during a "control" run
when no catalyst was passing through the tube). A large static charge
was observed by the probe when catalyst 1 was passing through the tube.
The probe detected substantively less electrostatic charge when catalyst 3
was passing through the tube.
Two catalysts (corresponding catalysts 3 and 6 from Table 1) were
tested for five days in the Technical Scale Reactor under continuous
copolymerization conditions. Catalyst 3 was successfully used to produce
hexene/ethylene copolymer for 33 hours. Then, without interrupting the
copolymerization a transition was made to the catalyst 6 and
polymerization was conducted for 60 more hours. No substantial reactor
fouling or agglomeration formation was observed during the experiment.
In contrast, comparative experiments with catalyst 1 typically produced
enough fouling to force termination of the polymerization reactions after
several hours and in some cases it was not even possible to establish
stable polymerization with catalyst 1 due to static/fouling conditions.
INDUSTRIAL APPLICABILITY
Highly active supported "single site" catalysts for the polymerization
of ethylene are prepared with a porous metal oxide support and a very
large amount of an antistatic agent. The use of the large amount of
antistatic agent reduces the tendency of the single site catalyst to foul the
polymerization reactor. The polyethylene produced with these catalysts
may be used to produce a wide variety of extruded and molded goods,
ranging from flexible plastic films to rigid plastic containers.

WE CLAIM:
1. An olefin polymerization catalyst comprising a porous metal oxide, a transition metal
catalyst system and an antistatic additive, wherein said antistatic additive comprises a
polysulfone and a solvent for said polysulfone and wherein said catalyst is further
characterized in that said antistatic additive is added to said porous metal oxide in an
amount of from 5,000 to 50,000 parts per million by weight based on the weight of said
porous metal oxide and have a pore volume of from 0.1 to 5 mL/g.
2. The catalyst as claimed in claim 1, wherein said transition metal catalyst system comprises
an organometallic catalyst compound and an activator.
3. The catalyst as claimed in claim 1, wherein said organometallic catalyst compound is a
group 4 metal complex selected from the group consisting of monocyclopentadienyl
complexes and bis (cyclopentadienyl) complexes.
4. The catalyst as claimed in claim 2 wherein said organometallic catalyst compound
comprises a group 4 metal complex characterized by having a bridged, bidentate
cyclopentadienylamine ligand.
5. The catalyst as claimed in claim 2, wherein said activator is an ionic activator comprising a
single boron atom and a substituent comprising an active hydrogen moiety.

6. A process for polymerizing at least one olefin selected from a the group consisting of C2 to
C10 alpha olefins in a polymerization reactor with an olefin polymerization catalyst
comprising a polysulfone and a solvent for said polysulfone and wherein said catalyst is
further characterized in that said antistatic additive is added to said porous metal oxide in
an amount of from 5,000 to 50,000 parts per million by weight based on the weight of said
porous metal oxide; further characterized in that said porous metal oxide is silica having a
pore volume of from 0.1 to 5 mL/g.
7. The process as claimed in claim 6 wherein said transition metal catalyst system comprises
an organometallic catalyst compound and an activator.
8. The process as claimed in claim 7 wherein said reactor is a gas phase reactor.


ABSTRACT

Title: AN OLEFIN POLYMERIZATION CATALYST
An olefin polymerization catalyst comprising a porous metal oxide, a transition metal catalyst
system and an antistatic additive, wherein said antistatic additive comprises a polysulfone and
a solvent for said polysulfone and wherein said catalyst is further characterized in that said
antistatic additive is added to said porous metal oxide in an amount of from 5,000 to 50,000
parts per million by weight based on the weight of said porous metal oxide and have a pore
volume of from 0.1 to 5 mL/g.

Documents:

4698-KOLNP-2008-(15-03-2012)-AMANDED CLAIMS.pdf

4698-KOLNP-2008-(15-03-2012)-AMANDED PAGES OF SPECIFICATION.pdf

4698-KOLNP-2008-(15-03-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

4698-KOLNP-2008-(15-03-2012)-FORM-1-1.pdf

4698-KOLNP-2008-(15-03-2012)-FORM-1.pdf

4698-KOLNP-2008-(15-03-2012)-FORM-2.pdf

4698-KOLNP-2008-(15-03-2012)-FORM-3.pdf

4698-KOLNP-2008-(15-03-2012)-FORM-5.pdf

4698-KOLNP-2008-(15-03-2012)-OTHERS.pdf

4698-KOLNP-2008-(15-03-2012)-PCT SEARCH REPORT.pdf

4698-KOLNP-2008-(15-03-2012)-PETITION UNDER RULE 137.pdf

4698-KOLNP-2008-(18-09-2012)-FORM-27.pdf

4698-kolnp-2008-abstract.pdf

4698-kolnp-2008-claims.pdf

4698-KOLNP-2008-CORRESPONDENCE 1.1.pdf

4698-kolnp-2008-correspondence.pdf

4698-kolnp-2008-description (complete).pdf

4698-KOLNP-2008-EXAMINATION REPORT.pdf

4698-kolnp-2008-form 1.pdf

4698-KOLNP-2008-FORM 18 1.1.pdf

4698-kolnp-2008-form 18.pdf

4698-kolnp-2008-form 2.pdf

4698-KOLNP-2008-FORM 26.pdf

4698-KOLNP-2008-FORM 3 1.1.pdf

4698-kolnp-2008-form 3.pdf

4698-KOLNP-2008-FORM 5 1.1.pdf

4698-kolnp-2008-form 5.pdf

4698-KOLNP-2008-GRANTED-ABSTRACT.pdf

4698-KOLNP-2008-GRANTED-CLAIMS.pdf

4698-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

4698-KOLNP-2008-GRANTED-FORM 1.pdf

4698-KOLNP-2008-GRANTED-FORM 2.pdf

4698-KOLNP-2008-GRANTED-SPECIFICATION.pdf

4698-kolnp-2008-international preliminary examination report.pdf

4698-kolnp-2008-international publication.pdf

4698-kolnp-2008-international search report.pdf

4698-KOLNP-2008-OTHERS.pdf

4698-kolnp-2008-pct priority document notification.pdf

4698-kolnp-2008-pct request form.pdf

4698-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf

4698-kolnp-2008-specification.pdf


Patent Number 253310
Indian Patent Application Number 4698/KOLNP/2008
PG Journal Number 28/2012
Publication Date 13-Jul-2012
Grant Date 11-Jul-2012
Date of Filing 19-Nov-2008
Name of Patentee NOVA CHEMICALS (INTERNATIONAL) S. A.
Applicant Address AVENUE DE LA GARE 14 CH-1700 FRIBOURG
Inventors:
# Inventor's Name Inventor's Address
1 JEREMIC, DUSAN 240 SANDS TONE DRIVE, NW. CALGARY ALBERTA T3K 3S6
2 MCKAY, IAN 96 CASTLEGLEN ROAD, NE CALGARY, ALBERTA T3J 1T1
3 MESQUITA, PAUL 71 SIENNA HEIGHTS WAY SW, CALGARY, ALBERTA T3H 3T6
4 JACOBSEN, GRANT, BERENT RINGLAAN 59, B-3080 TERVUREN
5 MASTROIANNI, SERGIO COURS SAINT MICHEL N92 ETTERBEEK, B-1040 BRUXELLES
PCT International Classification Number C08F 10/00,C08F 4/02
PCT International Application Number PCT/CA2007/000737
PCT International Filing date 2007-05-02
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0610668.6 2006-05-30 U.K.