Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
"~; ~ 'a-'
DOCKET NO. 05015.0397P1 (Formerly 71 I33)
PROCATALYSTS, CATALYST SYSTEMS, AND USE IN OLEFIN
POLYMERIZATION
Field of the Invention
This invention belongs to the field of organometalfic chemistry. in
particular,
this invention relates to certain novel supported organometallic solid
procatalysts and
catalyst systems particularly useful for olefin polymerization or
interpolymerization.
lo Backqround of the Invention
A particularly useful polymerization medium for producing polyethylene
polymers is a gas phase process. Examples of such are given in U.S. Patent
Nos.
3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749
and
5,541,270 and Canadian Patent No. 991,798 and Belgian Patent No. 839,380.
Ziegler-Natta type catalyst systems for the polymerization of olefins are well
known in the art and have been known at least since the issuance of U.S.
Patent No.
3,113,115. Thereafter, many patents have been issued relating to new or
improved
Ziegler-Natta type catalysts. Examples of such patents are U.S. Patents Nos.
3,594,330; 3,676,415; 3,644,318; 3,917,575; 4,105,847; 4,748,754; 4,256,866;
4,298,713; 4,311,752; 4,363,904; 4,481,301 and Reissue 33,683.
These patents disclose Ziegler-Natta type catalysts (referred to herein as
ZNCs) that are well known as typically consisting of a catalyst system
comprising a
transition metal-containing procatalyst, which typically contains titanium,
and an
organometallic cocatalyst, typically an organoaluminum compound. Optionally
used
with the catalyst are activators such as halogenated hydrocarbons and activity
modifiers such as electron donors.
In the earliest patents involving 'Ziegler Natta' catalysts for olefin
polymerization, titanium halides are treated with metal alkyls in order to
provide a
reduced solid, consisting primarily of TICI3 and typically admixed with the by-
products
of the reaction. In these systems, a solid which is primarily TiCl3 is formed
which is
used as the procatalyst for the polymerization of olefins. There are several
families
of patents describing the generation of solid TiCl3.
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U
DOCKET NO. 71133
Soluble Ziegler-Natta catalysts have also been described. U.S. Patent
No. 4,366,297 describes a process in which an ether adduct of TiCl4 is treated
with a
reducing agent to afford a soluble TiCl3 species, suggesting further that a
precipitate
forms in the absence of the ether. U.S. Patent No. 3,862,257 describes
hydrocarbon
s solutions of TiRCI3~AICl3 from which AlCl3 is removed by addition of a
modifier, in
order to provide low molecular weight waxes in a solution process. U.S. Patent
No.
4,319,010 describes a solution process for olefrn polymerization above 110
°C using
a soluble catalyst formulation comprising reacting a titanium (IV) compound
with the
reaction product of a magnesium compound solubilized by an aluminum alkyl,
while
to U.S. Patent No. 4,540,756 demonstrates the activity of the reaction product
of an
alkylaluminum activator with a tetravalent transition metal salt solubilized
by a
magnesium carboxylate, specifically referring to TiCl4. U.S. Patent No.
5,037,997
describes an ethylene dimerization catalyst formed from the reaction of
Ti(OR)4 +
AIRS + MgR2 which has activity of less than 10 Kg/g Ti~h. U.S. Patent Nos.
15 5,039,766 and 5,134,104 describe soluble titanium amido catalysts which are
reacted with an aluminum alkyl activator or alumoxane in the presence of the
substrate olefin.
Several patents describe supporting otherwise soluble catalysts. U.S. Patent
No. 3,634,384 describes generation of soluble titanium halide/ aluminum alkyl
2o species at low temperatures to which is added a hydroxylated solid support
which
forms Mg-O-Ti covalent bonds. U.S. Patent No. 3,655,812 describes a similar
procedure by generating a reduced titanium species in an arene solvent and
adding
a magnesium halide support to increase activity. U.S. Patent No. 4,409,126
describes a hydrocarbon soluble reaction product obtained by reacting an
alkoxide-
25 containing transition metal compound with an organometallic compound which
is
useful in the preparation of catalysts for polymerizing olefins. A variation
of this is
described in U.S. Patent No. 5,320,994 wherein a titanium alkoxide is reacted
with
an aluminum alkyl, followed by addition of a magnesium compound which forms
MgCl2 under the reaction conditions. This case further specifies the
importance of
3o an a, w -dihaloalkane in preventing over-reduction to TiCl2.
U.S. Patent No. 2,981,725 teaches the reaction of TiCl4 with various
supports, e.g. silicon carbide, followed by treatment AIEt2Cl as a cocatalyst.
The
supported catalyst shows an improvement of less than a factor of two over the
unsupported precipitated catalyst. U.S. Patent No. 4,426,315 describes
generation
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DOCKET NO. 71133
of a similar supported catalyst in which the titanium and aluminum compounds
are
added simultaneously to a sluny of a carrier, with any reaction occurring only
in the
presence of said carrier.
Certain soluble or "liquid" Ziegler-Natta catalyst systems are known which
utilize titanium chelates. For example, U.S. Patent Nos. 3,737,416 and
3,737,417
describe the reaction of titanium chelates with halogenating agents followed
by
activation with aluminum alkyls to provide catalysts which copolymerize a-
olefins and
butadiene. These activations are carried out at temperatures as low as -
78° C in the
presence of monomer. U.S. Patent No. 3,652,705 claims only the use of nitrite
1o electron donors reacted with TiCh prior to treatment with organoaluminum
compounds. These catalysts are used preferably in arene solution or slurry.
U.S.
Patent Nos. 4,482,639, 4,603,185, and 4,727,123 describe bimetallic complexes
with
monoanionic tridentate chelating ligands which are activated with aluminum
alkyls for
the polymerization of olefins, alkynes, and dienes. U.S. Patent No. 5,021,595
15 describes catalysts based on soluble trivalent metal (especially vanadium}
complexes of bidentate chelating ligands. These soluble complexes are prepared
by
reaction of the trivalent metal halide with compounds containing acidic
hydrogen, and
are activated for the polymerization of olefins with aluminum alkyls. U.S.
Patent No.
5,378,778 reports the reaction of titanium amides with organic oxygen-
containing
2o compounds having acidic hydrogens, followed by in-situ activation with
aluminum
alkyls to give highly active, unsupported olefin polymerization catalysts.
U.S. Patent
No. 5,840,646 reports Ti, Zr, or Hf dialkyl complexes of chelating
bis(alkoxide)
ligands with a tethered Lewis base attached to the ligand backbone. These
compounds may be used for the polymerization of olefins in the presence of an
25 activator which generates a cationic complex, such as trityl
tetrakis(pentafluorophenyl)borate or methyl alumoxane.
Aluminum alkyls are commonly used as activators or cocatalysts with Ziegler-
Natta catalysts, and there are some examples of compounds of the form AIR3."L"
(n
= 1 or 2), where each L is a monoanionic ligand. U.S. Patent No. 3,489,736
3o illustrates the use of various aluminum nitrogen compounds, including
carboxylic
acid amides, as cocatalysts in conjunction with an aluminum halide as Lewis
acid
with Ziegler-Natta catalysts such as TiCl3. U.S. Patent No. 3,723,348
describes use
of vanadium compounds with an activator which may be an aluminum alkoxide,
amide, carboxylate, or acetylacetonate, among others. U.S. Patent No.
3,786,032
Substitute Page 3
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DOCKET NO. 71133
utilizes the reaction product of an organoaluminum or organozinc with an oxime
or
hydroxyester as activators. U.S. Patent No. 3,883,493 utilizes aluminum
carbamates
in conjunction with another organoaluminum compound as cocatalysts. Conjugated
dienes may be polymerized using mixed titanium or vanadium halides, an
aluminum
trialkyl and a small amount of carbon disulfide, as reported in U.S. Patent
No.
3,948,869. U.S. Patent No. 4,129,702 discloses use of aluminum or zinc salts
of
carboxylic acid amides as activators with Ziegler-Natta catalysts, optionally
on a
support, for the polymerization of vinyl or vinylidene halides, noting the
improvement
of aging the co-catalyst to eliminate isocyanate. U.S. Patent No. 5,468,707
1o describes use of,bidentate, dianionic Group 13 element compounds as co-
catalysts.
U.S. Patent No. 5,728,641 also describes use of aluminum catecholate compounds
as a components in a four-component catalyst system which includes
organocyclic
compounds with two or more conjugated double bonds.
Aluminum chelates have also been used as external donors. U.S. Patent No.
15 3,313,791 discloses use of acetylacetonato aluminum alkoxides as external
donors
with a titanium trichloride and alkyl aluminum dihalide catalyst system. U.S.
Patent
No. 3,919,180 discusses the use of external donors which may be bidentate in
combination either with the titanium catalyst or the aluminum co-catalyst.
U.S.
Patent No. 5,777,120 describes the use of cationic aluminum amidinate
compounds
2o as single site catalysts for the polymerization of olefins.
U.S. Patent No. 3,534,006 describes a catalyst comprising Groups 4 - 6
metal compounds activated with bis(dialkylaluminoxy)alkane compounds. It
further
claims the use of additional external donors or promoters which include a wide
variety of nitrogen-containing compounds. U.S. Patent No. 4,195,069 describes
the
25 interaction of a TiCl4 complex with a complexing agent with an
organoaluminum
complex with a complexing agent. This interaction results in reduction of
TiCl4 to a
precipitate of TiCl3.
U.S. Patent No. 3,714,133 describes a catalytic system for producing high
molecular weight alternating copolymers of butadiene and alpha-olefins in high
yield.
3o The catalyst system is composed of an organoaluminum compound, a titanium
tetrahalide, and a carbonyl group - containing compound. The catalyst system
can
also contain a halogen containing compound, metal oxide or metalloid oxide,
whereby the catalytic properties of the catalyst system can be improved.
Substitute Page 4
fi; F~ ~ pV ';i
CA 02395710 2002-06-26
~~~~ ~r
~ ~~ ~4 ~~~~ '"~ "n z
~' ,. ,,~t,
DOCKET NO. ? 1133
phosphorus, arsenic, antimony, and bismuth, or mixtures thereof, X is
fluoride,
chloride, bromide, or iodide, and 0 < x s 4, with at least one alkylating
agent of the
formula LXERnYmHp, where each L is independently a monoanionic, bidentate
ligand
s bound to E by two atoms selected from the group consisting of oxygen,
sulfur,
selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, and bismuth, or
mixtures thereof, E is boron, aluminum, gallium, or indium, each R is
independently a
hydrocarbyl group, each Y is independently a monoanionic, monodentate ligand,
0 <
x s 2, n > 0, m >_ 0, p ~ 0, and x + n + m + p = 3, in at least one aprotic
solvent to
io provide a soluble species which is subsequently contacted with a support.
The
resulting solid procatalyst, with a cocatalyst, provides a catalyst system
suitable for
the polymerization or interpolymerization of olefins.
Detailed Description of the Invention
is
A solid procatalyst prepared by reacting at least one transition metal
compound of empirical formula ML"XX,~.x, where M is titanium, zirconium, or
hafnium,
each L is independently a monoanionic, bidentate ligand bound to M by two
atoms
selected from the group consisting of oxygen, sulfur, selenium, tellurium,
nitrogen,
2o phosphorus, arsenic, antimony, and bismuth, or mixtures thereof, X is
fluoride,
chloride, bromide, or iodide, and 0 < x <_ 4, with at least one alkylating
agent of the
formula LxER~YmHP, where each L is independently a monoanionic, bidentate
ligand
bound to E by two atoms selected from the group consisting of oxygen, sulfur,
selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, and bismuth, or
2s mixtures thereof, E is boron, aluminum, gallium, or indium, each R is
independently a
hydrocarbyl group, each Y is independently a monoanionic, monodentate ligand,
0 <
x <_ 2, n > 0, m z 0, p >_ 0 and x + n + m + p = 3, in at least one aprotic
solvent to
provide a soluble species which is subsequently contacted with a support.
Contacting the soluble species with the support includes depositing the
soluble
3o species on the support. The resulting solid procatalyst, with a cocatalyst,
provides a
catalyst system suitable for the polymerization ar interpolymerization of
olefins.
All mention herein to elements of Groups of the Periodic Table are made in
reference to the Periodic Table of the Elements, as published in uChemical and
Engineering News", 63(5), 27, 1985. In this format, the Groups are numbered 1
to
Substitute Page 5
'.~. CA 02395710 2002-06-26
DOCKET NO. 71133
18. The abbreviations Me (for methyl group), Et (for Ethyl group), TMA (for
trimethylaluminum), and TEAL (for triethylaluminum) are used herein.
The present invention comprises a solid procatalyst prepared by reacting a
transition metal compound of empirical formula MLxX~.x with an alkylating
agent of
the formula LXER~YmHp in an aprotic solvent to provide a soluble species which
is
subsequently contacted with a support. in the event of any precipitation
during the
generation of the soluble component(s), the precipitate must be redissolved,
filtered,
or otherwise eliminated prior to contacting the soluble species with a
support.
The molar ratio of the alkylating agent to the transition metal compound is
to preferably from about 0.1 to about 100. Preferably, the molar ratio of the
alkylating
agent to the transition metal compound is from about 0.25 to about 15. More
preferably, the molar ratio of the alkylating agent to the transition metal
compound is
from about 1 to about 5.
The at least one transition metal compound used in the process of the
i5 present invention can be any compound of the empirical formula,
MLxX4-x.
or mixtures thereof,
wherein M is selected from the group consisting of titanium, zirconium and
hafnium,
2o each L is independently a monoanionic, bidentate ligand bound to M by two
atoms selected from the group consisting of oxygen, sulfur, selenium,
tellurium,
nitrogen, phosphorus, arsenic, antimony, and bismuth, or mixtures thereof,
each X is independently selected from the group consisting of fluoride,
chloride, bromide, and iodide, and
25 0<xs4.
The transition metal compound (MLxX~.x), may be generated and/ or
introduced in any way to the aprotic solvent prior to contact with the
alkylating agent,
including dissolution of a pure species or by mixing, e.g., a metal halide
with the
conjugate acid of the ligand (L), a complex of the ligand, or a salt of the
tigand, in
3o situ, followed by treatment with alkylating agent.
Examples of the monoanionic, bidentate ligand L bound to M are the
conjugate bases of compounds containing acidic hydrogen and the conjugate
bases
of compounds containing an acidic carbon-hydrogen bond.
Substitute Page 6
CA 02395710 2002-06-26
DOGxET NO. 71133
Examples of the monoanionic, bidentate ligand L bound to M useful herein
which are the conjugate bases of compounds containing acidic hydrogen are
carboxylic acids, carboxylic acid amides, carboxylic acid phosphides,
thiocarboxylic
acids, dithiocarboxylic aads, thiocarboxylic acid amides, thiocarboxylic acid
phosphides, carbonic acid, carbamamic acids, ureas, thiocarbonic acid,
thioureas,
thiocarbamamic acids, dithiocarbamic acids, hydroxycarboxylic esters,
hydroxycarboxylic acid amides, amino acid esters, hydroxythiocarboxylic
esters,
hydroxydithiocarboxylic esters, hydroxythiocarboxylic acid amides,
hydroxycarboxylic thioesters, hydroxythiocarboxylic thioesters,
to hydroxydithiocarboxylic thioesters, mercaptocarboxylic esters,
mercaptocarboxylic
acid amides, mercaptothiocarboxylic esters, mercaptodithiocarboxylic esters,
mercaptothiocarboxylic acid amides, mercaptocarboxylic thioesters,
mercaptothiocarboxylic thioesters, mercaptodithiocarboxylic thioesters,
hydroxyketones, hydroxyaldehydes, hydroxyimines, mercaptoketones,
15 mercaptoaldehydes, mercaptoimines, hydroxythioketones,
hydroxythioaldehydes,
mercaptothioketones, mercaptothioaldehydes, 2-hydroxybenzaldehydes, 2-
mercaptobenzaldehydes, 2-aminobenzaldehydes, 2-hydroxybenzthioaldehydes, 2-
hydroxybenzoate esters, 2-hydroxybenzamides, 2-hydroxybenzoate thioesters, 2-
hydroxythiobenzoate esters, 2-hydroxythiobenzamides, 2-
20 hydroxybenzthioaldehydes, 2-mercaptobenzthioaldehydes, 2-
aminobenzthioaldehydes, 2-hydroxyarylketones, 2-mercaptoarylketones, 2-
aminoarylketones, 2-hydroxyarylimines, 2-mercaptoarylimines, 2-
aminoarylimines, 2-
hydroxyarylthioketones, 2-mercaptoarylthioketones, 2-aminoarylthioketones,
benzoins,2-pyrrolecarboxadehydes, 2-pyrrolethiocarboxadehydes, 2-
25 pyrrolecarboxaldimines, hydrocarbyl 2-pyrrolyl ketones, hydrocarbyl 2-
pyrrolyl
imines, hydrocarbyl 2-pyrrolyl thioketones, 2-indolecarboxadehydes, 2-
indolethiocarboxadehydes, 2-indolecarboxaldimines, hydrocarbyl 2-indolyl
ketones,
hydrocarbyl 2-indolyl imines, hydrocarbyl 2-indolyl thioketones,
hydroxyquinolines,
tropolones, aminotropolones, aminotropone imines.
3o Examples of the monoanionic, bidentate ligand L bound to M useful herein
which are the conjugate bases of compounds containing an acidic carbon-
hydrogen
bond are 1,3-diketones, betaketoacid esters, betaketoacid amides, 3-
nitroketones, 3-
nitroacid esters, 3-nitroacid amides, phthalate monoesters, di(2-
furyl)alkanes, bis(5-
(2,3-dihydrofuryl))alkanes, di(2-thiophenyl)alkanes, bis(5-(2,3-
Substitute Page 7
~~' CA 02395710 2002-06-26
°° M:
DOCKET NO. 71133
dihydrothiophenyl))alkanes, di(2-pyridyl~lkanes, malonate diesters,
betaketoimines,
1,3-diimines, betaiminoacid esters, betaiminoacid amides, 3-nitroimines,
alkylsulfinylacetate esters, alkylsulfonylacetate esters,
bis(alkylsulfinyl)alkanes,
bis(alkylsulfonyl)alkanes.
Preferred examples of the monoanionic, bidentate ligand L bound to M useful
herein are the conjugate bases of 1,3-diketones such as acetylacetone, 3,5-
heptanedione, 2,6-dimethyl-3,5-heptanedione, 5,7-undecanedione,
benzoylacetone,
dibenzoylmethane, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-
hexafluoroacetylacetone,
2,2,6,6-tetramethyl-3,5-heptanedione, mono- and di-imine analogs of the above-
to listed 1,3-diketones, 2-hydroxybenzene carboxaldehydes, the imine analogs
of the
above-listed compounds.
Mixtures of monoanionic, bidentate ligands L bound to M may be used as the
monoanionic, bidentate ligand L bound to M.
Mixtures of compounds of the above empirical formula MLXX,,.X may also be
15 used herein as the transition metal compound.
The at least one alkylating agent used in the present invention can be any
organometallic compound of the empirical formula,
LxER"Yn,Hp,
or mixtures thereof,
20 wherein,
each L is independently a monoanionic, bidentate ligand bound to E by two
atoms selected from the group consisting of oxygen, sulfur, selenium,
tellurium,
nitrogen, phosphorus, arsenic, antimony, and bismuth, or mixtures thereof;
E is selected from the group consisting of boron, aluminum, gallium, and
25 indium;
each R is independently a hydrocarbyl group,
each Y is independently a monoanionic, monodentate ligand,
0<xs2,n>O,m>_O,pZO,and
x+n+m+p=3.
3o The term "hydrocarbyl group", as used herein, denotes a monovalent, linear,
branched, cyclic, or polycyclic group which contains carbon and hydrogen
atoms.
The hydrocarbyl group may optionally contain atoms in addition to carbon and
hydrogen selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table.
Examples of monovalent hydrocarbyls include the following: C,-C~ alkyl; C~-C~
alkyl
Substitute Page 8
CA 02395710 2002-06-26
~~ ,
DOCKET NO. 71133
substituted with one or more groups selected from C,-C~ alkyl, C3-C,5
cycloalkyl or
aryl; C3-C,5 cycloalkyl; C3-C,5 cycloalkyl substituted with one or more groups
selected from C,-C~ alkyl, C3-C,5 cycloalkyl or aryl; Ce-C,5 aryl; and Ce-C,5
aryl
substituted with one or more groups selected from C,-C~ alkyl, C3-C,s
cycloalkyl or
aryl; where aryl preferably denotes a substituted or unsubstituted phenyl,
napthyl, or
anthracenyl group.
The alkylating agent (LxER"YmHp), may be generated and/ or introduced in
any way to the aprotic solvent prior to contact with the alkylating agent,
including
dissolution of a pure species or by mixing, for example, a compound of
empirical
1o formula ER"+,YmHP with the ligand (L), a complex of the ligand, or a salt
of the ligand,
in situ, followed by treatment with alkylating agent.
Examples of the monoanionic, bidentate ligand L bound to E are the
conjugate bases of compounds containing acidic hydrogen and the conjugate
bases
of compounds containing an acidic carbon-hydrogen bond.
1s Examples of the monoanionic, bidentate ligand L bound to E useful herein
which are the conjugate bases of compounds containing acidic hydrogen are
carboxylic acids, carboxylic acid amides, carboxylic acid phosphides,
thiocarboxylic
acids, dithiocarboxylic acids, thiocarboxylic acid amides, thiocarboxylic acid
phosphides, carbonic aad, carbamamic acids, ureas, thiocarbonic acid,
thioureas,
2o thiocarbamamic acids, dithiocarbamic acids, hydroxycarboxylic esters,
hydroxycarboxylic acid amides, amino acid esters, hydroxythiocarboxylic
esters,
hydroxydithiocarboxylic esters, hydroxythiocarboxylic acid amides,
hydroxycarboxylic thioesters, hydroxythiocarboxylic thioesters,
hydroxydithiocarboxylic thioesters, mercaptocarboxylic esters,
mercaptocarboxylic
25 acid amides, mercaptothiocarboxylic esters, mercaptodithiocarboxylic
esters,
mercaptothiocarboxylic acid amides, mercaptocarboxylic thioesters,
mercaptothiocarboxylic thioesters, mercaptodithiocarboxylic thioesters,
hydroxyketones, hydroxyaldehydes, hydroxyimines, mercaptoketones,
mercaptoaldehydes, mercaptoimines, hydroxythioketones, hydroxythioaldehydes,
3o mercaptothioketones, mercaptothioaldehydes, 2-hydroxybenzaldehydes, 2-
mercaptobenzaldehydes, 2-aminobenzaldehydes, 2-hydroxybenzthioaldehydes, 2-
hydroxybenzoate esters, 2-hydroxybenzamides, 2-hydroxybenzoate thioesters, 2-
hydroxythiobenzoate esters, 2-hydroxythiobenzamides, 2-
hydroxybenzthioaldehydes, 2-mercaptobenzthioaldehydes,
Substitute Page 9
R ~~~~ ~r .
CA 02395710 2002-06-26
~ ~~ ~ _ ,
DOCKET NO. 71133
2-aminobenzthioaldehydes, 2-hydroxyarylketones, 2-mercaptoarylketones, 2-
aminoarylketones, 2-hydroxyarylimines, 2-mercaptoarylimines, 2-
aminoarylimines,
2-hydroxyarylthioketones, 2-mercaptoarylthioketones, 2-aminoarylthioketones,
benzoins,2-pyrrolecarboxadehydes, 2-pyrrolethiocarboxadehydes, 2-
s pyrrolecarboxaldimines, hydrocarbyl 2-pyrrolyl ketones, hydrocarbyl 2-
pyrrolyl
imines, hydrocarbyl 2-pyrrolyl thioketones, 2-indolecarboxadehydes, 2-
indolethiocarboxadehydes, 2-indolecarboxaldimines, hydrocarbyl 2-indolyl
ketones,
hydrocarbyl 2-indolyl imines, hydrocarbyl 2-indolyl thioketones,
hydroxyquinolines,
tropolones, aminotropolones, aminotropone imines.
to Examples of the monoanionic, bidentate ligand L bound to E useful herein
which are the conjugate bases of compounds containing an acidic carbon-
hydrogen
bond are 1,3-diketones, betaketoacid esters, betaketoacid amides, 3-
nitroketones,
3-nitroacid esters, 3-nitroacid amides, phthalate monoesters, di(2-
furyi)alkanes,
bis(5-(2,3-dihydrofuryl))alkanes, di(2-thiophenyl)alkanes, bis(5-(2,3-
1s dihydrothiophenyl))alkanes, di(2-pyridyl)alkanes, malonate diesters,
betaketoimines,
1,3-diimines, betaiminoacid esters, betaiminoacid amides, 3-nitroimines,
alkylsulfinylacetate esters, alkylsulfonylacetate esters,
bis(alkylsulfinyl)alkanes,
bis(alkylsulfonyl)alkanes.
Preferred examples of the monoanionic, bidentate ligand L bound to E useful
2o herein are the conjugate bases of 1,3-diketones such as acetylacetone, 3,5-
heptanedione, 2,6-dimethyl-3,5-heptanedione, 5,7-undecanedione,
benzoylacetone,
dibenzoylmethane, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-
hexafluoroacetylacetone,
2,2,6,6-tetramethyl-3,5-heptanedione, mono- and di-irnine analogs of the above-
listed 1,3-diketones, 2-hydroxybenzene carboxaldehydes, the imine analogs of
the
2s above-listed compounds.
Mixtures of monoanionic, bidentate ligands L bound to E may be used as
the monoanionic, bidentate ligand L bound to E.
Examples of the monoanionic, monodentate ligand Y include the halides,
-OR, -OBR2, -OSR, -ONR2, -OPR2, -NR2, -N(R)BR2, -N(R)OR, -N(R)SR, -N(R)NR2,
30 -N(R)PR2, -N(BR2)2, -N=CR2, -N=NR; -N=PR, -SR, -SBR2, -SOR, -SNR2, -SPR2,
-PR2. Each R is independently a hydrocarbyl group, as defined above. Examples
of
halides are fluoride, chloride, bromide, and iodide.
Examples of alkoxides are methoxide, ethoxide, n-propoxide, i-propoxide,
cyclopropyloxide, n-butoxide, i-butoxide, s-butoxide, t-butoxide,
cyclobutyloxide,
Substitute Page 10
~~ ~ ,: CA 02395710 2002-06-26
z ' .rw g ~ f , r F m '. = r
sad .;~ ~.,.~a' ,YZ.,d~? .~'a~pv ~ $ t
s: '?.
DOCKET NO. 71133
n-amyloxide, i-amyloxide, s-amyloxide, t-amyloxide, neopentoxide,
cyGopentyloxide,
n-hexoxide, cyGohexyloxide, heptoxide, octoxide, nonoxide, decoxide,
undecoxide,
dodecoxide, 2-ethyl hexoxide, phenoxide, 2,6-dimethylphenoxide, 2,6-di-i-
propylphenoxide, 2,6-diphenylphenoxide, 2,6-dimesitylphenoxide, 2,4,6-
trimethylphenoxide, 2,4,6-tri-i-propylphenoxide, 2,4,6-triphenylphenoxide,
2,4,6-
trimesitylphenoxide, benzyloxide, menthoxide, halogenated alkoxides such as
trifluoromethoxide, trifluoroethoxide, trifluoro-i-propoxide, hexafluoro-i-
propoxide,
heptafluoro-i-propoxide, trifluoro-t-butoxide, hexafluoro-t-butoxide,
trifluoromethoxide,
trichloroethoxide, trichloro-i-propoxide.
to Examples of thiolates are methylthiolate, ethylthiolate, n-propylthiolate,
i-
propylthiolate, cyclopropylthiolate, n-butylthiolate, i-butylthiolate, s-
butylthiolate, t-
butylthiolate, cyclobutylthiolate, n-amylthiolate, i-amylthiolate, s-
amylthiolate, t-
amylthiolate, neopentylthiolate, cyclopentylthiolate, n-hexylthiolate,
cyclohexylthiolate, phenylthiolate, 2,6-dimethylphenylthiolate, 2,6-di-i-
1s propylphenylthiolate, 2,6-diphenylphenylthiolate, 2,6-
dimesitylphenylthiolate, 2,4,6-
trimethylphenylthiolate, 2,4,6-tri-i-propylphenylthiolate, 2,4,6-
triphenylphenylthiolate,
2,4,6-trimesitylphenylthiolate, benzylthiolate, heptylthiolate, octylthiolate,
nonylthiolate, decylthiolate, undecylthiolate, dodecylthiolate, 2-ethyl
hexylthiolate,
menthylthiolate, halogenated alkylthiolates such as trifluoromethylthiolate,
2o trifluoroethylthiolate, trifluoro-i-propylthiolate, hexafluoro-i-
propylthiolate, heptafluoro-
i-propylthiolate, trifluoro-t-butylthiolate, hexafluoro-t-butylthiolate,
trifluoromethylthiolate, trichloroethylthiolate, trichloro-i-propylthiolate.
Examples of amides are dimethylamide, diethylamide, di-n-propylamide, di-i-
propylamide, dicyclopropylamide, di-n-butylamide, di-i-butylamide, di-s-
butylamide,
25 di-t-butylamide, dicyclobutylamide, di-n-amylamide, di-i-amylamide, di-s-
amylamide,
di-t-amylamide, dicyclopentylamide, dineopentylamide, di-n-hexylamide,
dicyclohexylamide, diheptylamide, dioctylamide, di-nonylamide, didecylamide,
diundecylamide, didodecylamide, di-2-ethyl hexylamide, diphenylamide, bis-2,6-
dimethylphenylamide, bis-2,6-di-i-propylphenylamide, bis-2,6-
diphenylphenylamide,
3o bis-2,6-dimesitylphenylamide, bis-2,4,6-trimethylphenylamide, bis-2,4,6-tri-
i-
propylphenylamide, bis-2,4,6-triphenyiphenytamide, bis-2,4,6-
trimesitylphenylamide,
dibenzylamide, dihexylamide, dicyclohexylamide, diociylamide, didecylamide,
dioctadecylamide, diphenylamide, dibenzylamide, bis-2,6-dimethylphenylamide,
Substitute Page 11
h awo.
1~ry CA 02395710 2002-06-26
$x_~,
DOCKET NO. 71133
2,6-bis-i-propylphenylamide, bis-2,6-diphenylphenylamide, diallylamide, di-
propenylamide, N-methylanilide; N-ethylanilide; N-propylanilide; N-i-
propylanilide; N-
butyfanilide; N-i-butylanilide; N-amylanilide; N-i-amylanilide; N-
octylanilide; N-
cyclohexylanilide, silyl amides such as bis(trimethylsilyl)amide,
bis(triethylsilyl)amide,
bis(dimethylphenylsilyl)amide, bis(t-butyldimethylsilyl)amide, bis(t-
butyldiphenylsilyl)amide, phenyl(trimethylsilyl)amide,
phenyl(triethylsilyl)amide,
phenyl(trimethylsilyl)amide, methyl(trimethylsilyl)amide,
ethyt(trimethylsilyl)amide, n-
propyl(trimethylsilyl)amide, i-propyl(trimethylsilyl)amide,
cyclopropyl(trimethylsilyl)amide, n-butyl(trimethylsilyl)amide, i-
1o butyl(trimethylsilyl)amide, s-butyl(trimethylsilyl)amide, t-
butyl(trimethylsilyl)amide,
cyclobutyl(trimethylsilyl)amide, n-amyl(trimethylsilyl)amide, i-
amyl(trimethylsilyl)amide, s-arnyl(trimethylsilyl)amide, t-
amyl(trimethylsityl)amide,
neopentyl(trimethylsilyl)amide, cyclopentyl(trimethylsilyl)amide, n-
hexyl(trimethylsilyt)amide, cyclohexyl(trimethylsilyl)amide,
heptyl(trimethylsilyl)amide
and triethylsilyl trimethylsilylamide, heterocyclic amides such as the
conjugate bases
of pyrrole, pyrrolidine, piperidine, piperazine, indole, imidazole, azole,
thiazole,
purine, phthalimide, azacycloheptane, azacyclooctane, azacyclononane,
azacyclodecane, their substituted derivatives.
Examples of phosphides are dimethylphosphide, diethylphosphide,
2o dipropylphosphide, dibutylphosphide, diamylphosphide, dihexylphosphide,
dicyclohexylphosphide, diphenylphosphide, dibenzylphosphide, bis-2,6-
dimethylphenylphosphide, 2,6-di-i-propylphenylphosphide, 2,6-
diphenylphenylphosphide, the conjugate bases of cyclic phosphines such as
phosphacyclopentane, phosphacyclohexane, phosphacycloheptane,
phosphacyclooctane, phosphacyclononane, phosphacyclodecane.
Prefen-ed for use herein as the monoanionic, monodentate ligand Y are
fluoride, chloride, bromide, methoxide, ethoxide, n-propoxide, i-propoxide,
butoxide,
neopentoxide, benzyloxide, triiluoromethoxide, and trifluoroethoxide.
Mixtures of monoanionic, monodentate ligands Y may be used as the
3o monoanionic, monodentate ligand Y.
Mixtures of the above alkylating agents can also be utilized herein as the
alkylating agent.
The at least one aprotic solvent is a solvent which does not contain hydrogen
atoms which may be removed by any of the species dissolved in said solvent(s),
Substitute Page 12
.( s~ ~'3 ">2'~ ~gx'~" '-~a
'a~~= CA 02395710 2002-06-26 f]
,. ss~y~~~
r ~ M. t ; fir. r ~.c~~~-c.,~;,. c a ,~ ~ '~ t ~k ,-su?'~~a ~ -r
~~'~~d' os~a~.~~ 2~~~ ~aESC ~~~~; ~s~~ a
'~ ~'~uw~34'.~15~4.54~F~7.L~Nf6~~ y
~s,..~ucai:,i~,.a~~a.~earl:~.~ 'rs-.,.,:Ktr''~~.u .'"E.,.t~~.
DOCKET NO. 71133
under the conditions used, in the form of a proton. Examples of such solvents
include aliphatic, aromatic, and halogenated hydrocarbons, optionally
containing
other elements from Groups 13, 14, 15, or 16, inorganic solvents such as CS2,
POCI3, S02. Preferably the solvent will be an aliphatic, aromatic, or
halogenated
hydrocarbon. More preferably the solvent will be an aliphatic, aromatic, or
halogenated hydrocarbon containing from 4 to 40 carbon atoms, optionally
containing up to 10 heteroatoms. Most preferably, the solvent is pentane,
heptane,
hexane, benzene, toluene, dichlorornethane, or 1,2-dichloroethane.
Any inorganic or organic supports) may be used in the present invention.
lfl Examples of suitable inorganic supports are clays, metal oxides, metal
hydroxides,
metal halogenides or outer metal. salts, such as sulphates, carbonates,
phosphates,
nitrates and silicates. Further examples of inorganic supports suitable for
use herein
are compounds of metals from Groups 1 and 2 of the of the Periodic Table of
the
Elements, such as salts of sodium or potassium and oxides or salts of
magnesium or
is calcium, for instance the chlorides, sulphates, carbonates, phosphates or
silicates of
sodium, potassium, magnesium or calcium and the oxides or hydroxides of, for
instance, magnesium or calcium: Also suitable for use are inorganic oxides
such as
silica, titanic, alumina, zirconia, chromic, boron oxide, silanized silica,
silica
hydrogels, silica xerogels, silica aerogels, and mixed oxides such as tales,
2o silicalchromia, silicalchromia/titania, silicalalurnina, silica/titania,
silica/magnesia,
silicalmagnesia/titania, aluminum phosphate gels, silica co-gels. The
inorganic
oxides may contain carbonates, nitrates, sulfates and oxides such as Na2C03,
KZCO3, CaCO3, MgC03, NaZS04, AI2(S04)3, BaSO4, KNO3, Mg(NO3)Z, A1(N03)3,
Na20, K20 and Li20. Supports containing at least one component selected from
the
2s group consisting of MgCl2, Si02, AI20~ or mixtures thereof as a main
component are preferred.
Examples of suitable organic supports include polymers such as, for
example, functionalized polyethylene, functionalized polypropylene,
functionalized
interpolymers of ethylene and alpha-olefins, polystyrene, functionalized
polystyrene,
3o polyamides and polyesters.
Examples of suitable polymeric inorganic supports include carbosiloxanes,
phosphaanes, siloxanes, and hybrid materials such as polymer/silica hybrids.
Preferred for use herein are inorganic oxides such as silica, titanic,
alumina,
and mixed oxides such as tales, silica/chromia, silicalchromialtitania,
silicalalumina,
Substitute Page,l3
r.a" a~r'p
~~4
a~' rc - CA 02395710 2002-06-26
.r "~~ s,,wr~u nu
DOCKETN0.71133 CA 02395710 2002-06-26
silica/titania, and Group 2 halogenides such as magnesium chloride, magnesium
bromide, calcium chloride, and calcium bromide, and inorganic oxide supports
containing magnesium chloride deposited or preapitated on the surface of the
above-mentioned oxide.
Most preferred for use herein are inorganic oxide supports containing
magnesium chloride deposited or precipitated on the surface of the above-
mentioned
oxides such as magnesium chloride on silica.
In a further embodiment of the present invention it has been found that solid
procatalysts as described above can be produced comprising at least one
internal
1o electron donor. A solid procatalyst is prepared by reacting at least one
transition
metal compound of empirical formula MLxXøx, where M is titanium, zirconium, or
hafnium, each L is independently a monoanionic, bidentate ligand bound to M by
two
atoms selected from the group consisting of oxygen, sulfur, selenium,
tellurium,
nitrogen, phosphorus, arsenic, antimony, and bismuth, or mixtures thereof, X
is
15 fluoride, chloride, bromide, or iodide, and 0 < x 5 4, with at least one
alkylating agent
of the formula LxER~YmHP, where each L is independently a monoanionic,
bidentate
ligand bound to E by two atoms selected from the group consisting of oxygen,
sulfur,
selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, and bismuth, or
mixtures thereof, E is boron, aluminum, gallium, or indium, each R is
independently a
2o hydrocarbyl group, each Y is independently a monoanionic, monodentate
ligand, 0 <
x s 2, n > 0, m z 0, p z 0 and x + n + m + p = 3, and at least one internal
electron
donor in at least one aprotic solvent to provide a soluble species which is
subsequently contacted with a support. Contacting the soluble species with the
support includes depositing the soluble species on the support. The nau~ing
solid
25 procatalyst, with a cocatalyst, provides a catalyst system suitable for the
polymerization or interpolymerization of olefins.
The molar ratio of the internal electron donor to the transition metal
compound is preferably from about 0.1 to about 100. Preferably, the molar
ratio of
the internal electron donor to the transition metal compound is from about
0.25 to
3o about 15. More preferably, the molar ratio of the internal electron donor
to the
transition metal compound is from about 1 to about 5.
Examples of the internal electron donor are carboxylic acid esters,
anhydrides, acid halides, ethers, thioethers, aldehydes, ketones, imines,
amines,
amides, nitrites, isonitriles, cyanates, isocyanates, thiocyanates,
isothiocyanates,
Substitute Page 14
.r.~...v ;~E~~~~ 'll..J.~t~~).'~~ L
".r,~F.'"ia'u:~d~iawktiaxs'. i:ram '°~~"..aoat . ~.u~M:~.s
DOCKETN0.71133 CA 02395710 2002-06-26
thioesters, dithioesters, carbonic esters, hydrocarbyl carbamates, hydrocarbyl
thiocarbamates, hydrocarbyl dithiocarbamates, urethanes, phosphines, sutfldes,
phosphine oxides, phosphamides, sulfoxides, sulfones, sulfonamides,
organosilicon
compounds containing at least one oxygen atom, and nitrogen, phosphorus,
arsenic
or antimony compounds connected to an organic group through a carbon or oxygen
atom.
Examples of ethers useful herein as the internal electron donor are any
compounds containing at least one C-O-C ether linkage. Included within the
ether
compounds are compounds containing heteroatoms, which are atoms other than
io carbon, selected from Groups 13, 14, 1~, 16 and 17 of the Periodic Table of
Elements. Examples ethers are dialkyl ethers, diaryl ethers, dialkaryl ethers,
diaralkyl ethers, alkyl aryl ethers, alkyl alkaryl ethers, alkyl aralkyl
ethers, aryl alkaryl
ethers, aryl aralkyl ethers and alkaryl aralkyl ethers. Included within the
ethers are
compounds such as dimethyl ether, diethyl ether; dipropyl ether, diisopropyl
ether,
15 dibutyl ether, diisoamyl ether, di-tart-butyl ether, Biphenyl ether,
dibenzyl ether,
divinyl ether, butyl methyl ether, butyl ethyl ether, sec-butyl methyl ether,
tart-butyl
methyl ether; cyclopentyl methyl ether, cyclohexyl ethyl ether, tart-amyl
methyl ether,
sec butyl ethyl ether, chloromethyl methyl ether; trimethylsilylmethyl methyl
ether,
bis(trimethylsilylmethyl) ether, bis(2,2,2-trifluoroethyl) ether; methyl
phenyl ether;
2o ethylene oxide; propylene oxide; 1,2-epoxybutane; cyciopentene oxide;
epichtorohydrin; furan; 2,3-dihydrofuran; 2,5-dihydrofuran; tetrahydrofuran; 2-
methyltetrahydrofuran; 2,5-dimethyltetrahydrofuran; 2-methylfuran; 2,5-
dimethylfuran; tetrahydropyran; 1,2-epoxybut-3-ene; styrene oxide; 2-
ethylfuran;
oxazole; 1,3,4-oxadiazole; 3,4-dichloro-1,2-epoxybutane; 3,4-dibromo-1,2-
25 epoxybutane ; dimethoxymethane; 1,1-dimethoxyethane; 1,1,1-
trimethoxymethane;
1,1,1-trimethoxyethane; 1,1,2-trimethoxyethane; 1,1-cfimethoxypropane; 1,2-
dimethoxypropane; 2,2-dimethoxypropane; 1,3-dimethoxypropane; 1,1,3-
trimethoxypropane; 1,4-dimethoxybutane; 1,2-dimethoxybenzene; 1,3-
dimethoxybenzene; 1,4-dimethoxybenzene; ethylene glycol dimethyl ether; . . ,
_. " ._ . .
3o di(ethylene glycol) dimethyl ether; di(ethylene glycol) diethyl ether,
di(ethylene glycol)
dibutyi ether; di(ethylene glycol) tart-butyl methyl ether; tri(ethylene
glycol) dimethyl
ether; tri(ethylene glycol) diethyl ether, tetra(ethylene glycol) dimethyl
ether; 2,2-
diethyl-1,3-dimethoxypropane; 2-methyl-2-ethyl-1,3-dimethoxypropane; 2-
methoxyfuran; 3-methoxyfuran; 1,3-dioxolane; 2-methyl-1,3-dioxolane; 2,2-
dimethyl-
Substitute Page 15
-.e~;:~.-...:.w~d::a~K.u:...~.;.;:~.~ H~ wb;~:;.dlae...~,:'',.~ F..1;~ ~~~
DOC~E'TNO. T1133 CA 02395710 2002-06-26
1,3-dioxolane; 2-ethyl-2-methyl-1,3-dioxolane; 2,2-tetramethylene-1,3-
dioxolane; 2,2-
pentamethylene-1,3-dioxolane; 1,3-dioxane; 1,4-dioxane; 4-methyl-1,3-dioxane;
1,3,5-trioxane and 3,4-epoxytetrahydrofuran.
Preferred ether compounds for use herein as the internal electron donor are
tetrahydrofuran, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl
ether, dioctyl
ether, tart-butyl methyl ether, trirnethylene oxide, 1,2-dirnethoxyethane, 1,2-
dimethoxypropane, 1,3-dimethoxypropane, 1,2-dimethoxybutane, 1,3-
dimethoxybutane, 1,4-dimethoxybutane, and tetrahydropyran.
Examples of thioethers useful herein as the internal electron donor are any
to compounds containing at least one C-S-C thioether linkage. Included within
the
thioether compounds are compounds containing heteroatoms, which are atoms
other
than carbon, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table
of
Elements. Examples of thioethers are dialkyl thioethers, diaryl thioethers,
dialkaryl
thioethers, diaralkyl thioethers, alkyl aryl thioethers, alkyl alkaryl
thioethers, alkyl
i5 aralkyl thioethers, aryl alkaryl thioethers, aryl aralkyl thioethers and
alkaryl aralkyl
thioethers. Included are compounds such as dimethyl sulfide; diethyl sulfide;
dipropyl sulfide; diisopropyl sulfide; dibutyl sulfide; dipentyl sulfide;
dihexyl sulfide;
dioctyl sulfide; diisoamyl sulfide; di-tart-butyl sulfide; Biphenyl suede;
dibenzyl
sulfide; divinyl sulfide; dialfyl sulfide; dipropargyl sulfide; dicyclopropyl
sulfide;
2o dicyclopentyl sulfide; dicyclohexyl sulfide; allyl methyl sulfide; alfyl
ethyl sulfide; allyl
cyclohexyl sulfide; allyl phenyl sulfide; allyl benzyl sulfide; allyl 2-tolyl
sulfide; allyl 3-
tolyl sulfide; benzyl methyl sulfide; benzyl ethyl sulfide; benzyl isoamyl
sulfide; benzyl
chloromethyJ sulfide; benzyl cyclohexyl sulfide; benzyl phenyl sulfide; benzyl
1-
naphthyl sulfide; benzyl 2-naphthyl sulfide; butyl methyl sulfide; butyl ethyl
sulfide;
25 sec-butyl methyl sulfide; tent-butyl methyl sulfide; butyl cyclopentyl
sulfide; butyl 2-
chloroethyl sulfide; cyclopentyl methyl sulfide; cyclohexyl ethyl sulfide;
cyclohexyl
vinyl sulfide; tart-amyl methyl sulfide; seo-butyl ethyl sulfide; tart-butyl
ethyl sulfide;
tart-amyl ethyl sulfide; cyclododecyl methyl sulfide; bis(2-cyclopenten-1-yl)
sulfide; 1-
methylthio-1,3-cyctohexadiene; 1-methylthio-1,4-cyclohexadiene;. chloromethyl
.
3o methyl sulfide; chlorornethyl ethyl sulfide; bis(2-tolyl) sulfide;
trimethylsilylmethyl
methyl sulfide; trimethylene sulfide; thiophene; 2,3-dihydrothiophene; 2,5-
dihydrothiophene; tetrahydrothiophene; 2-methyltetrahydrothiophene; 2,5-
dimethyltetrahydrothiophene; 4,5-dihydro-2-methylthiophene; 2-methylthiophene;
2,5-dimethylthiophene; 3-bromothiophene; 2,3-benzothiophene;
Substitute Page 16
~,17
w.....~..,1...........>.~...~",.::~,.~ ~i~c.~=~=.~4,; "~'~' a i.~~.r
....~.a,~,~, r.
DOCKETN0.71133 CA 02395710 2002-06-26
2-methylbenzothiophene; dibenzothiophene; isobenzothiophene; 1,1-
bis(methylthio)ethane; 1,1,1-tris(methylthio)ethane; 1,1,2-
tris(methylthio)ethane; 1,1-
bis{methylthio)propane; 1,2-bis(methylthio)propane; 2,2-
bis(methylthio)propane; 1,3-
bis(methylthio)propane; 1,1,3-tris(methylthio)propane; 1,4-
bis{methylthio)butane; 1,2-
bis(methylthio)benzene; 1,3-bis(methylthio)benzene; 1,4-
bis(methylthio)benzene;
ethylene glycol dimethyi sulfide; ethylene glycol diethyl sulfide; ethylene
glycol divinyl
sulfide; ethylene glycol Biphenyl sulfide; ethylene glycol tart-butyl methyl
sulfide;
ethylene glycol tart-butyl ethyl sulfide; 2,5-bis(methylthio)thiophene; 2-
methylthiothiophene; 3-methylthiothiophene; 2-methylthiotetrahydropyran; 3-
methylthiotetrahydropyran; 1,3-dithiolane; 2-methyl-1,3-dithiolane; 2,2-
dirnethyl-1,3-
dithiolane; 2-ethyl-2-methyl-1,3-dithiolane; 2,2-tetramethylene-1,3-
dithiolane; 2,2-
pentamethylene-1,3-dithiolane; 2-vinyl-1,3-dithiolane; 2-chloromethyl-1,3-
dithiolane;
2-methylthio-1,3-dithiolane; 1,3-dithiane; 1,4-dithiane; 4-methyl-1,3-
dithiane; 1,3,5-
trithiane; 2-(2-ethylhexyl)-1,3-bis(methylthio)propane; 2-isopropyl-1,3-
bis(methylthio)propane; 2-butyl-1,3-bis(methylthio)propane; 2-sec-butyl-1,3-
bis(methylthio)propane; 2-tent-butyl-1,3-bis(methylthio)propane; 2-cyclohexyl-
1,3-
bis{methylthio)propane; 2-phenyl-1,3-bis(methy(thio)propane; 2-cumyl-1,3-
bis(methylthio)propane; 2-(2-phenylethyl~1,3-bis(methylthio)propane; 2-(2-
cyclohexylethyl~1,3-bis(methyfthio)propane; 2-(p-chlorophenyl~l,3-
2o bis(methylthio)propane; 2-(p-fluorophenyl)-1,3-bis(methylthio)propane; 2-
(diphenylmethyl)-1,3-bis(methylthio)propane; 2,2-dicyclohexyi-1,3-
bis(methylthio)propane; 2,2-diethyl-1,3-bis(methylthio)propane; 2,2-dipropyl-
'1,3-
bis(methylthio)propane; 2,2-diisopropyl-1,3-bis(methylthio)propane; 2,2-
dibutyl-1,3-
bis(methytthio)propane; 2,2-diisobutyl-1,3-bis(methylthio)propane; 2-methyl-2-
ethyl-
1,3-bis(methylthio)propane; 2-methyl-2-propyl-1,3-bis(methytthio)propane; 2-
methyl-2-butyl-1,3-bis(methylthio)propane; 2-methyl-2-benzyl-1,3-
bis(methylthio)propane; 2-methyl-2-methylcyclohexy!-1,3-
bis(methytthio)propane; 2-
isopropyl-2-isopentyl-1,3-bis(methylthio)propane; 2,2-bis(2-cyclohexylmethyl)-
1,3-
bis(methylthio)propane. .
3o Any amine may be used herein as the internal electron donor. Included are
amine compounds containing heteroatoms, which are atoms other than carbon,
selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements.
Examples of amines are primary, secondary and tertiary alkyl, aryl, alkaryl
and
aralkyt substituted amines. Examples of amines are ammonia; methylamine;
Substitute Page 17
u,1$
aLJ.I~V~ ~y'°,,i t'. ~t~' ~1w ~~~~U
~~,i""~inrsf:.:v.~~, '~rM:°41~'~~a~is~''wu.''n ~~ 4~w4.w~Gii:
DOCKETN0.71133 CA 02395710 2002-06-26
ethylamine; propylamine; isopropylamine; buiyfamine; isobutylamine;
arnylamine;
isoamylamine; ociylamine; cydohexylamine; aniline; dimethylamine;
diethylamine;
dipropyfamine; diisopropylamine; dibutylamine; diisobutylamine; diamyfamine;
diisoamylamine; dioctyfamine; dicyciohexylamine; trimethylamine;
triethyfamine;
tripropylamine; triisopropyfamine; tributylamine; triisobutyfamine;
triamylamine;
triisoamylamine; triodylamine; tricydohexylamine; N-methylaniline; N-
ethylaniline; N-
propylaniline; N-isopropyianiline; N-butylaniline; N-isobutylaniline; N-
amylaniline; N-
isoamylaniline; N-octyfaniline; N-cydohexylaniline; N,N-dimethylaniline; N,N-
diethylanitine; N,N-dipropylaniline; N,N-diisopropylaniiine; N,N-
dibutylaniline; N,N-
1o diisobutylaniline; N,N-diamylanlline; N,N-diisoamylaniline; N,N-
dioctylaniline; N,N-
dicydohexylaniline; azetidine; 1-methylazetidine; 1-ethylazetidine; 1-
propylazetidine;
1-isopropytazetidine; 1-butylazetidine; 1-isobutylazetidine; 1-amylazetidine;
1-
isoamylazetidine; pyrrolidine; N-methylimidazole; 1-methylpyrrolidine; 1-
ethylpyrrolidine; 1-propylpyrrolidine; 1-isopropylpyrrolidine; 1-
butylpyrrolidine; 1-
15 isobutylpyrrotidine; 1-amylpyn-olidine; 1-isoamylpyrrolidine; 1-
octyfpyrrolidine; 1-
cyclohexylpyrrolidine; 1-phenylpyrrolidine; piperidine; 1-methylpiperidine; 1-
ethylpiperidine; 1-propylpiperidine; 1-isopropylpiperidine; 1-butytpiperidine;
1-
isobutylpiperidine; 1-arnylpiperidine; 1-isoamylpiperidine; 1-octylpiperidine;
1-
cyciohexylpiperidine; 1-phenylpiperidine; piperazine; 1-methylpiperazine; 1-
2o ethytpiperazine; 1-propylpiperazine; 1-isopropylpiperazine; 1-
butylpiperazine; 1-
isobutylpiperazine; 1-amytpiperazine; 1-isoamylpiperazine; 1-octylpiperazine;
1-
cydohexylpiperazine; 1-phenylpiperazine; 1,4-dimethylpiperazine; 1,4-
diethylpiperazine; 1,4-dipropylpiperazine; 1,4-diisopropylpiperazine; 1,4-
dibutylpiperazine; 1,4-diisobutylpiperazine; 1,4-diamylpiperazine; 1,4-
25 diisoamylpiperazine; 1,4-dioctylpiperazine; 1,4-dicyclohexylpiperazine; 1,4-
diphenylpiperazine; pyridine; 2-methyl pyridine; 4-methyl pyridine;
hexamethyldisilazane; morpholine; N-methylmorpholine.
Examples of carboxylic add esters useful herein as the internal electron
donor are any carboxylic acid ester compounds containing at least one C(=O}-0-
C
3o ester linkage. Examples of carboxylic acid esters are saturated or
unsaturated
aliphatic, alicydic, or aromatic compounds containing an ester linkage.
Included
within the carboxylic acid esters are compounds containing heteroatorns, which
are
atoms other than carbon, selected from Groups 13, 14, 15, 16 and 17 of the
Periodic
Table of Elements. Further examples are carboxylic acid esters such as methyl
Substitute Page 18
1~t
~'s"'",~e''~~.~,"~-3~ .u~rv v ~ ~ rt4 fi:
DOCKETN0.71133 CA 02395710 2002-06-26
formats; methyl acetate; ethyl acetate; vinyl acetate; propyl acetate; butyl
acetate;
isopropyl acetate; isobutyl acetate; ociyt acetate; cyclohexyl acetate; ethyl
propionate; ethyl valerate; methyl chloroacetate; ethyl dichloroacetate,
methyl
methacrylate; ethyl crotonate; ethyl pivalate; methyl benzoate; ethyl
benzoate; propyl
benzoate; butyl benzoate; isobutyl benzoate; isopropyl benzoate; octy!
benzoate;
cyclohexyl benzoate; phenyl benzoate; benzyl benzoate; methyl 2-
methylbenzoate;
ethyl 2-methylbenzoate; propyl 2-methylbenzoate; isopropyl 2-methylbenzoate;
butyl
2-methylbenzoate; isobutyl 2-methylbenzoate; oetyl 2-methylbenzoate;
cyclohexyl 2-
methylbenzoate; phenyl 2-methylbenzoate; benzyl 2-methylbenzoate; methyl 3-
io methylbenzoate; ethyl 3-methylbenzoate; propyl 3-methylbenzoate; isopropyl
3-
methylbenzoate; butyl 3-methylbenzoate; isobutyl 3-methylbenzoate; octyl 3-
methylbenzoate; cyclohexyl 3-methylbenzoate; phenyl 3-methylbenzoate; benzyl 3-
methylbenzoate; methyl 4-methylbenzoate; ethyl 4-methylbenzoate; propyl 4-
methylbenzoate; isopropyl 4-methylbenzoate; bufyl 4-methylbenzoate; isobutyl
.4-
15 methylbenzoate; octyl 4-methylbenzoate; cyclohexyl 4-methylbenzoate; phenyl
4-
methylbenzoate; benzyl ~4-methylbenzoate; methyl o-chlorobenzoate; ethyl o-
chlorobenzoate; propyl o-chforobenzoate; isopropyl o-chiorobenzoate; butyl o-
chlorobenzoate; isobutyl o-chlorobenzoate; amyl o-chlorobenzoate; isoamyl o-
chiorobenzoate; octyl o-chlorobenzoate; cyclohexyl o-chlorobenzoate; phenyl o-
2o chlorobenzoate; benzyl o-chlorobenzoate; methyl m-chlorobenzoate; ethyl m-
chiorobenzoate; propyl m-chiorobenzoate; isopropyl m-chforobenzoate; butyl m-
chlorobenzoate; isobutyl m-chlorobenzoate; amyl m-chlorobenzoate; isoamyf m-
chlorobenzoate; octyl m-chlorobenzoate; cydohexyl m-chlorobenzoate; phenyl m-
chlorobenzoate; benzyl m-chlorobenzoate; methyl p-chlorobenzoate; ethyl p-
25 chlorobenzoate; propyl p-chlorobenzoate; isopropyl p-chlorobenzoate; butyl
p-chiorobenzoate; isobutyi p-chlorobenzoate; amyl p-chlorobenzoate; isoarnyl p-
chlorobenzoate; octyl p-chforobenzoate; cyclohexyl p-chiorobenzoate; phenyl p-
chlorobenzoate; benzyl p-chlorobenzoate; dimethyl maleate; dimethyl phthalate;
diethyl phthalate; dipropyl phthalate; dibutyl phthalate; diisobutyl
phthalate; methyl
3o ethyl phthalate; methyl propyl phthalate; methyl butyl phthalate; methyl
isobutyl
phthalate; ethyl propyl phthalate; ethyl butyl phthalate; ethyl isobutyl
phthalate; propyl
butyl phthalate; propyl isobutyl phthalate; dimethyl terephthalate; diethyl
terephthalate; dipropyl terephthalate; dibutyl terephthalate; diisobutyl
terephthalate;
methyl ethyl terephthalate; methyl propyl terephthalate; methyl butyl
terephthalate;
Substitute Page 19
aV: a;.n,.''~
,~~ i
n.
3ii~..i ::.; ~3a
~.~- ~..~.~.. , " ,, uu.~u iul~,~V
DOCKETNO.71133 CA 02395710 2002-06-26
.' methyl isobutyl terephthalate; ethyl propyl terephthalate; ethyl butyl
terephthalate;
ethyl isobutyl terephthalate; propyl butyl terephthalate; propyl isobutyl
terephthatate;
dimethyl isophthalate; diethyl isophthalate; dipropyl isophthalate; dibutyt
isophthalate;
diisobutyl isophthatate; methyl ethyl isophthalate; methyl propyl
isophthalate; methyl
butyl isophthalate; methyl isobutyl isophthalate; ethyl propyl isophthalate;
ethyl butyl
isophthalate; ethyl isobutyl isophthalate; propyi butyl isophthalate; propyl
isobutyl
isophthalate, cellulose acetate, cellulose butyrate, mixed esters of
cellulose.
Examples of thioesters useful herein as the internal electron donor are
compounds containing at least one C{=Oj-S-C thioester linkage. Examples are
1o saturated or unsaturated aliphatic, alicyclic, or aromafic compounds
containing a
thioester linkage. Included within the thioesters are compounds containing
heteroatoms, which are atoms other than carbon, selected from Groups 13, 14,
15,
16 and 17 of the Periodic Table of Elements. Examples of thioesters are methyl
thiolacetate; ethyl thiolacetate; propyl thiolacetate; isopropyl thiolacetate;
butyl
1s thiolacetate; isobutyl thiolacetate; amyl thiolacetate; isoamyl
thiolacetate; octyl
thiolacetate; cyclohexyl thiolacetate; phenyl thiolacetate; 2-chloroethyl
thiolacetate;
3-chloropropy! thiolacetate; methyl thiobenzoate; ethyl thiobenzoate; propyl
thiobenzoate; isopropyl thiobenzoate; butyl thiobenzoate; isobutyl
thiobenzoate; amyl
thiobenzoate; isoamyl thiobenzoate; octyl thiobenzoate; cyclohexyl
thiobenzoate;
2o phenyl thiobenzoate; 2-chloroethyl thiobenzoate; 3-chloropropyl
thiobenzoate.
Examples of amides useful herein as the infernal electron donor are
compounds containing at least one C{=O)-N amide linkage. Examples are
saturated
or unsaturated aliphatic, alicyclic, or aromatic compounds containing an amide
linkage. Included within the amides are compounds containing heteroatoms,
which
2s are atoms other than carbon, selected from Groups 13, 14, 15, 16 and 1 T of
the
Periodic Table of Elements. Examples amides are formamide; acetamide;
propionamide; isobutyramide; trimethylacetamide; hexanoamide; octadecanamide;
cyclohexanecarboxamide; 1-adamantanecarboxamide; acrylamide; methacrylamide;
2-fluoroacetamide; 2-chloroacetamide; 2-bromoacetamide; 2,2-
dichloroacetarnide;
30 2,2,2-trifluoroacetamide; 2,2,2-trichloroacetamide; 2-chloropropionamide;
benzamide; N-methylformamide; N-ethylformamide; N-propylformamide; N-
butylformamide; N-isobutylformamide; N-amylformamide; N-cyclohexylforrnamide;
Substitute Page 20
~2~':i
F~,",;,.
wyr ,racy ,.~ ~ ~'~7r"
x~
DOCKETN0.71133 CA 02395710 2002-06-26
formanilide; N-methylacetamide; N-ethylacetamide; N-propylacetamide; N-
butylacetamide; N-isobutylacetamide; N-amylacetamide; N-cycfohexylacetamide;
acetanilide; N-methylpropionamide; N-ethylpropionamide; N-propyipropionamide;
N-
butylpropionamide; N-isobutylpropionarnide; N-amyipropionamide; N-
cyclohexyipropionamide; N-phenylpropionamide; N-methylisobutyramide; N-
methyltrimethylacetamide; N-methylhexanoamide; N-methyloctadecanamide; N-
methylacrylamide; N-methylmethacrylamide; N-methyl-2 fiuoroacetamide; N-
rnethyl-
2-chloroacetamide; N-methyl-2-bromoacetamide; N-methyl-2,2-dichloroacetarnide;
N-methyt-2,2,2-trifiuoroacetamide; N-methyl-2,2,2-trichioroacetamide; N-methyl-
2-
to chloropropionamide; N,N-dimethylfonnamide; N,N-diethylformamide; N,N-
diisopropylformamide; N,N-dibutyiformamide; N-methylfomianilide; N,N-
dimethylacetamide; N,N-diethylacetamide; N,N-diisopropylacetamide; N,N-
dibutylacetamide; N-methylacetanilide; N,N-dimethylpropionamide; N,N-
diethylpropionamide; N,N-diisopropylpropionamide; N,N-dibutyipropionamide; N,N-
dirnethylisobutyramide; N,N-dimethyltrimethylacetamide; N,N-
dimethylhexanoamide;
N,N-dimethyloctadecanamide; N,N-dimethylacrylamide; N,N-
dimethylmethacrylamide; N,N-dimethyl-2-fluoroacetamide; N,N-dimethyl-2-
chloroacetamide; N,N-dimethyl-2-bromoacetamide; N,N-dimethyi-2,2-
dichloroacetamide; N,N-dimethyl-2,2,2-trifluoroacetamide; N,N-diethyl-2,2,2-
2o trifluoroacetamide; N,N-diisopropyl-2,2,2-trifluoraacetamide; N,N-dibutyl-
2,2,2-
trifluoroacetamide; N,N-dimethyl-2,2,2-trichloroacetamide; N,N-diethyl-2,2,2-
trichloroacetamide; N,N-diisopropyl-2,2,2-trichioroacetamide; N,N-dibutyl-
2,2,2-
trichloroacetamide; N,N-dimethyl-2-chloropropionamide; 1-acetylazetidine; 1-
acetylpyrrolidine; 1-acetylpiperidine; 1-acetyfpiperazine; 1-acetylpiperazine;
1,4-
2s diacetylpiperazine.
Examples of anhydrides useful herein as the internal electron donor are
compounds containing at least one C(=O)-O-C(=O) anhydride Linkage. Examples
are
saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing an
anhydride linkage. Included within the anhydrides are compounds containing
30 heteroatoms, which are atoms other than carbon, selected from Groups 13,
14, 15,
16 and 17 ofithe Periodic Table of Elements. Examples of anhydrides are acetic
anhydride; propionic anhydride; butyric anhydride; isobutyric anhydride;
valeric
anhydride; trimethyfacetic anhydride; hexanoic anhydride; heptanoic anhydride;
decanoic anhydride; lauric anhydride; myristic anhydride; palmitic anhydride;
stearic
Substitute Page 21
~~P
IJ:1~IJVr ' H~. ~~~~t.
,~~.. .~~.°.-~'t~ ~;:~sraw..~':,,, ~w.~~ ~U~U J IJ.U l
t7r~~ ~.::v..
DOCKETN0.7I133 CA 02395710 2002-06-26
anhydride; docosanoic anhydride; crotonic anhydride; methacrylic anhydride;
oleic
anhydride; Iinoleic anhydride; chloroacetic anhydride; iodoacetic anhydride;
dichloroacetic anhydride; trifluoroacetic anhydride; chlorodifluoroacetic
anhydride;
trichloroacetic anhydride; pentafluoropropionic anhydride; heptafluorobutyric
anhydride; succinic anhydride; methylsuccinic anhydride; 2,2-dimethylsuccinic
anhydride; itaconic anhydride; rnaleic anhydride; glutaric anhydride;
diglycolic
anhydride; benzoic anhydride; phenylsuccinic anhydride; phenyfmaleic
anhydride;
homophthalic anhydride; isatoic anhydride; phthalic anhydride;
tetrafluorophthalic
anhydride; tetrabromophthalic anhydride, mixed anhydrides.
Examples of acid halides useful herein as the internal electron donor are
compounds containing at (east one -C(=OrX acid halide group where X is a
halogen.
Examples are saturated or unsaturated aliphatic, alicyclic, or aromatic
compounds
containing an acid halide group. Included within the acid halides are
compounds
containing heteroatorns, which are atoms other than carbon, selected from
Groups
is 13, 14, 15, 16 and 1 T of the Periodic Table of Elements. Examples of acid
halides
are acetyl chloride; acetyl bromide; chloroacetyl chloride; dichloroacetyl
chloride;
trichloroacetyl chloride; trifluoroacetyl chloride; tribromoacetyl chloride;
propionyl
chloride; propionyl bromide; butyryl chloride; isobutyryl chloride;
trimethylacetyl
chloride; 3-cyclopentylpropionyl chloride; 2-chloropropionyl chloride; 3-
2o chloropropionyl chloride; tert-butylacetyl chloride; isovaleryl chloride;
hexanoyl
chloride; heptanoyl chloride; decanoyl chloride; lauroyl chloride; myristoyl
chloride;
palmitoyl chloride; stearoyl chloride; oleoyl chloride; cyclopentanecarbonyl
chloride;
oxalyl chloride; malonyl dichloride; succinyl chloride glutaryl dichloride;
adipoyl
chloride; pimeloyl chloride; suberoy) chloride; azelaoyl chloride; sebacoyl
chloride;
25 dodecanedioyl dichloride; methoxyacetyl chloride; acetoxyacetyl chloride.
Examples of aldehydes useful herein as the internal electron donor are
compounds containing at least one C-C(=OrH aldehyde group. Examples are
saturated or unsaturated aliphatic, alicydic, or aromatic compounds containing
an
3o aldehyde group. Included within the aldehydes are compounds containing
heteroatoms; which are atoms other than carbon, selected from Groups 13, 14,
15,
16 and 17 of the Periodic Table of Elements. Examples of aldehydes are
formaldehyde; acetaldehyde; propionaldehyde; isobutyraldehyde;
trimethylacetaldehyde; butyraldehyde; 2-methylbutyraldehyde; valeraldehyde;
Substitute Page 22
~3. -~~ ~~:
~~ ~ ~~n 1
~:w.
u. ~u .,vrv wr..~ rtys.4i~3~ #~,.~~.w~..5~i c,~Lu.~.''--',~v,werL,:.,~:s.
a~...~W:~"a~.a~~,~saa --F ".~
DOCKETN0.71133 CA 02395710 2002-06-26
isovaleraldehyde; hexanal; 2-ethylhexanal; heptaldehyde; decyi aldehyde;
crotonaldehyde; acrolein; methacrolein; 2-ethylacrolein; chloroacetaldehyde;
iodoacetaldehyde; dichloroacetaldehyde; trifluoroacetaldehyde;
chlorodifluoroacetaldehyde; trichloroacetaldehyde; pentafluoropropionaldehyde;
heptafluorobutyraldehyde; phenylacetaldehyde; benzaldehyde; o-tolualdehyde; m-
tofualdehyde; p-tolualdehyde; trans-annamaldehyde; traps-2-
nitrocinnamaldehyde;
2-bromobenzaldehyde; 2-chlorobenzaldehyde; 3-chlorobenzaldehyde; 4-
chlorobenzaldehyde.
Examples of ketones useful herein as the internal electron donor are
io compounds containing at least one C-C(=O)-C ketone linkage. Examples are
saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing a
ketone linkage. Included wiifiin the ketones are compounds containing
heteroatorns,
which are atoms other than carbon, selected from Groups 13, 14, 15, 16 and 17
of
the Periodic Table of Elements. Examples of ketones are acetone; 2-butanone; 3-
methyl-2-butanone; pinacolone; 2-pentanone; 3-pentanone; 3-methyl-2-pentanone;
4-methyl-2-pentanone; 2-methyl-3-pentanone; 4,4-dimethyl-2-pentanone; 2,4.-
dimethyl-3-pentanone; 2,2,4,4-tetramethyl-3-pentanone; 2-hexanone; 3-hexanone;
5-
methyl-2-hexanone; 2-methyl-3-hexanone; 2-heptanone; 3-heptanone; 4-heptanone;
2-methyl-3-heptanone; 5-methyl-3-heptanone; 2,6-dimethyl-4-heptanone; 2-
octanone; 3-octanone; 4-octanone; acetophenone; benzophenone; mesityl oxide;
hexafluoroacetone; perttuoro-2-butanone; 1,1,1-trichloroacetone.
Examples of nitrites useful herein as the internal electron donor are
compounds containing at least one C-C N nitrite group. Examples are saturated
or
unsaturated aliphatic, alicyciic, or aromatic compounds containing a nitrite
group.
2s Included within the nitrites are compounds containing heteroatoms, which
are atoms
other than carbon, selected from Groups 13, 14, 15, 16 and 17 of the Periodic
Table of Elements. Examples of nitrites are acetonitrile; propionitrile;
isopropionitrile;
butyronitrile; isobutyronitrile; valeronitrile; isovaleronitrile;
trimethylacetonitrile;
hexanenitrile; heptanenitrile; heptyl cyanide; ociyl cyanide; undecanenitrile;
3o malononitrile; succinonitrile; glutaronitrile; adiponitrile; sebaconitrile;
ally) cyanide;
acrylonitrile; crotononitrile; methacrylonitrile; fumaronitrile;
tetracyanoethylene;
cyclopentanecarbonitrile; cyclohexanecarbonitrile; dichloroacetonitrile;
fluoroacetonitrile; trichloroacetonitrile; benzonitrile; benzyl cyanide; 2-
methylbenzyl
Substitute Page 23
~aa:
29'''4'~~'~2(~.~~1:-
,C~i~~~'~ a ~, v y~ ~,~~~i H~',~ t.IJi~,~~~'~' ~J~
.i~~:i'.~,. ,:~.'.","'y ..
DOCKETN0.71133 CA 02395710 2002-06-26
cyanide; 2-chlorobenzonitrile; 3-chlorobenzonifile; 4-chlorobenzonitrile; o-
tolunitrile;
rn-tolunitrile; p-tolunitrile.
Examples of isonitriles or isocyanides useful herein as the internal electron
donor are compounds containing at least one C-N C isocyanide group. Examples
are saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing a
isocyanide group. Included within the isocyanides are compounds containing
heteroatoms, which are atoms other than carbon, selected from Groups 13, 14,
15,
16 and 17 of the Periodic Table of Elements. Examples of isacyanides are
methyl
isocyanide; ethyl isocyanide; propyl isocyanide; isopropyl isocyanide; n-butyl
1o isocyanide; t buiyl isocyanide; s-butyl isocyanide; pentyl cyanide; hexyl
isocyanide;
heptyl isocyanide; octyl isocyanide; nonyl isocyanide; decyl isocyanide;
undecane
isocyanide; benzyl isocyanide; 2-methylbenzyl isocyanide; 2-chlorobenzo
isocyanide;
3-chlorobenzo isocyanide; 4-chlorobenzo isocyanide; o-toluyl isocyanide; m
toluyl
isocyanide; p-toiuyl isocyanide; phenyl isocyanide dichloride; 1,4-phenyfene
is diisocyanide.
Examples of thiocyanates useful herein as the internal electron donor are
compounds containing at least one GSCN thiocyanate group. Examples are
saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing a
thiacyanate group. Included within the thiocyanates are compounds containing
2o heteroatoms, which are atoms other than carbon, selected from Groups 13,
14, 15,
16 and 17 of the Periodic Table of Elements. Examples of thiocyanates are
methyl
thiocyanate; ethyl thiocyanate; propyl thiocyanate; isopropyl thiocyanate; n-
butyl
thiocyanate; t-butyl thiocyanate; s-butyl thiocyanate; pentyl thiocyanate;
hexyl
thiocyanate; heptyl thiocyanate; octyi thiocyanate; nonyl thiocyanate; decyl
25 thiocyanate; undecane thiocyanate; benzyl thiocyanate; phenyl thiocyanate;
4'
bromophenyacyl thiocyanate; 2-methylbenzyl thiocyanate; 2-chlorobenzo
thiocyanate; 3-chlorobenzo thiocyanate; 4-chlorobenzo thiocyanate; o-toluyl
thiocyanate; m-toluyl thiocyanate; p-toluyl thiocyanate.
Examples of isothiocyanates useful herein as the internal electron donor are
3o compounds containing at least one C-NCS isothiocyanate group. Examples are
saturated or unsaturated aliphatic; alicyclic, or aromatic compounds
containing a
isothiocyanate group. Included within the isothiocyanates are compounds
containing heteroatoms, which are atoms other than carbon, selected from
Groups
13, 14, 15, 16 and 17 of the Periodic Table of Elements. Examples of
Substitute Page 24
F~
4
";
~v~au'y~~,
wrw..vw ~ y r. tlJU hLsl
~k~:' 'k r~r .,.:,.,uS,vxh- a . ...,,;:1 ,.. ' ~8;~".i:w~s0.i~'.'~s~5. a:t,.,
DOCKETN0.71133 CA 02395710 2002-06-26
isothiocyanates are methyl isothiocyanate; ethyl isothiocyanate; propyl
isothiocyanate; isopropyl isothiocyanate; n-butyl isothiocyanate; t-butyl
isothiocyanate; s-butyl isothiocyanate; pentyl isothiocyanate; hexyl
isothiocyanate;
heptyl isothiocyanate; octyl isothiocyanate; nonyl isothiocyanate; decyl
isothiocyanate; undecane isothiocyanate; phenyl isothiocyanate; benzyl
isothiocyanate; phenethyl isothiocyanate; o-tolyl isothiocyanate; 2
fluorophenyl
isothiocyanate; 3-fluorophenyl isothiocyanate; 4-fluorophenyl isothiocyanate;
2-
nitrophenyl isothiocyanate; 3-nit<-ophenyl isothiocyanate; 4-nitrophenyl
isothiocyanate; 2-chlorophenyl isothiocyanate; 2-bromophenyl isothiocyanate; 3-
1o chlorophenyl isothiocyanate; 3-bromophenyl isothiocyanate; 4-chlorophenyl
isothiocyanate; 2,4-dichlorophenyl isothiocyanate; R-(+}-alpha-methylbenzyl
isothiocyanate; S-(-alpha-methylbenzyl isothiocyanate; 3-isoprenyl-alpha,alpha-
dimethylbenzyl isothiocyanate; traps-2-phenylcyclopropyl isothiocyanate; 1,3-
bis(isocyanatomethyl)-benzene; 1,3-bis(1-isocyanato-1-methylethyl)benzene; 2-
i5 ethylphenyl isothiocyanate; benzoyl isothiocyanate; 1-naphthyl
isothiocyanate;
benzoyl isothiocyanate; 4-bromophenyl isothiocyanate; 2-methoxyphenyl
isothiocyanate; m-tolyl isothiocyanate; alpha, alpha, alpha-trlfluoro-m-tolyl
isothiocyanate; 3 fluorophenyl isothiocyanate; 3-chlorophenyl isothiocyanate;
3-
bromophenyl isothiocyanate; 1,4-phenylene diisothiocyanate; 1-isothlocyanato-4-
20 (traps-4-propylcyclohexyl}benzene; 1-(traps-4-hexylcyclohexyl)-4-
isothiocyanatobenzene; 1-isothiocyanato-4-(traps-4-octylcyclohexyl} benzene; 2-
methylbenzyl isothiocyanate; 2-chlorobenzo isothiocyanate; 3-chlorobenzo
isothiocyanate; 4-chlorobenzo isothiocyanate; m-toluyl isothiocyanate; p-
toluyl
isothiocyanate.
25 Examples of sulfoxides useful herein as the internal electron donor are
compounds containing at feast one GS(=O~C sulfoxo group. Examples are
saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing a sulfoxo group. Included within the sulfoxides are compounds
. ~ntaining heteroatoms, which are atoms other than carbon, selected from
Groups
30 13, 14, 15, 16 and 17 of the Periodic Table of Elements. Examples of
sulfoxides are
methyl sulfoxide; ethylsulfoxide; propylsulfoxide; butyl sulfoxide; pentyl
sulfoxide;
hexyl sulfoxide; heptyl sulfoxide; octyl sulfoxide; nonyl sulfoxide; decyl
sulfoxide;
phenyl sulfoxide; p-tolyl sulfoxide; m-tolyl sulfoxide; o-tolyl sulfoxide;
methyl phenyl
sulfoxide; (R} - (+) - methyl p-tolyl sulfoxide; (S) - (-) - methyl phenyl
sulfoxide;
Substitute Page 25
i ~ ~d~ ~ ~T F. ;,
4 .y~,
....r_F~ ~ ~~,46L~ t~ T~~~ ;
.~.°_.1'Ta,Sv~l.? n..~,."'+_'."-:,"u.,,
DOCKET NO. 71133
phenyl vinyl sulfoxide; 4-chlorophenyl sulfoxide; methyl
(phenyfsulfinyl)acetate;
benzyl sulfoxide; tetramethylene sulfoxide; methyl methylsulflnylmethyl
sulfide; dl-
methionine sulfoxide; dl-methionine sulfoximine.
Examples of sulfones useful herein as the internal electron donor are
compounds containing at least one C-S(=O)rC sulfone group. Examples are
saturated or unsaturated aliphatic, alicyclic, or aromatic compounds
containing a
sulfone group. Included within the sulfones are compounds containing
heteroatoms,
which are atoms other than carbon, selected from Groups 13, 14, 15, 16 and 17
of
the Periodic Table of Elements. Examples of sulfones are methyl sulfone; ethyl
to sulfone; propyl sulfone; butyl sulfone; methyl vinyl sulfone; ethyl vinyl
sulfone; divinyl
sulfone; phenyl vinyl sulfone; allyl phenyl sulfone; cis-1,2-
bis(phenylsulfonyl)ethylene; 2-(phenylsulfonyl)tetrahydropyran; chloromethyl
phenyl
sulfone; bromomethyl phenyl sulfone; phenyl tribromomethyl sulfone; 2-
chloroethyl
phenyl sulfone; methylthiomethyl phenyl sulfone; (phenylsulfonyl)acetonitrile;
15 chloromethyl p-tolyl sulfone; N, N-bis(p-tolylsulfonylmethyl~ethylamine;
methylthiomethyl p-tolyl sulfone; 2-(phenylsulfonyl)acetophenone; methyl
phenylsutfonylacetate; 4-fluorophenyl methyl sulfone; 4-chlorophenyl 2-chloro-
1,1,2-
trifluoroethyl sulfone; tosylmethyl isocyanide; phenyl sulfone; benzyl
sulfone; phenyl
traps-styryl sulfone; 1-methyl-2-((phenylsulfonyl)methyl~benzene;l-bromomethyl-
2-
20 ((phenylsulfonyl~methyl)benzene; p-tolyl sulfone;
bis(phenylsulfonyl)methane; 4-
chlorophenyl phenyl sulfone; 4-fluorophenyl sulfone; 4-chlorophenyl sulfone;
4,4'-
sulfonylbis(methyl benzoate); 9-oxo-9H-thioxanthene-3-carbonitrile 10,10-
dioxide;
tetramethylene sulfone; 3-methylsulfolane; 2,4-dimethylsulfolane; traps-3,4-
dichlorotetrahydrothiophene 1,1-dioxide; traps-3,4-dibromotetrahydrothiophene
1,1-
25 dioxide; 3,4-epoxytetrahydrothiophene-1,1-dioxide; butadiene sulfone; 3-
ethyl-2,5-
dihydrothiophene-1,1-dioxide.
Examples of phosphorous compounds useful herein as the internal electron
donor are saturated or unsaturated aliphatic, alicyclic, or aromatic
phosphorous
compounds having 2 to 50 carbon atoms containing at least one phosphorous
atom.
3o Included within the phosphorous compounds are compounds containing
heteroatoms, which are atoms other than carbon, selected from Groups 13, 14,
15,
16 and 17 of the Periodic Table of Elements. Examples of phosphorous compounds
are trimethylphosphine; triethylphosphine; trimethyl phosphite; methyl
phosphite;
hexamethylphosphorus triamide; hexamethylphosphoramide; tripiperidinophosphine
Substitute Page 26
~f~~~, ,~
CA 02395710 2002-06-26
~~w, x ~.
DOCKET NO. 71133
oxide; triphenylphosphine; tri-p-tolylphosphine; tri-m-tolylphosphine; tri-o-
tolylphosphine; methyldiphenylphosphine; ethyldiphenylphosphine;
isopropyldiphenylphosphine; allyldiphenylphosphine;
cyclohexyldiphenyiphosphine;
benzyldiphenylphosphine; di-tert-butyl dimethylphosphoramidite; di-tert-butyl
diethylphosphoramidite; di-tert-butyl diisopropylphosphoramidite; diallyl
diisopropylphosphoramidite.
Examples of organosilicon compounds useful herein as the internal electron
donor are saturated or unsaturated aliphatic, alicyclic, or aromatic
organosilicon
compounds having 2 to 50 carbon atoms containing at least one oxygen atom.
1o Included within the organosilicon compounds are compounds containing
heteroatoms, which are atoms other than carbon, selected from Groups 13, 14,
15,
16 and 17 of the Periodic Table of Elements. Examples of organosilicon
compounds
are tetramethyl orthosilicate; tetraethyl orthosilicate; tetrapropyl
orthosilicate;
tetrabutyl orthosilicate; trichloromethoxysilane; trichloroethoxysilane;
is trichloropropoxysilane; trichloroisopropoxysilane; trichlorobutoxysilane;
trichloroisobutoxysilane; dichlorodimethoxysilane; dichlorodiethoxysilane;
dichlorodipropoxysilane; dichlorodiisopropoxysilane; dichlorodibutoxysilane;
dichlorodiisobutoxysilane; chlorotrimethoxysilane; chlorotriethoxysilane;
chlorotripropoxysilane; chlorotriisopropoxysilane; chlorotributoxysilane;
2o chlorotriisobutoxysilane; dimethylmethoxysilane; diethylmethoxysilane;
dipropylmethoxysilane; diisopropylmethoxysilane; dibutylmethoxysilane;
diisobutyimethoxysilane; dipentylmethoxysilane; dicyclopentylmethoxysilane;
dihexylmethoxysilane; dicyclohexylmethoxysilane; diphenylmethoxysilane;
dimethylethoxysilane; diethylethoxysilane; dipropylethoxysilane;
2s diisopropylethoxysilane; dibutylethoxysilane; diisobutylethoxysilane;
dipentylethoxysilane; dicyclopentylethoxysilane; dihexylethoxysilane;
dicyclohexylethoxysilane; diphenylethoxysilane; trimethylmethoxysilane;
triethylmethoxysilane; tripropylmethoxysilane; triisopropylmethoxysilane;
tributylmethoxysilane; triisobutylmethoxysitane; tripentylmethoxysilane;
3o tricyclopentylmethoxysilane; trihexylmethoxysilane;
tricyclohexylmethoxysilane;
triphenylmethoxysilane; trirnethylethoxysilane; triethylethoxysilane;
tripropylethoxysilane; triisopropylethoxysilane; tributylethoxysilane;
triisobutylethoxysilane; tripentylethoxysilane; tricyGopentylethoxysilane;
trihexylethoxysilane; tricyclohexylethoxysilane; triphenylethoxysilane;
Substitute Page 27
CA 02395710 2002-06-26
DOCKET NO. 71133
dimethyldimethoxysilane; diethyldimethoxysilane; dipropyldimethoxysilane;
diisopropyldimethoxysilane; dibutyldimethoxysilane; diisobutyldimethoxysilane;
dipentyldimethoxysilane; dicyclopentyldimethoxysilane; dihexyldimethoxysilane;
dicyclohexyldimethoxysilane; diphenyldimethoxysilane; dimethyldiethoxysitane;
diethyldiethoxysilane; dipropyldiethoxysilane; diisopropyldiethoxysilane;
dibutyldiethoxysilane; diisobutyldiethoxysilane; dipentyldiethoxysilane;
dicyclopentyldiethoxysilane; dihexyldiethoxystlane;
dicyclohexyldiethoxysilane;
diphenyldiethoxysilane;cyclopentylmethyldimethoxysilane;
cyclopentylethyldimethoxysilane; cyclopentylpropyldimethoxysilane;
io cyclopentylmethyldiethoxysilane; cyclopentylethyldiethoxysilane;
cyclopentylpropyldiethoxysilane; cyclohexylmethyldimethoxysilane;
cyclohexylethyldimethoxysilane; cyclohexylpropyldimethoxysilane;
cyclohexylmethyldiethoxysilane; cyclohexylethyldiethoxysilane;
cyclohexylpropyldiethoxysilane; methyltrimethoxysilane; ethyltrimethoxysilane;
vinyltrimethoxysilane; propyltrimethoxysilane; isopropyltrimethoxysilane;
butyltrimethoxysilane; isobutyltrimethoxysilane; tert-butyltrimethoxysilane;
phenyltrimethoxysilane; norbomanetrimethoxysilane; methyltriethoxysilane;
ethyltriethoxysilane; vinyltriethoxysilane; propyltriethoxysilane;
isopropyltriethoxysilane; butyltriethoxysilane; isobutyltriethoxysilane; tert-
butyltriethoxysilane; phenyltriethoxysilane; norbomanetriethoxysilane; 2,3-
dimethyl-
2-(trimethoxysilyl)butane; 2,3-dimethyl-2-(triethoxysilyl)butane; 2,3-dimethyl-
2-
(tripropoxysilyl)butane; 2,3-dimethyl-2-(triisopropoxysilyl)butane; 2,3-
dimethyl-2-
(trimethoxysilyl)pentane; 2,3-dimethyl-2-(triethoxysilyl)pentane; 2,3-dimethyl-
2-
(tripropoxysilyl)pentane; 2,3-dimethyl-2-(triisopropoxysilyl)pentane; 2-methyl-
3-ethyl-
2-(trimethoxysilyl)pentane; 2-methyl-3-ethyl-2-(triethoxysilyl)pentane; 2-
methyl-3-
ethyl-2-(tripropoxysilyl)pentane; 2-methyl-3-ethyl-2-
(triisopropoxysilyl)pentane; 2,3,4-
trimethyl-2-(trimethoxysilyl)pentane; 2,3,4-trimethyl-2-
(triethoxysilyl)pentane; 2,3,4-
trimethyl-2-(tripropoxysilyl)pentane; 2,3,4-trimethyl-2-
(triisopropoxysilyl)pentane; 2,3-
dimethyl-2-(trimethoxysilyl)hexane; 2,3-dimethyl-2-(triethoxysilyl)hexane; 2,3-
3o dimethyl-2-(tripropoxysilyl)hexane; 2,3-dimethyl-2-
(triisopropoxysilyl)hexane; 2,4-
dirnethyl-3-ethyl-2-(trimethoxysilyl)pentane; 2,4-dimethyl-3-ethyl-2-
(triethoxysilyl)pentane; 2,4-dimethyl-3-ethyl-2-(tripropoxysilyl)pentane; 2,4-
dimethyl-
3-ethyl-2-(triisopropoxysilyl)pentane; 2,4-dimethyl-3-isopropyl-2-
(trimethoxysilyl)pentane; 2,4-dimethyl-3-isopropyl-2-(triethoxysilyl)pentane;
Substitute Page 28
CA 02395710 2002-06-26 '~g~ ~E~' ' "'~'
~~,' ~. ~ ~~~~
'~
aaa;..~ ~'
DOCKET NO. 71133
2,4-dimethyl-3-isopropyl-2-(tripropoxysilyl)pentane; 2,4-dimethyl-3-isopropyl-
2-
(triisopropoxysilyl)pentane; hexamethyldisiloxane; 1,1,1,3,3,3-
hexamethyldisilazane.
The present invention also provides a catalyst system comprising
s (A) at least one solid procatalyst as described above; and
(B) at least one cocatalyst
The solid procatalyst may or may not include an internal electron donor, as
described herein.
to The molar ratio of the cocatalyst to the transition metal in the solid
procatalyst
preferably is from about 0.1 to about 1000. Preferably, the molar ratio of the
cocatalyst to the transition metal in the solid procatalyst is from about 1 to
about 250.
Most preferably, the molar ratio of the cocatalyst to the transition metal in
the solid
procatalyst is from about 5 to about 100.
15 The at least one cocatalyst used in the present invention can be any
organometallic compound, or mixtures thereof, that can activate the solid
procatalyst
in the polymerization or interpolymerization of olefins. For example, the
cocatalyst
component may contain an element of Groups 1, 2, 11, 12, 13 and/or 14 of the
above-referenced Periodic Table of the Elements. Examples of such elements are
20 lithium, magnesium, copper, zinc, boron, aluminum, silicon, tin.
Preferably, the cocatalyst is at least one compound of the empirical formula,
R"EY,"Hp or (QER)q,
or mixtures thereof,
wherein,
2s each R is independently a hydrocarbyl group;
E is selected from the group consisting of boron, aluminum, gallium, and
indium;
each Y is independently a monoanionic, monodentate ligand;
Q is selected from the group consisting of -O-, -S-, -N(R)-, -N(OR)-, -N(SR)-,
30 -N(NR2~, -N(PR2~, -P(R)-, -P(OR)-, -P(SR)-, and -P(NR2~;
n>O,mz0,pz0,andn+m+p=3; and
qz1.
Substitute Page 29
CA 02395710 2002-06-26 ~~ ~~~-~~~a" ~~~-~_"~~'
5~$Fv'°v"
~t~a~,i~;
DOCKET NO. 71133
The term "hydrocarbyl group", as used herein, denotes a monovalent, linear,
branched, cyclic, or polycyclic group which contains carbon and hydrogen
atoms.
The hydrocarbyl group may optionally contain atoms in addition to carbon and
hydrogen selected from Groups 13, 14, 15, 16, and 17 of the Periodic Table.
s Examples of monovalent hydrocarbyls include the following: C,-C~ alkyl; C,-
Coo alkyl
substituted with one or more groups selected from C~-C~ alkyl, C3-C~5
cycloatkyl or
aryl; C3-C,s cycloalkyl; C3-C,5 cycloalkyl substituted with one or more groups
selected from C,-C~ alkyl, C3-C~5 cycloalkyl or aryl; C~-C~5 aryl; and CB-C,5
aryl
substituted with one or more groups selected from C,-C~ alkyl, C3-C~5
cycloalkyl or
to aryl; where aryl preferably denotes a substituted or unsubstituted phenyl,
napthyl, or
anthracenyl group.
Examples of the monoanionic, monodentate ligand Y include the halides,
-OR, -OBR2, -OSR, -ONR2, -OPRZ, -NRZ, -N(R)BR2, -N(R)OR, -N(R)SR, -N(R)NR2,
-N(R)PR2, -N(BR2)2, -N=CR2, -N=NR, -N=PR, -SR, -SBR2, -SOR, -SNR2, -SPR2,
-PR2. Each R is independently a hydrocarbyl group, as defined above. Examples
of
halides are fluoride, chloride, bromide, and iodide.
Examples of alkoxides are methoxide, ethoxide, n-propoxide, i-propoxide,
cyclopropyloxide, n-butoxide, i-butoxide, s-butoxide, t-butoxide,
cyclobutyloxide, n-
amyloxide, i-amyloxide, s-amyloxide, t-amyloxide, neopentoxide,
cyclopentyloxide, n-
2o hexoxide, cyclohexyioxide, heptoxide, octoxide, nonoxide, decoxide,
undecoxide,
dodecoxide, 2-ethyl hexoxide, phenoxide, 2,6-dimethylphenoxide, 2,6-di-i-
propylphenoxide, 2,6-diphenylphenoxide, 2,6-dimesitylphenoxide, 2,4,6-
trimethylphenoxide, 2,4,6-tri-i-propylphenoxide, 2,4,6-triphenylphenoxide,
2,4,6-
trimesitylphenoxide, benryloxide, menthoxide, halogenated alkoxides such as
trifluoromethoxide, trifluoroethoxide, trifluoro-i-propoxide, hexafluoro-i-
propoxide,
heptafluoro-i-propoxide, trifluoro-t-butoxide, hexafluoro-t-butoxide,
trifluoromethoxide, trichloroethoxide, trichloro-i-propoxide.
Examples of thiolates are methylthiolate, ethylthiolate, n-propylthiolate, i-
propylthiolate, cyclopropylthiolate, n-butylthiolate, i-butylthiolate, s-
butylthiolate, t-
3o butylthiolate, cyclobutylthiolate, n-amylthiolate, i-amylthiolate, s-
arnylthiolate, t-
amylthiolate, neopentylthiolate, cyclopentylthiolate, n-hexylthiolate,
cyclohexylthiolate, phenylthiolate, 2,6-dimethylphenylthiolate, 2,6-di-i-
propylphenylthiolate, 2,6-diphenylphenylthiolate, 2,6-dimesitylphenylthiolate,
2,4,6-
trimethylphenylthiolate, 2,4,6-tri-i-propylphenylthiolate, 2,4,6-
triphenylphenylthiolate,
Substitutc Page 30
s~ ~.<
CA 02395710 2002-06-26
.t
DOCKET NO. 71133
2,4,6-trimesitylphenylthiolate, benrylthiolate, heptylthiolate, octylthiolate,
nonylthiolate, decylthiolate, undecylthiolate, dodecylthiolate, 2-ethyl
hexylthiolate,
menthylthiolate, halogenated alkylthiolates such as trifluoromethylthiolate,
trifluoroethylthiolate, trifluoro-i-propylthiolate, hexafluoro-i-
propylthiolate, heptafluoro-
i-propylthiolate, trifluoro-t-butylthiolate, hexafluoro-t-butylthiolate,
trifluoromethylthiolate, trichloroethylthiolate, trichloro-i-propylthiolate.
Examples of amides are dimethylamide, diethylamide, di-n-propylamide, di-i-
propylamide, dicyclopropylamide, di-n-butylamide, di-i-butylamide, di-s-
butylamide,
di-t-butylamide, dicyclobutylamide, di-n-amylamide, di-i-amylamide, di-s-
amylamide,
1o di-t-amylamide, dicyclopentylamide, dineopentylamide, di-n-hexylamide,
dicyclohexylamide, diheptylamide, dioctylamide, di-nonylamide, didecylamide,
diundecylamide, didodecylamide, di-2-ethyl hexylamide, diphenylamide, bis-2,6-
dimethylphenylamide, bis-2,6-di-i-propylphenylamide, bis-2,6-
diphenylphenylamide,
bis-2,6-dimesitylphenylamide, bis-2,4,6-trimethylphenylamide, bis-2,4,6-tri-i-
15 propylphenylamide, bis-2,4,6-triphenylphenylamide, bis-2,4,6-
trimesitylphenylamide,
dibenzylamide, dihexylamide, dicyclohexylamide, dioctylamide, didecylamide,
dioctadecylamide, diphenylamide, dibenzylamide, bis-2,6-dimethylphenylamide,
2,6-
bis-i-propylphenylamide, bis-2,6-diphenylphenylamide, diallylamide, di-
propenylamide, N-methylanilide; N-ethylanilide; N-propylanilide; N-i-
propylanilide; N-
20 butylanilide; N-i-butylanilide; N-amylanilide; N-i-amylanilide; N-
octylanilide; N-
cyclohexylanilide; silyl amides such as bis(trimethylsilyl)amide,
bis(triethylsilyl)amide,
bis(dimethylphenylsilyl)amide, bis(t-butyldimethylsilyl)amide, bis(t-
butyldiphenylsilyl)amide, phenyl(trimethylsilyl)amide,
phenyl(triethylsilyl)amide,
phenyl(trimethylsilyl)amide, methyl(trimethylsilyl)amide,
ethyl(trimethylsilyl)amide, n-
25 propyl(trimethylsilyl)amide, i-propyl(trimethylsilyl)amide,
cyclopropyl(trimethylsilyl)amide, n-butyl(trimethylsilyl)amide, i-
butyl(trimethylsilyl)amide, s-butyl(trimethylsilyl)amide, t-
butyl(trimethylsilyl)amide,
cyclobutyi(trimethylsilyl)amide, n-amyl(trimethylsilyl)amide, i-
amyl(trimethylsilyl)amide, s-amyl(trimethylsilyl)amide, t-
amyl(trimethylsilyl)amide,
3o neopentyl(trimethylsilyl)amide, cyclopentyl(trimethylsilyl)amide, n-
hexyl(trimethylsilyf)amide, cyclohexyl(trimethylsilyl)amide,
heptyl(trimethylsilyl)amide
and triethylsilyl trimethylsilylamide, heterocyclic amides such as the
conjugate bases
of pyrrole, pyrrolidine, piperidine, piperazine, indole, imidazole,
Substitute Pagc 31
CA 02395710 2002-06-26 '~~f ~ ~~~ '°~._" ~°
~ ~~"'~~~
DOCKET NO. 71133
azole, thiazole, purine, phthalimide, azacycloheptane, azacyclooctane,
azacyclononane, azacyclodecane, their substituted derivatives.
Examples of phosphides are dimethylphosphide, diethylphosphide,
dipropylphosphide, dibutylphosphide, diamylphosphide, dihexylphosphide,
dicyclohexylphosphide, diphenylphosphide, dibenzylphosphide, bis-2,6-
dimethylphenylphosphide, 2,6-di-i-propylphenylphosphide, 2,6-
diphenylphenylphosphide, the conjugate bases of cyclic phosphines such as
phosphacyclopentane, phosphacyclohexane, phosphacycloheptane,
phosphacyclooctane, phosphacyclononane, phosphacyclodecane.
to Preferred for use herein as the monoanionic, monodentate ligand Y are
fluoride, chloride, bromide, methoxide, ethoxide, n-propoxide, i-propoxide,
butoxide,
neopentoxide, benzyloxide, trifluoromethoxide, and trifluoroethoxide.
Mixtures of monoanionic, monodentate ligands Y may be used as the
monoanionic, monodentate ligand Y.
i5 Examples of the cocatalysts useful in the process of the present invention
where E is boron in the formula R"EY,"HP include trimethylborane;
triethylborane; tri-
n-propylborane; tri-n-butylborane; tri-n-pentylborane; triisoprenylborane; tri-
n-
hexylborane; tri-n-heptylborane; tri-n-octylborane; triisopropylborane;
triisobutylborane; tris(cylcohexylmethyl)borane; triphenylborane;
2o tris(pentafluorophenyl)borane; dimethylborane; diethylborane; di-n-
propylborane; di-
n-butylborane; di-n-pentylborane; diisoprenylborane; di-n-hexylborane; di-n-
heptylborane; di-n-0ctylborane; diisopropylborane; diisobutylborane;
bis(cylcohexylmethyl)borane diphenylborane; bis(pentafluorophenyl)borane;
dimethylboron chloride; diethylboron chloride; di-n-propyiboron chloride; di-n-
25 butylboron chloride; di-n-pentylboron chloride; diisoprenylboron chloride;
di-n-
hexylboron chloride; di-n-heptylboron chloride; di-n-octylboron chloride;
diisopropylboron chloride; diisobutylboron chloride;
bis(cylcohexylmethyl)boron
chloride; diphenylboron chloride; bis(pentafluorophenyl)boron chloride;
diethylboron
fluoride; diethylboron bromide; diethylboron iodide; dimethylboron methoxide;
3o dimethylboron ethoxide; diethylboron ethoxide; dimethylboron methoxide;
dimethylboron ethoxide; diethylboron ethoxide; methylboron dichloride;
ethylboron
dichloride; n-propylboron dichloride; n-butylboron dichloride; n-pentylboron
dichloride; isoprenylboron dichloride; n-hexylboron dichloride; n-heptylboron
dichloride; n-octylboron dichloride; isopropylboron dichloride; isobutylboron
Substitute Page 32
,~~;~, CA 02395710 2002-06-26
DOCKET NO. 71133
dichloride; (cylcohexylmethyl)boron dichloride; phenylboron dichloride;
pentafluorophenylboron dichloride; chloromethylboron methoxide;
chloromethylboron
ethoxide; chloroethylboron ethoxide.
Examples of the cocatalysts useful in the process of the present invention
s where E is aluminum in the formula R"EYmHp include trimethylaluminum;
triethylaluminum; tri-n-propylaluminum; tri-n-butylaluminum; tri-n-
pentylaluminum;
triisoprenylaluminum; tri-n-hexylaluminum; tri-n-heptylaluminum; tri-n-
octylaluminum;
triisopropylaluminum; triisobutylaluminum; tris(cylcohexylmethyl) aluminum;
dimethylaluminum hydride; diethylaluminum hydride; di-n-propylaluminum
hydride;
io di-n-butylaluminum hydride; di-n-pentylaluminum hydride;
diisoprenylaluminum
hydride; di-n-hexylaluminum hydride; di-n-heptylaluminum hydride; di-n-
octylaluminum hydride; diisopropylaluminum hydride; diisobutylaluminum
hydride;
bis(cylcohexylmethyl)aluminum hydride; dimethylaluminum chloride;
diethylaluminum
chloride; di-n-propylaluminum chloride; di-n-butylaluminum chloride; di-n-
15 pentylaluminum chloride; diisoprenylaluminum chloride; di-n-hexylaluminum
chloride;
di-n-heptylaluminum chloride; di-n-octylaluminum chloride; diisopropylaluminum
chloride; diisobutylaluminum chloride; bis(cylcohexylrnethyl)aluminum
chloride;
diethylaluminum fluoride; diethylaluminum bromide; diethylaluminum iodide;
dimethylaluminum methoxide; dimethylaluminum ethoxide; diethylaluminum
2o ethoxide; methylaluminum dichloride; ethylaluminum dichloride; n-
propylaluminum
dichloride; n-butylaluminum dichloride; n-pentylaluminum dichloride;
isoprenylaluminum dichloride; n-hexylaluminum dichloride; n-heptylaluminum
dichloride; n-octylaluminum dichloride; isopropylaluminum dichloride;
isobutylaluminum dichloride; (cylcohexylmethyl)aluminum dichloride;
25 chloromethylaluminum methoxide; chloromethylaluminum ethoxide;
chloroethylaluminum ethoxide.
Other examples of suitable cocatalysts include the alumoxanes, especially
methylalumoxane. Other examples of suitable cocatalysts of empirical formula
(QER)q include alumimines.
3o Preferred for use herein as cocatalysts are trialkylaluminums such as
trimethylaluminurn, triethylaluminum, tri-n-propylaluminum, tri-n-
butylaluminum,
triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-2-
methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum; and
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminurn
Substitute Page 33
CA 02395710 2002-06-26 ~ '~~ ~~' ~~. .°'
34' 1~~~1 ~IG
a , , ~ k s gil '~ '.~" cue a~~~'s", ~ ~ ~. '~'a~~;, ~ ~,y
~~~
DOCKET NO. 71133
chloride, dibutylaluminum chloride, diisobutylaluminum chloride,
diethylaluminum
bromide and diethylaluminum iodide; and atkylaluminum sesquihalides such as
methylaluminum sesquichloride, ethylaluminum sesquichloride, n-butylaluminum
sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquifluoride,
ethylaluminum sesquibromide and ethylaluminum sesquiiodide.
Most preferred for use herein as cocatalysts are trialkylaluminums such as
trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
triisobutylaluminum, tri-n-
octylaluminum and dialkylaluminum halides such as dimethylaluminum chloride,
diethylaluminum chloride, diisobutylaluminum chloride and alkylaluminum
to sesquihalides such as methylaluminum sesquichloride, and ethylaluminum
sesquichloride.
Mixtures of the above cocatalysts can also be utilized herein as the
cocatalyst.
is In a further aspect of the invention, there is provided a process for
polymerizing or interpolymerizing olefins using the catalyst systems of the
invention,
which comprise a solid procatalyst and a cocatalyst as set forth herein.
Preferably, the present invention provides a process for polymerizing
ethylene and/or interpolymerizing ethylene and at least one or more other
olefins)
2o comprising contacting, under polymerization conditions, the ethylene and/or
ethylene
and at least one or more olefins) with the catalyst system of the present
invention.
The polymerization or interpolymerization process of the present invention
may be carried out using any conventional process. For example, there may be
utilized polymerization or interpolymerization in suspension, in solution, in
super-
2s critical fluid or in gas phase media. All of these polymerization or
interpolymerization processes are well known in the art.
A particularly desirable method for producing polyethylene polymers and
interpolymers according to the present invention is a gas phase polymerization
process preferably utilizing a fluidized bed reactor. This type reactor and
means for
30 operating the reactor are well known and completely described in U.S
Patents Nos.
3,709,853; 4,003,712; 4,011,382; 4,012,573; 4,302,566; 4,543,399; 4,882,400;
5,352,749; 5,541,270; Canadian Patent No. 991,798 and Belgian Patent No.
839,380. These patents disclose gas phase polymerization processes wherein the
polymerization medium is either mechanically agitated or fluidized by the
continuous
Substitute Page 34
CA 02395710 2002-06-26 ~~'~s r~
35-, ~~~w~~'~~
DOCKET NO. 71133
flow of the gaseous monomer and diluent. The entire contents of these patents
are
incorporated herein by reference.
In general, the polymerization process of the present invention may be
effected as a continuous gas phase process such as a fluid bed process. A
fluid bed
reactor for use in the process of the present invention typically comprises a
reaction
zone and a so-called velocity reduction zone. The reaction zone comprises a
bed of
growing polymer particles, formed polymer particles and a minor amount of
catalyst
particles fluidized by the continuous flow of the gaseous monomer and diluent
to
remove heat of polymerization through the reaction zone. Optionally, some of
the
io recirculated gases may be cooled and compressed to form liquids that
increase the
heat removal capacity of the circulating gas stream when readmitted to the
reaction
zone. A suitable rate of gas flow may be readily determined by simple
experiment.
Make up of gaseous monomer to the circulating gas stream is at a rate equal to
the
rate at which particulate polymer product and monomer associated therewith is
withdrawn from the reactor and the composition of the gas passing through the
reactor is adjusted to maintain an essentially steady state gaseous
composition
within the reaction zone. The gas leaving the reaction zone is passed to the
velocity
reduction zone where entrained particles are removed. Finer entrained
particles and
dust may be removed in a cyclone and/or fine filter. The gas is passed through
a
2o heat exchanger wherein the heat of polymerization is removed, compressed in
a
compressor and then returned to the reaction zone.
In more detail, the reactor temperature of the fluid bed process herein ranges
from about 30°C to about 110°C. In general, the reactor
temperature is operated at
the highest temperature that is feasible taking into account the sintering
temperature
of the polymer product within the reactor.
The process of the present invention is suitable for the production of
polymers of olefins andlor interpolymers of olefins and at least one or more
other
olefins. Preferably, the process of the present invention is suitable for the
production
of polymers of ethylene and/or interpolymers of ethylene and at least one or
more
other olefins. Preferably the olefins are alpha-olefins. The olefins, for
example, may
contain from 2 to 16 carbon atoms. Particularly preferred for preparation
herein by
the process of the present invention are linear polyethylene polymers and
interpolymers. Such linear polyethylene polymers or interpolymers are
preferably
linear homopolymers of ethylene and linear interpolymers of ethylene and at
least
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one alpha-olefin wherein the ethylene content is at least about 50% by weight
of the
total monomers involved. Examples of alpha-olefins that may be utilized herein
are
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octane, 4-methylpent-1-
ene, 1-decene, 1-dodecene, 1-hexadecene. Also utilizable herein are polyenes
such
s as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-
vinylcyclohex-1-ene, 1,5-cyclooctadiene, 5-vinylidene-2-norbornene and 5-vinyl-
2-
norbornene, and olefins formed in situ in the polymerization or
interpolymerization
medium. When olefins are formed in situ in the polymerization or
interpolymerization
medium, the formation of linear polyethylene polymers or interpolymers
containing
io long chain branching may occur.
Examples of the polymers or interpolymers that can be produced by the
process of the present invention include polymers of ethylene and
interpolymers of
ethylene and at least one or more alpha-olefins having 3 to 16 carbon atoms
wherein
ethylene comprises at least about 50% by weight of the total monomers
involved.
1s The olefin polymers or interpolymers of the present invention may be
fabricated into films by any technique known in the art. For example, films
may be
produced by the well known cast film, blown film and extrusion coating
techniques.
Further, the olefin polymers or interpolymers may be fabricated into other
articles of manufacture, such as molded articles, by any of the well known
2o techniques.
In the process of the invention, the solid procatalyst, cocatalyst, or
catalyst
system can be introduced in any manner known in the art. For example, the
solid
procatalyst can be introduced directly into the polymerization or
interpolymerization
medium in the form of a slurry or a dry free flowing powder. The solid
procatalyst
25 can also be used in the form of a prepolymer obtained by contacting the
solid
procatalyst with one or more olefins in the presence of a cocatalyst.
The molecular weight of the olefin polymers or interpolymers produced by the
present invention can be controlled in any known manner, for example, by using
hydrogen. The molecular weight control may be evidenced by an increase in the
3o melt index (I2) of the polymer or interpolymer when the molar ratio of
hydrogen to
ethylene in the polymerization or interpolymerization medium is increased.
The invention will be more readily understood by reference to the following
examples. There are, of course, many other forms of this invention which will
become obvious to one skilled in the art, once the invention has been fully
disclosed,
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DOCxET NO. 71133
and it will accordingly be recognized that these examples are given for the
purpose
of illustration only, and are not to be construed as limiting the scope of
this invention
in any way.
Examples
In the following examples the test procedures listed below were used in
evaluating the analytical and physical properties of the polymers herein.
1o a) The molecular weight distribution (MWD), the ratio of M""/M", of the
ethylene/olefin interpolymers are determined with a Waters Get
Permeation Chromatograph Series 150 equipped with Ultrastyrogel
columns and a refractive index detector. The operating temperature of the
instrument was set at 140 °C, the eluting solvent was o-
dichlorobenzene,
is and the calibration standards included 10 polystyrenes of precisely known
molecular weight, ranging from a molecular weight of 1000 to a molecular
weight of 1.3 million, and a polyethylene standard, NBS 1475;
b) Melt Index (MI), 12, is determined in accord with ASTM D-1238, condition
E, measured at 190 °C, and reported as decigrams per minute;
2o c) High Load Melt Index (HLMI), IZ,, is measured in accord with ASTM D-
1238, Condition F, measured at 10.0 times the weight used in the melt
index test above;
d) Melt Flow Ratio (MFR) = I2~II2 or High Load Melt IndexIMelt Index.
2s Examples 1 -12 were carried out in a nitrogen-filled Vacuum Atmospheres
He-43-2 glove box. Solvents and hexene were purified by passage through a bed
of
activated alumina followed by passage through a bed of BASF R-311 copper
catalyst
under 172 kPa (25 psi) nitrogen pressure prior to entering the glove box.
Ethylene
and hydrogen were purified by passage through a bed of BASF R-311 copper
3o catalyst prior to entering the glove box. Solvents and gases are introduced
into the
glove box using 3.2 mm (1/8 inch) steel tubing terminating with ball valves.
All other
reagents were obtained from commercial sources and used as received. In
examples 2, 4, and 11 - 12, there was utilized SylopoITM 5550 support from
Grace
Davison.
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DOCKET NO. 71133
Example 1 (comparative,)
A solution was prepared by adding 0.0981 mL of 2,2,6,6-
s tetramethylheptanedione to a solution of 0.0590 mL EtzAlCl in 2 mL toluene.
The
resulting solution was stirred for 30 minutes.
The above solution was added to a solution of 114 mg of Ti(2,2,6,6-
tetramethylheptanedionate)CI2 in 2.0 mL toluene with stirring, followed by
addition of
1.0 mL toluene. The resulting solution was stirred for 120 seconds.
to
Example 2
A solution was prepared by adding 0.0981 mL of 2,2,6,6-
tetramethylheptanedione to a solution of 0.0590 mL Et2AICl in 2 mL toluene.
The
15 resulting solution was stirred for 30 minutes.
The above solution was added to a solution of 114 mg of Ti(2,2,6,6-
tetramethylheptanedionate)CI2 in 2.0 mL toluene with stirring, followed by
addition of
1.0 mL toluene. The resulting solution was stirred for 120 seconds. 1.0 mL of
the
resulting solution was added to a stirred slung of 500 mg SylopolT~ 5550
support in
20 6.0 mL toluene. The resulting slung was stirred for 30 minutes and filtered
using a
fritted glass funnel. The solid procatalyst powder was then washed with
pentane and
dried in vacuo for 30 minutes.
Example 3 (comparative)
A solution was prepared by adding to a solution of 0.090 mL Me3Al in 4 mL
toluene, 5 mL of a solution of 0.196 mL of 2,2,6,6-tetramethylheptanedione in
toluene at a rate of 2 - 4 dropslsec. The resulting solution was stirred for
60
3o minutes. The resulting solution was then added to a 10 mL volumetric flask
followed
by addition of toluene to make a 10.0 rnL solution.
To 5.0 mL of the above solution was added 114 mg of Ti(2,2,6,6-
tetramethylheptanedionate)CI2 with stirring. The resulting solution was
stirred for
120 seconds.
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DOCKET NO. 71133
Example 4
A solution was prepared by adding to a solution of 0.090 mL Me3Al in 4 mL
toluene, 5 mL of a solution of 0.196 mL of 2,2,6,6-tetramethylheptanedione in
toluene at a rate of 2 - 4 dropslsec. The resulting solution was stirred for
60
minutes. The resulting solution was then added to a 10 mL volumetric flask
followed
by addition of toluene to make a 10.0 mL solution.
To 5.0 mL of the above solution was added 114 mg of Ti(2,2,6,6-
tetramethylheptanedionate)CI2 with stirring. The resulting solution was
stirred for
120 seconds. 1.0 mL of the resulting solution was added to a stirred slurry of
500
mg SylopoITM 5550 support in 6.0 mL toluene. The resulting slung was stirred
for 30
minutes and filtered using a fritted glass funnel. The solid pnxatalyst powder
was
then washed with pentane and dried in vacuo for 30 minutes.
Examples 5 -10
In the following examples 5 -10 the materials produced in examples 1 - 4
were utilized in carrying out polymerization reactions. The polymerization
reactions
were carried out in a 12 oz. Fischer-Porter aerosol reaction vessel. This is a
bottle-
2o type design using a rubber to glass sealing head. Installation of the
reactor head
provides a seal which will safely hold 690 kPa (100 psi). Heat is applied via
a 1"
wide heating tape wrapped around a stainless steel protective wire mesh
screen.
Gas or liquid monomers can be added through a rnulti-port addition head as
desire
Pressures and volumes can al! be maintained at the source prior to addition
into the
vessel.
Comparative Examples 5 and 8
In carrying out comparative examples 5 and 8, the following procedure was
utilized. 0.0075 mL of trimethyl aluminum was added to a solution of 15 mL
hexene
3o in 100 mL heptane, and the resulting solution was heated to 90 °C.
The solution of
example 1 was then added and the reactor sealed. Excess pressure was vented
from the reaction vessel. 55.2 kPa (8 psi) hydrogen pressure was added.
Ethylene
was added to give a total pressure of 662 kPa (96 psi), and this pressure was
maintained for one hour by continuous ethylene feed. After this time, the
reaction
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DOCKET NO. 71133
vessel pressure was vented and the vessel removed from the glove box.
Approximately 300 mL of reagent grade acetone was added to the slurry and the
slurry was cooled to room temperature. The slurry was mixed with a blender.
filtered, and washed with acetone. The resulting powder was dried in a vacuum
oven for at least four hours at 40 - 50 °C.
Examples 6. 7. 9, and 10
In carrying out examples 6, 7, 9, and 10, the following procedure was
utilized.
l0 100 mL heptane was added to the reaction vessel. 1.0 mL of this heptane was
added to the solid procatalyst of example 2 to form a slurry, and 0.0075 mL of
trimethyl aluminum was added. The resulting slurry was added to the reaction
vessel. The vessel was sealed, and was heated to 90 °C. Excess pressure
was
vented from the reaction vessel. 55.2 kPa (8 psi) hydrogen pressure was added.
Hexene was added using ethylene pressure, giving a total pressure of 662 kPa
(96
psi). This pressure was maintained for one hour by continuous ethylene feed.
After
this time, the reaction vessel pressure was vented and the vessel removed from
the
glove box. Approximately 300 mL of reagent grade acetone was added to the
slurry
and the slurry was cooled to room temperature. The slurry was mixed with a
2o blender, filtered, and washed with acetone. The resulting powder was dried
in a
vacuum oven for at least four hours at 40 - 50 °C.
Further details concerning examples 5 -10 are reported in Table 1.
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DOCKET NO. 71133
Table
1.
Polymerization
data.
CatalystAmount PolymerKg Poly-Mg Poly-
from of Yield mer/ mer/ MWD Mn Mw
Exam 1e Exam Catal Ti hr mol Mw/Mn K K
1e st Ti
hr
1 1.0 mL 0.3 0.13 0.006 41 1.1 44
6 2 4.5 mg 6.0 296 14.2 4.7 24.8117
7 2 4.5 m 5.3 262 12.5 5.2 26.3137
8 3 1.0 mL 0.0 - - - - -
9 4 4.5 mg 6.2 306 14.7 4.4 25.2112
4 4.5 mg 5.3 262 12.5 4.7 26.7125
From the data above, it is observed that the activity (Kg Polymer/g Ti hr)
5 resulting from the use of a supported solid procatalyst as compared to. the
activity
resulting form the use of a soluble unsupported procatalyst is increased.
Further, it
is observed that the molecular weight distribution (Mw/Mn) of the polymer
produced
using a supported solid procatalyst as compared with the polymer produced
using a
soluble unsupported catalyst is decreased.
to In the following Examples 11 and 12, there are described the preparation of
additional solid procatalysts. It is expected that the solid procatalysts of
Examples
11 and 12 can be used in the preparation of catalyst systems that will be
useful in the
polymerization and interpolymerization of olefins.
Example 11
A solution was prepared by adding 0.0981 mL of 2,2,6,6-
tetramethylheptanedione to a solution of 0.0590 mL Et2AICl in 2 mL toluene.
The
resulting solution was stirred for 30 minutes.
2o The above solution was added to a solution of 114 mg of Ti(2,2,6,6-
tetramethylheptanedionate)CI2 in 2.0 mL toluene with stirs-ing, followed by
addition of
1.0 mL toluene. The resulting solution was stirred for 120 seconds. 0.0381 mL
tetrahydrofuran was added to this solution. The resulting solution was stirred
for 120
seconds. 1.0 mL of the resulting solution was added to a stirred slurry of 500
mg
SylopoITM 5550 support in 6.0 mL toluene. The resulting slurry was stirred for
30
minutes and filtered using a fritted glass funnel. The solid procatalyst
powder was
then washed with pentane and dried in vacuo for 30 minutes.
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Example 12
A solution was prepared by adding to a solution of 0.090 mL Me3Al in 4 mL
toluene, 5 mL of a solution of 0.196 mL of 2,2,6,6-tetramethylheptanedione in
toluene at a rate of 2 - 4 dropslsec. The resulting solution was stirred for
60
minutes. The resulting solution was then added to a 10 mL volumetric flask
followed
by addition of toluene to make a 10.0 ml solution.
To 5.0 mL of the above solution was added 114 mg of Ti(2,2,6,6-
to tetramethylheptanedionate)CI2 with stirring. The resulting solution was
stirred for
120 seconds. 0.0381 mL tetrahydrofuran was added to this solution. The
resulting
solution was stirred for 120 seconds. 1.0 mL of the resulting solution was
added to a
stirred slurry of 500 mg SylopolT~" 5550 support in 6.0 mL toluene. The
resulting
slung was stirred for 30 minutes and filtered using a fritted glass funnel.
The solid
procatalyst powder was then washed with pentane and dried in vacuo for 30
minutes.
It should be clearly understood that the forms of the invention herein
described are illustrative only and are not intended to limit the scope of the
invention.
2o The present invention includes all modifications falling within the scope
of the
following claims.
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