U.S. patent application number 09/932549 was filed with the patent office on 2002-05-16 for polymerization process for producing easier processing polymers.
Invention is credited to Crowther, Donna J., Lue, Ching-Tai.
Application Number | 20020058828 09/932549 |
Document ID | / |
Family ID | 23184023 |
Filed Date | 2002-05-16 |
United States Patent
Application |
20020058828 |
Kind Code |
A1 |
Crowther, Donna J. ; et
al. |
May 16, 2002 |
Polymerization process for producing easier processing polymers
Abstract
The present invention relates to a process for polymerizing
olefin(s) utilizing a cyclic bridged metallocene-type catalyst
system to produce enhanced processability polymers.
Inventors: |
Crowther, Donna J.;
(Baytown, TX) ; Lue, Ching-Tai; (Houston,
TX) |
Correspondence
Address: |
UNIVATION TECHNOLOGIES LLC
5555 SAN FELIPE SUITE 1950
HOUSTON
TX
77056
US
|
Family ID: |
23184023 |
Appl. No.: |
09/932549 |
Filed: |
August 17, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09932549 |
Aug 17, 2001 |
|
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09306142 |
May 6, 1999 |
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Current U.S.
Class: |
556/11 |
Current CPC
Class: |
B01J 31/1608 20130101;
C08F 4/65916 20130101; C08F 210/16 20130101; C08F 10/00 20130101;
C08F 4/65912 20130101; B01J 31/2295 20130101; Y10S 526/943
20130101; B01J 2531/48 20130101; C07F 17/00 20130101; B01J
2531/0288 20130101; Y10S 526/901 20130101; C08F 2420/09 20210101;
C08F 10/00 20130101; C08F 4/65927 20130101; C08F 210/16 20130101;
C08F 210/14 20130101; C08F 2500/12 20130101; C08F 2500/18 20130101;
C08F 2500/10 20130101 |
Class at
Publication: |
556/11 |
International
Class: |
C07F 017/00 |
Claims
We claim:
1. Cyclotrimethylenesilyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride.
2. Cyclotetramethylenesilyl (tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride.
3. Cyclotrimethylenesilyl(tetramethyl cyclopentadienyl) (3-methyl
cyclopentadienyl) zirconium dichloride.
4. Cyclotrimethylenesilyl (tetramethyl cyclopentadienyl)
(2,3,5-trimethyl cyclopentadienyl) zirconium dichloride.
5. Cyclotrimethylenesilyl bis(tetra methyl cyclopentadienyl)
zirconium dichloride.
Description
RELATED APPLICATION DATA
[0001] The present application is a divisional of U.S. patent
application Ser. No. 09/306,142, filed May 6, 1999, now issued as
U.S. Pat. No. ______.
FIELD OF THE INVENTION
[0002] The present invention relates to a process for polymerizing
olefin(s) to produce polymers having improved processability. Also,
the invention is directed to a bulky ligand metallocene-type
catalyst compound and catalyst system for use in the polymerization
of olefin(s) to produce polymers that are easier to process into
various articles of manufacture. In particular, the invention is
directed to cyclic bridged bulky ligand metallocene-type catalyst
systems, their use in a polymerization process, and products
produced therefrom.
BACKGROUND OF THE INVENTION
[0003] Processability is the ability to economically process and
shape a polymer uniformly. Processability involves such elements as
how easily the polymer flows, melt strength, and whether or not the
extrudate is distortion free. Typical bulky ligand metallocene-type
catalyzed polyethylenes (mPE) are somewhat more difficult to
process than low density polyethylenes (LDPE) made in a high
pressure polymerization process. Generally, mPE's require more
motor power and produce higher extruder pressures to match the
extrusion rate of LDPE's. Typical mPE's also have lower melt
strength which, for example, adversely affects bubble stability
during blown film extrusion, and they are prone to melt fracture at
commercial shear rates. On the other hand, however, mPE's exhibit
superior physical properties as compared to LDPE's.
[0004] It is now common practice in the industry to add various
levels of an LDPE to an mPE to increase melt strength, to increase
shear sensitivity, i.e., to increase flow at commercial shear
rates; and to reduce the tendency to melt fracture. However, these
blends generally have poor mechanical properties as compared with
neat mPE.
[0005] Traditionally, metallocene catalysts produce polymers having
a narrow molecular weight distribution. Narrow molecular weight
distribution polymers tend to be more difficult to process. The
broader the polymer molecular weight distribution the easier the
polymer is to process. A technique to improve the processability of
mPE's is to broaden the products' molecular weight distribution
(MWD) by blending two or more mPE's with significantly different
molecular weights, or by changing to a polymerization catalyst or
mixture of catalysts that produce broad MWD polymers.
[0006] In the art specific bulky ligand metallocene-type catalyst
compound characteristics have been shown to produce polymers that
are easier to process. For example, U.S. Pat. No. 5,281,679
discusses bulky ligand metallocene-type catalyst compounds where
the bulky ligand is substituted with a substituent having a
secondary or tertiary carbon atom for the producing of broader
molecular weight distribution polymers. U.S. Pat. No. 5,470,811
describes the use of a mixture of bulky ligand metallocene-type
catalysts for producing easy processing polymers. Also, U.S. Pat.
No. 5,798,427 addresses the production of polymers having enhanced
processability using a bulky ligand metallocene-type catalyst
compound where the bulky ligands are specifically substituted
indenyl ligands.
[0007] A need exists in the industry for a process using a bulky
ligand metallocene-type catalyst to produce more easily processable
polymers.
SUMMARY OF THE INVENTION
[0008] This invention relates to a polymerization process utilizing
a bridged bulky ligand metallocene-type catalyst system for
producing polymer products that have excellent processability and
enhanced physical properties. Also, the invention is directed to
improved bridged bulky ligand metallocene-type catalyst compounds
having a cyclic bridge, catalyst systems comprising these
compounds, and polymerizing processes utilizing these
compounds.
[0009] The preferred polymerization processes are a gas phase or a
slurry phase process, most preferably a gas phase process.
[0010] In an embodiment, the invention provides for a process for
polymerizing ethylene alone or in combination with one or more
other olefin(s) in the presence of a cyclic bridged
metallocene-type catalyst compound, preferably an achiral cyclic
bridged metallocene-type catalyst compound, even more preferably an
achiral cyclic bridged metallocene-type catalyst compound having
two substituted bulky ligands and an activator. In a most preferred
embodiment, the cyclic bridged metallocene-type catalyst compound
has two bulky ligands only one of which is a substituted bulky
ligand.
[0011] In another embodiment, the invention relates to a gas phase
or slurry phase process for polymerizing olefin(s) using a cyclic
bridged metallocene-type catalyst system to produce a polymer
product having a M.sub.Z/M.sub.W greater than or equal to 3 and an
I.sub.21/I.sub.2 of greater than 35. In this embodiment, it is
particularly preferred that a supported cyclic bridged
metallocene-type catalyst system is used.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Introduction
[0013] The invention relates to a polymerization process for
producing easy processing polymers using a cyclic bridged bulky
ligand metallocene-type catalyst system. It has been suprisingly
discovered that using the cyclic bridged metallocene-type catalysts
of the invention, particularly in a slurry or gas phase
polymerization process, produces polymers that have a high Melt
Index Ratio (MIR). MIR is simply the ratio of I.sub.21/I.sub.2,
where I.sub.21 is measured by ASTM-D-1238-F and I.sub.2 known as
Melt Index (MI) is measured by ASTM-D-1238-E.
[0014] Bulky Ligand Metallocene-Type Catalyst Compounds
[0015] Generally, bulky ligand metallocene-type catalyst compounds
include half and full sandwich compounds having one or more bulky
ligands bonded to at least one metal atom. Typical bulky ligand
metallocene-type compounds are generally described as containing
one or more bulky ligand(s) and one or more leaving group(s) bonded
to at least one metal atom.
[0016] In one preferred embodiment, at least one bulky ligand is
.eta.-bonded to a metal atom, most preferably .eta..sup.5-bonded to
the metal atom.
[0017] The bulky ligands are generally represented by one or more
open, acyclic, or fused ring(s) or ring system(s) or a combination
thereof. These bulky ligands, preferably ring(s) or ring system(s)
are typically composed of atoms selected from Groups 13 to 16 atoms
of the Periodic Table of Elements, preferably the atoms are
selected from the group consisting of carbon, nitrogen, oxygen,
silicon, sulfur, phosphorous, boron and aluminum or a combination
thereof. Most preferably the ring(s) or ring system(s) are composed
of carbon atoms such as but not limited to those cyclopentadienyl
ligands or cyclopentadienyl-type ligand structures or other similar
functioning ligand structure such as a pentadiene, a
cyclooctatetraendiyl or an imide ligand. The metal atom is
preferably selected from Groups 3 through 15 and the lanthanide or
actinide series of the Periodic Table of Elements. Preferably the
metal is a transition metal from Groups 4 through 12, more
preferably 4, 5 and 6, and most preferably the metal is from Group
4.
[0018] In one embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention are represented by the
formula:
L.sup.AL.sup.BMQ.sub..eta. (I)
[0019] where M is a metal atom from the Periodic Table of the
Elements and may be a Group 3 to 12 metal or from the lanthanide or
actinide series of the Periodic Table of Elements, preferably M is
a Group 4, 5 or 6 transition metal, more preferably M is a Group 4
transition metal, even more preferably M is zirconium, hafnium or
titanium. The bulky ligands, L.sup.A and L.sup.B, are open,
acyclic, or fused ring(s) or ring system(s) such as unsubstituted
or substituted, cyclopentadienyl ligands or cyclopentadienyl-type
ligands, heteroatom substituted and/or heteroatom containing
cyclopentadienyl-type ligands. Non-limiting examples of bulky
ligands include cyclopentadienyl ligands, indenyl ligands,
benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands,
cyclooctatetraendiyl ligands, azenyl ligands, azulene ligands,
pentalene ligands, phosphoyl ligands, pyrrolyl ligands, pyrozolyl
ligands, carbazolyl ligands, borabenzene ligands and the like,
including hydrogenated versions thereof, for example
tetrahydroindenyl ligands. In one embodiment, L.sup.A and L.sup.B
may be any other ligand structure capable of .eta.-bonding to M,
preferably .eta..sup.3-bonding to M, and most preferably
.eta..sup.5-bonding to M. In another embodiment, L.sup.A and
L.sup.B may comprise one or more heteroatoms, for example,
nitrogen, silicon, boron, germanium, sulfur and phosphorous, in
combination with carbon atoms to form an open, acyclic, or
preferably a fused, ring or ring system, for example, a
hetero-cyclopentadienyl ancillary ligand. Other L.sup.A and L.sup.B
bulky ligands include but are not limited to bulky amides,
phosphides, alkoxides, aryloxides, imides, carbolides, borollides,
porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
Independently, each L.sup.A and L.sup.B may be the same or
different type of bulky ligand that is bonded to M.
[0020] Independently, each L.sup.A and L.sup.B may be unsubstituted
or substituted with a combination of substituent groups R.
Non-limiting examples of substituent groups R include one or more
from the group selected from hydrogen, or linear, branched alkyl
radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl
radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy
radicals, aryloxy radicals, alkylthio radicals, dialkylamino
radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals,
carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy
radicals, acylamino radicals, aroylamino radicals, straight,
branched or cyclic, alkylene radicals, or combination thereof.
Non-limiting examples of alkyl substituents R include methyl,
ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl,
benzyl or phenyl groups and the like, including all their isomers,
for example tertiary butyl, isopropyl, and the like. Other
hydrocarbyl radicals include fluoromethyl, fluroethyl,
difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl
substituted organometalloid radicals including trimethylsilyl,
trimethylgermyl, methyldiethylsilyl and the like; and
halocarbyl-substituted organometalloid radicals including
tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,
bromomethyldimethylgermyl and the like; and disubstitiuted boron
radicals including dimethylboron for example; and disubstituted
pnictogen radicals including dimethylamine, dimethylphosphine,
diphenylamine, methylphenylphosphine, chalcogen radicals including
methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.
Non-hydrogen substituents R include the atoms carbon, silicon,
boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur,
germanium and the like, including olefins such as but not limited
to olefinically unsaturated substituents including vinyl-terminated
ligands, for example but-3-enyl, prop-2-enyl, hex-5-enyl and the
like. Also, at least two R groups, preferably two adjacent R
groups, are joined to form a ring structure having from 3 to 30
atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon,
germanium, aluminum, boron or a combination thereof. Also, a
substituent group R group such as 1-butanyl may form a carbon sigma
bond to the metal M.
[0021] Other ligands may be bonded to the metal M, such as at least
one leaving group Q. For the purposes of this patent specification
and appended claims the term "leaving group" is any ligand that can
be abstracted from a bulky ligand metallocene-type catalyst
compound to form a bulky ligand metallocene-type catalyst cation
capable of polymerizing one or more olefin(s). In one embodiment, Q
is a monoanionic labile ligand having a sigma-bond to M. Depending
on the oxidation state of the metal, the value for n is 0, 1 or 2
such that formula (I) above represents a neutral bulky ligand
metallocene-type catalyst compound. Non-limiting examples of Q
ligands include weak bases such as amines, phosphines, ethers,
carboxylates, dienes, hydrocarbyl radicals having from 1 to 20
carbon atoms, hydrides or halogens and the like or a combination
thereof. In another embodiment, two or more Q's form a part of a
fused ring or ring system. Other examples of Q ligands include
those substituents for R as described above and including
cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl,
tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy,
propoxy, phenoxy, bis(N-methylanilide), dimethylamide,
dimethylphosphide radicals and the like.
[0022] The bridged bulky ligand metallocene-type catalyst compounds
of the invention include those of formula (I) where L.sup.A and
L.sup.B are bridged to each other by a cyclic bridging group, A.
For the purposes of this patent application and appended claims,
the cyclic bridging group A comprises greater than 3 non-hydrogen
atoms, preferably greater than 3 carbon atoms forming a ring or
ring system about at least one other Group 13 to 16 atom.
Non-limiting examples of Group 13 to 16 atoms include at least one
of a carbon, oxygen, nitrogen, silicon, boron, germanium and tin
atom or a combination thereof. In a preferred embodiment, the
cyclic bridging group A contains a carbon, silicon or germanium
atom, most preferably A contains at least one silicon atom. The
atoms forming the ring system of A may be substituted with
substituents as defined above for R.
[0023] Non-limiting examples of cyclic bridging groups A include
cyclo-tri or tetra-alkylene silyl or include cyclo-tri or
tetra-alkylene germyl groups, for example, cyclotrimethylenesilyl
group or cyclotetramethylenesilyl group.
[0024] Other examples of cyclic bridging groups are represented by
the following structures: 1
[0025] In a preferred embodiment, the bulky ligand metallocene-type
catalyst compounds of the invention include
cyclotrimethylenesilyl(tetram- ethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride,
cyclotetramethylenesilyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride, cyclotrimethylenesilyl
(tetramethyl cyclopentadienyl) (2-methyl indenyl) zirconium
dichloride, cyclotrimethylenesilyl(tetramethyl cyclopentadienyl)
(3-methyl cyclopentadienyl) zirconium dichloride,
cyclotrimethylenesilyl bis(2-methyl indenyl) zirconium dichloride,
cyclotrimethylenesilyl(tetram- ethyl cyclopentadienyl)
(2,3,5-trimethyl cyclopentadienyl) zirconium dichloride, and
cyclotrimethylenesilyl bis(tetra methyl cyclopentadienyl) zirconium
dichloride.
[0026] In another embodiment, the bulky ligand metallocene-type
catalyst compound of the invention is represented by the
formula:
(C.sub.5H.sub.4-dR.sub.d) (R'A.sub.xR') (C.sub.5H.sub.4-dR.sub.d) M
Qg-.sub.2 (II)
[0027] where M is a Group 4, 5, 6 transition metal,
(C.sub.5H.sub.4-dR.sub.d) is an unsubstituted or substituted,
cyclopentadienyl ligand or cyclopentadienyl-type bulky ligand
bonded to M, each R, which can be the same or different, is
hydrogen or a substituent group containing up to 50 non-hydrogen
atoms or substituted or unsubstituted hydrocarbyl having from 1 to
30 carbon atoms or combinations thereof, or two or more carbon
atoms are joined together to form a part of a substituted or
unsubstituted ring or ring system having 4 to 30 carbon atoms,
R'A.sub.XR' is a cyclic bridging group, where A is one or more of,
or a combination of carbon, germanium, silicon, tin, phosphorous or
bridging two (C.sub.5H.sub.4-dR.sub.d) rings, and the two R''s form
a cyclic ring or ring system with A; more particularly,
non-limiting examples of cyclic bridging group A may be represented
by R'.sub.2C, R'.sub.2Si, R'.sub.2Ge and R'P, where the two R''s
are joined to form a ring or ring system. In one embodiment, R' is
a hydrocarbyl containing a heteroatom, for example boron, nitrogen,
oxygen or a combination thereof. The two R''s may be independently,
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, hydrocarbyl-substituted organometalloid,
halocarbyl-substituted organometalloid, where the two R''s may be
joined to form a ring or ring system having from 2 to 100
non-hydrogen atoms, preferably from 3 to 50 carbon atoms; and
independently, each Q can be the same or different is a hydride,
substituted or unsubstituted, linear, cyclic or branched,
hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides,
aryloxides, amides, phosphides, or any other univalent anionic
ligand or combination thereof; also, two Q's together may form an
alkylidene ligand or cyclometallated hydrocarbyl ligand or other
divalent anionic chelating ligand, where g is an integer
corresponding to the formal oxidation state of M, and d is an
integer selected from 0, 1, 2, 3 or 4 and denoting the degree of
substitution, x is an integer from 1 to 4.
[0028] In one embodiment, the cyclic bridged bulky ligand
metallocene-type catalyst compounds are those where the R
substituents on the bulky ligands L.sup.A, L.sup.B,
(C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) are substituted
with the same or different number of substituents on each of the
bulky ligands. In another embodiment, the bulky ligands L.sup.A,
L.sup.B, (C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) are
different from each other.
[0029] In a preferred embodiment, the bulky ligands of the
metallocene-type catalyst compounds of formula (I) and (II) are
asymmetrically substituted. In another preferred embodiment, at
least one of the bulky ligands L.sup.A, L.sup.B,
(C.sub.5H.sub.4-dR.sub.d) of formulas (I) and (II) is
unsubstituted.
[0030] In the most preferred embodiment, the cyclic bridged
metallocene-type catalyst compounds of the invention are
achiral.
[0031] Other bulky ligand metallocene-type catalysts compounds
useful in the invention include cyclic bridged heteroatom,
mono-bulky ligand metallocene-type compounds. These types of
catalysts and catalyst systems are described in, for example, PCT
publication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506,
WO96/00244 and WO 97/15602 and U.S. Pat. Nos. 5,057,475, 5,096,867,
5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European
publication EP-A-0 420 436, all of which are herein fully
incorporated by reference. Other bulky ligand metallocene-type
catalyst compounds and catalyst systems useful in the invention may
include those described in U.S. Pat. Nos. 5,064,802, 5,145,819,
5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106,
5,329,031, 5,304,614, 5,677,401, 5,723,398 and 5,753,578 and PCT
publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144 and
European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513
380, EP-A1-0 816 372, EP-A2-0 839 834 and EP-B1-0 632 819, all of
which are herein fully incorporated by reference.
[0032] In another embodiment, the cyclic bridged bulky ligand
metallocene-type catalyst compound is represented by the
formula:
L.sup.CAJMQ.sub.n (III)
[0033] where M is a Group 3 to 10 metal atom or a metal selected
from the Group of actinides and lanthanides of the Periodic Table
of Elements, preferably M is a Group 4 to 10 transition metal, and
more preferably M is a Group 4, 5 or 6 transition metal, and most
preferably M is a Group 4 transition metal in any oxidation state,
especially titanium; LC is a substituted or unsubstituted bulky
ligand bonded to M; J is bonded to M; A is bonded to L and J; J is
a heteroatom ancillary ligand; and A is a cyclic bridging group; Q
is a univalent anionic ligand;
[0034] and n is the integer 0,1 or 2. In formula (III) above,
L.sup.C, A and J form a fused ring system. In an embodiment,
L.sup.C of formula (III) is as defined above for L.sup.A in formula
(I), and A, M and Q of formula (III) are as defined above in
formula (I).
[0035] In another embodiment of this invention the bulky ligand
metallocene-type catalyst compound useful in the invention is
represented by the formula:
(C.sub.5H.sub.5-y-xR.sub.x) (R'A.sub.yR')
(JR'.sub.z-1-y)M(Q).sub.n(L').su- b.w (IV)
[0036] where M is a transition metal from Group 4 in any oxidation
state, preferably, titanium, zirconium or hafnium, most preferably
titanium in either a+2, +3 or +4 oxidation state. A combination of
compounds represented by formula (IV) with the transition metal in
different oxidation states is also contemplated. L.sub.C is
represented by (C.sub.5H.sub.5-y-xR.sub.x) and is a bulky ligand as
described above. For purposes of formula (IV) R.sub.0 means no
substituent. More particularly (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ring or cyclopentadienyl-type ring or ring system
which is substituted with from 0 to 4 substituent groups R, and "x"
is 0, 1, 2, 3 or 4 denoting the degree of substitution. Each R is,
independently, a radical selected from a group consisting of 1 to
30 non-hydrogen atoms. More particularly, R is a hydrocarbyl
radical or a substituted hydrocarbyl radical having from 1 to 30
carbon atoms, or a hydrocarbyl-substituted metalloid radical where
the metalloid is a Group 14 or 15 element, preferably silicon or
nitrogen or a combination thereof, and halogen radicals and
mixtures thereof. Substituent R groups also include silyl, germyl,
amine, and hydrocarbyloxy groups and mixtures thereof. Also, in
another embodiment, (C.sub.5H.sub.5-y-xR.sub.x) is a
cyclopentadienyl ligand in which two R groups, preferably two
adjacent R groups are joined to form a ring or ring system having
from 3 to 50 atoms, preferably from 3 to 30 carbon atoms. This ring
system may form a saturated or unsaturated polycyclic
cyclopentadienyl-type ligand such as those bulky ligands described
above, for example, indenyl, tetrahydroindenyl, fluorenyl or
octahydrofluorenyl.
[0037] The (JR'.sub.z-1-y) of formula (IV) is a heteroatom
containing ligand in which J is an element with a coordination
number of three from Group 15 or an element with a coordination
number of two from Group 16 of the Periodic Table of Elements.
Preferably J is a nitrogen, phosphorus, oxygen or sulfur atom with
nitrogen being most preferred. Each R' is, independently, a radical
selected from the group consisting of hydrocarbyl radicals having
from 1 to 20 carbon atoms, or as defined for R in formula (I)
above; the "y" is 1 to 4, preferably 1 to 2, most preferably y is
1, and the "z" is the coordination number of the element J. In one
embodiment, in formula (IV), the J of formula (III) is represented
by (JR'.sub.z-1-y).
[0038] In formula (IV) each Q is, independently, any univalent
anionic ligand such as halogen, hydride, or substituted or
unsubstituted hydrocarbyl having from 1 to 30 carbon atoms,
alkoxide, aryloxide, sulfide, silyl, amide or phosphide. Q may also
include hydrocarbyl groups having ethylenic unsaturation thereby
forming a .eta..sup.3 bond to M. Also, two Q's may be an
alkylidene, a cyclometallated hydrocarbyl or any other divalent
anionic chelating ligand. The integer n may be 0, 1, 2 or 3.
[0039] The (R"A.sub.yR") of formula (IV) is a cyclic bridging group
where A is a Group 13 to 16 element, preferably a Group 14 and 15
element, most preferably a Group 14 element. Non-limiting examples
of A include one or more of, or a combination of carbon, silicon,
germanium, boron, nitrogen, phosphorous, preferably at least one
silicon atom. The two R"'s for a ring or ring system about A, the
two R''s together having from 3 to 100 non-hydrogen atoms,
preferably from 3 to 50 carbon atom.
[0040] Optionally associated with formula (IV) is L', a Lewis base
such as diethylether, tetraethylammonium chloride, tetrahydrofuran,
dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the
like; and w is a number from 0 to 3. Additionally, L' may be bonded
to any of R, R' or Q and n is 0, 1, 2 or 3.
[0041] Activator and Activation Methods for the Bulky Ligand
Metallocene-Type Catalyst Compounds
[0042] The above described cyclic bridged bulky ligand
metallocene-type catalyst compounds are typically activated in
various ways to yield catalyst compounds having a vacant
coordination site that will coordinate, insert, and polymerize
olefin(s).
[0043] For the purposes of this patent specification and appended
claims, the term "activator" is defined to be any compound or
component or method which can activate any of the bulky ligand
metallocene-type catalyst compounds of the invention as described
above. Non-limiting activators, for example may include a Lewis
acid or a non-coordinating ionic activator or ionizing activator or
any other compound including Lewis bases, aluminum alkyls,
conventional-type cocatalysts and combinations thereof that can
convert a neutral bulky ligand metallocene-type catalyst compound
to a catalytically active bulky ligand metallocene cation. It is
within the scope of this invention to use alumoxane or modified
alumoxane as an activator, and/or to also use ionizing activators,
neutral or ionic, such as tri (n-butyl) ammonium tetrakis
(pentafluorophenyl) boron or a trisperfluorophenyl boron metalloid
precursor or a trisperfluoronaphtyl boron metalloid precursor that
would ionize the neutral bulky ligand metallocene-type catalyst
compound.
[0044] In one embodiment, an activation method using ionizing ionic
compounds not containing an active proton but capable of producing
both a bulky ligand metallocene-type catalyst cation and a
non-coordinating anion are also contemplated, and are described in
EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568, which
are all herein incorporated by reference.
[0045] There are a variety of methods for preparing alumoxane and
modified alumoxanes, non-limiting examples of which are described
in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,
5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,
5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,
5,391,529, 5,693,838, 5,731,253, 5,731,451 5,744,656 and European
publications EP-A-0 561 476, EP-B 1-0 279 586 and EP-A-0 594-218,
and PCT publication WO 94/10180, all of which are herein fully
incorporated by reference.
[0046] Ionizing compounds may contain an active proton, or some
other cation associated with but not coordinated to or only loosely
coordinated to the remaining ion of the ionizing compound. Such
compounds and the like are described in European publications
EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-500 944,
EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157,
5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124
and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,
1994, all of which are herein fully incorporated by reference.
[0047] Other activators include those described in PCT publication
WO 98/07515 such as tris (2, 2', 2"-nonafluorobiphenyl)
fluoroaluminate, which publication is fully incorporated herein by
reference. Combinations of activators are also contemplated by the
invention, for example, alumoxanes and ionizing activators in
combinations, see for example, PCT publications WO 94/07928 and WO
95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which
are herein fully incorporated by reference. WO 98/09996
incorporated herein by reference describes activating bulky ligand
metallocene-type catalyst compounds with perchlorates, periodates
and iodates including their hydrates. WO 98/30602 and WO 98/30603
incorporated by reference describe the use of lithium
(2,2'-bisphenyl-ditrimethylsilicate).cndot.4THF as an activator for
a bulky ligand metallocene-type catalyst compound. Also, methods of
activation such as using radiation (see EP-B 1 -0 615 981 herein
incorporated by reference), electrochemical oxidation, and the like
are also contemplated as activating methods for the purposes of
rendering the neutral bulky ligand metallocene-type catalyst
compound or precursor to a bulky ligand metallocene-type cation
capable of polymerizing olefins.
[0048] It is further contemplated by the invention that other
catalysts can be combined with the cyclic bridged bulky ligand
metallocene-type catalyst compounds of the invention. For example,
see U.S. Pat. Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015,
5,470,811, and 5,719,241 all of which are herein fully incorporated
herein reference.
[0049] In another embodiment of the invention one or more bulky
ligand metallocene-type catalyst compounds or catalyst systems may
be used in combination with one or more conventional-type catalyst
compounds or catalyst systems. Non-limiting examples of mixed
catalysts and catalyst systems are described in U.S. Pat. Nos.
4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867,
5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCT
Publication WO 96/23010 published Aug. 1, 1996, all of which are
herein fully incorporated by reference.
[0050] Method for Supporting
[0051] The above described cyclic bulky ligand metallocene-type
catalyst compounds and catalyst systems may be combined with one or
more support materials or carriers using one of the support methods
well known in the art or as described below. In the preferred
embodiment, the method of the invention uses a polymerization
catalyst in a supported form. For example, in a most preferred
embodiment, a bulky ligand metallocene-type catalyst compound or
catalyst system is in a supported form, for example deposited on,
bonded to, contacted with, or incorporated within, adsorbed or
absorbed in, or on, a support or carrier.
[0052] The terms "support" or "carrier" are used interchangeably
and are any support material, preferably a porous support material,
for example, talc, inorganic oxides and inorganic chlorides. Other
carriers include resinous support materials such as polystyrene,
functionalized or crosslinked organic supports, such as polystyrene
divinyl benzene polyolefins or polymeric compounds, zeolites,
clays, or any other organic or inorganic support material and the
like, or mixtures thereof.
[0053] The preferred carriers are inorganic oxides that include
those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred
supports include silica, alumina, silica-alumina, magnesium
chloride, and mixtures thereof. Other useful supports include
magnesia, titania, zirconia, montmorillonite (EP-B 1 0 511 665) and
the like. Also, combinations of these support materials may be
used, for example, silica-chromium, silica-alumina, silica-titania
and the like.
[0054] It is preferred that the carrier, most preferably an
inorganic oxide, has a surface area in the range of from about 10
to about 700 m.sup.2/g, pore volume in the range of from about 0.1
to about 4.0 cc/g and average particle size in the range of from
about 5 to about 500 .mu.m. More preferably, the surface area of
the carrier is in the range of from about 50 to about 500
m.sup.2/g, pore volume of from about 0.5 to about 3.5 cc/g and
average particle size of from about 10 to about 200 .mu.m. Most
preferably the surface area of the carrier is in the range is from
about 100 to about 400 m.sup.2/g, pore volume from about 0.8 to
about 3.0 cc/g and average particle size is from about 5 to about
100 .mu.m. The average pore size of the carrier of the invention
typically has pore size in the range of from 10 to 1000 .ANG.,
preferably 50 to about 500 .ANG., and most preferably 75 to about
350 .ANG..
[0055] Examples of supporting the bulky ligand metallocene-type
catalyst systems of the invention are described in U.S. Pat. Nos.
4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,
5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,
5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,
5,723,402, 5,731,261, 5,759,940, 5,767,032 and 5,770,664 and U.S.
application Ser. Nos. 271,598 filed Jul. 7, 1994 and 788,736 filed
Jan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO
96/06187 and WO 97/02297 all of which are herein fully incorporated
by reference.
[0056] In one embodiment, the cyclic bridged bulky ligand
metallocene-type catalyst compounds of the invention may be
deposited on the same or separate supports together with an
activator, or the activator may be used in an unsupported form, or
may be deposited on a support different from the supported bulky
ligand metallocene-type catalyst compounds of the invention, or any
combination thereof.
[0057] There are various other methods in the art for supporting a
polymerization catalyst compound or catalyst system of the
invention. For example, the cyclic bridged bulky ligand 10
metallocene-type catalyst compound of the invention may contain a
polymer bound ligand as described in U.S. Pat. Nos. 5,473,202 and
5,770,755, which is herein fully incorporated by reference; the
bulky ligand metallocene-type catalyst system of the invention may
be spray dried as described in U.S. Pat. No. 5,648,310, which is
herein fully incorporated by reference; the support used with the
cyclic bridged bulky ligand metallocene-type catalyst system of the
invention is functionalized as described in European publication
EP-A-0 802 203, which is herein fully incorporated by reference, or
at least one substituent or leaving group is selected as described
in U.S. Pat. No. 5,688,880, which is herein fully incorporated by
reference.
[0058] In a preferred embodiment, the invention provides for a
supported cyclic bridged bulky ligand metallocene-type catalyst
system that includes an antistatic agent or surface modifier that
is used in the preparation of the supported catalyst system as
described in PCT publication WO 96/11960, which is herein fully
incorporated by reference. The catalyst systems of the invention
can be prepared in the presence of an olefin, for example
hexene-1.
[0059] A preferred method for producing the supported cyclic
bridged bulky ligand metallocene-type catalyst system of the
invention is described below and is described in U.S. application
Ser. Nos. 265,533, filed Jun. 24, 1994 and 265,532, filed Jun. 24,
1994 and PCT publications WO 96/00245 and WO 96/00243 both
published Jan. 4, 1996, all of which are herein fully incorporated
by reference. In this preferred method, the cyclic bridged bulky
ligand metallocene-type catalyst compound is slurried in a liquid
to form a metallocene solution and a separate solution is formed
containing an activator and a liquid. The liquid may be any
compatible solvent or other liquid capable of forming a solution or
the like with the cyclic bridged bulky ligand metallocene-type
catalyst compounds and/or activator of the invention. In the most
preferred embodiment the liquid is a cyclic aliphatic or aromatic
hydrocarbon, most preferably toluene. The cyclic bridged bulky
ligand metallocene-type catalyst compound and activator solutions
are mixed together and added to a porous support or the porous
support is added to the solutions such that the total volume of the
bulky ligand metallocene-type catalyst compound solution and the
activator solution or the bulky ligand metallocene-type catalyst
compound and activator solution is less than four times the pore
volume of the porous support, more preferably less than three
times, even more preferably less than two times; preferred ranges
being from 1.1 times to 3.5 times range and most preferably in the
1.2 to 3 times range.
[0060] Procedures for measuring the total pore volume of a porous
support are well known in the art. Details of one of these
procedures is discussed in Volume 1, Experimental Methods in
Catalytic Research (Academic Press, 1968) (specifically see pages
67-96). This preferred procedure involves the use of a classical
BET apparatus for nitrogen absorption. Another method well known in
the art is described in Innes, Total Porosity and Particle Density
of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical
Chemistry 332-334 (March, 1956).
[0061] The mole ratio of the metal of the activator component to
the metal of the supported cyclic bridged bulky ligand
metallocene-type catalyst compounds are in the range of between
0.3:1 to 1000:1, preferably 20:1 to 800:1, and most preferably 50:1
to 500:1. Where the activator is an ionizing activator such as
those based on the anion tetrakis(pentafluorophenyl)boron, the mole
ratio of the metal of the activator component to the metal
component of the cyclic bridged bulky ligand metallocene-type
catalyst is preferably in the range of between 0.3:1 to 3:1. Where
an unsupported cyclic bridged bulky ligand metallocene-type
catalyst system is utilized, the mole ratio of the metal of the
activator component to the metal of the cyclic bridged bulky ligand
metallocene-type catalyst compound is in the range of between 0.3:1
to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1
to 2000:1.
[0062] In one embodiment of the invention, olefin(s), preferably
C.sub.2 to C.sub.30 olefin(s) or alpha-olefin(s), preferably
ethylene or propylene or combinations thereof are prepolymerized in
the presence of the cyclic bridged bulky ligand metallocene-type
catalyst system of the invention prior to the main polymerization.
The prepolymerization can be carried out batchwise or continuously
in gas, solution or slurry phase including at elevated pressures.
The prepolymerization can take place with any olefin monomer or
combination and/or in the presence of any molecular weight
controlling agent such as hydrogen. For examples of
prepolymerization procedures, see U.S. Pat. Nos. 4,748,221,
4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and
European publication EP-B-0279 863 and PCT Publication WO 97/44371
all of which are herein fully incorporated by reference.
[0063] In one embodiment the polymerization catalyst is used in an
unsupported form, preferably in a liquid form such as described in
U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication
EP-A-0 593 083, all of which are herein incorporated by reference.
The polymerization catalyst in liquid form can be fed to a reactor
as described in PCT publication WO 97/46599, which is fully
incorporated herein by reference.
[0064] In one embodiment, the cyclic bridged metallocene-type
catalysts of the invention can be combined with a carboxylic acid
salt of a metal ester, for example aluminum carboxylates such as
aluminum mono, di- and tri- stearates, aluminum octoates, oleates
and cyclohexylbutyrates, as described in U.S. application Ser. No.
09/113,216, filed Jul. 10, 1998.
[0065] Polymerization Process
[0066] The catalysts and catalyst systems of the invention
described above are suitable for use in any polymerization process
over a wide range of temperatures and pressures. The temperatures
may be in the range of from -60.degree. C. to about 280.degree. C.,
preferably from 50.degree. C. to about 200.degree. C., and the
pressures employed may be in the range from 1 atmosphere to about
500 atmospheres or higher.
[0067] Polymerization processes include solution, gas phase, slurry
phase and a high pressure process or a combination thereof.
Particularly preferred is a gas phase or slurry phase
polymerization of one or more olefins at least one of which is
ethylene or propylene.
[0068] In one embodiment, the process of this invention is directed
toward a solution, high pressure, slurry or gas phase
polymerization process of one or more olefin monomers having from 2
to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more
preferably 2 to 8 carbon atoms. The invention is particularly well
suited to the polymerization of two or more olefin monomers of
ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,
hexene-1, octene-1 and decene-1.
[0069] Other monomers useful in the process of the invention
include ethylenically unsaturated monomers, diolefins having 4 to
18 carbon atoms, conjugated or nonconjugated dienes, polyenes,
vinyl monomers and cyclic olefins. Non-limiting monomers useful in
the invention may include norbomene, norbomadiene, isobutylene,
isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted
styrene, ethylidene norbornene, dicyclopentadiene and
cyclopentene.
[0070] In the most preferred embodiment of the process of the
invention, a copolymer of ethylene is produced, where with
ethylene, a comonomer having at least one alpha-olefin having from
4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and
most preferably from 4 to 8 carbon atoms, is polymerized in a gas
phase process.
[0071] In another embodiment of the process of the invention,
ethylene or propylene is polymerized with at least two different
comonomers, optionally one of which may be a diene, to form a
terpolymer.
[0072] In one embodiment, the invention is directed to a
polymerization process, particularly a gas phase or slurry phase
process, for polymerizing propylene alone or with one or more other
monomers including ethylene, and/or other olefins having from 4 to
12 carbon atoms. Polypropylene polymers may be produced using the
particularly bridged bulky ligand metallocene-type catalysts as
described in U.S. Pat. Nos. 5,296,434 and 5,278,264, both of which
are herein incorporated by reference.
[0073] Typically in a gas phase polymerization process a continuous
cycle is employed where in one part of the cycle of a reactor
system, a cycling gas stream, otherwise known as a recycle stream
or fluidizing medium, is heated in the reactor by the heat of
polymerization. This heat is removed from the recycle composition
in another part of the cycle by a cooling system external to the
reactor. Generally, in a gas fluidized bed process for producing
polymers, a gaseous stream containing one or more monomers is
continuously cycled through a fluidized bed in the presence of a
catalyst under reactive conditions. The gaseous stream is withdrawn
from the fluidized bed and recycled back into the reactor.
Simultaneously, polymer product is withdrawn from the reactor and
fresh monomer is added to replace the polymerized monomer. (See for
example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,
5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661
and 5,668,228, all of which are fully incorporated herein by
reference.)
[0074] The reactor pressure in a gas phase process may vary from
about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably
in the range of from about 200 psig (1379 kPa) to about 400 psig
(2759 kPa), more preferably in the range of from about 250 psig
(1724 kPa) to about 350 psig (2414 kPa).
[0075] The reactor temperature in a gas phase process may vary from
about 30.degree. C. to about 120.degree. C., preferably from about
60.degree. C. to about 115.degree. C., more preferably in the range
of from about 70.degree. C. to 110.degree. C., and most preferably
in the range of from about 70.degree. C. to about 95.degree. C.
[0076] Other gas phase processes contemplated by the process of the
invention include those described in U.S. Pat. Nos. 5,627,242,
5,665,818 and 5,677,375, and European publications EP-A-0 794 200,
EP-A-0 802 202 and EP-B-634 421 all of which are herein fully
incorporated by reference.
[0077] In a preferred embodiment, the reactor utilized in the
present invention is capable and the process of the invention is
producing greater than 500 lbs of polymer per hour (227 Kg/hr) to
about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer,
preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably
greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably
greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably
greater than 35,000 lbs/hr (15,900 Kg/hr), still even more
preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most
preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater
than 100,000 lbs/hr (45,500 Kg/hr).
[0078] A slurry polymerization process generally uses pressures in
the range of from about 1 to about 50 atmospheres and even greater
and temperatures in the range of 0.degree. C. to about 120.degree.
C. In a slurry polymerization, a suspension of solid, particulate
polymer is formed in a liquid polymerization diluent medium to
which ethylene and comonomers and often hydrogen along with
catalyst are added. The suspension including diluent is
intermittently or continuously removed from the reactor where the
volatile components are separated from the polymer and recycled,
optionally after a distillation, to the reactor. The liquid diluent
employed in the polymerization medium is typically an alkane having
from 3 to 7 carbon atoms, preferably a branched alkane. The medium
employed should be liquid under the conditions of polymerization
and relatively inert. When a propane medium is used the process
must be operated above the reaction diluent critical temperature
and pressure. Preferably, a hexane or an isobutane medium is
employed.
[0079] A preferred polymerization technique of the invention is
referred to as a particle form polymerization, or a slurry process
where the temperature is kept below the temperature at which the
polymer goes into solution. Such technique is well known in the
art, and described in for instance U.S. Pat. No. 3,248,179 which is
fully incorporated herein by reference. Other slurry processes
include those employing a loop reactor and those utilizing a
plurality of stirred reactors in series, parallel, or combinations
thereof. Non-limiting examples of slurry processes include
continuous loop or stirred tank processes. Also, other examples of
slurry processes are described in U.S. Pat. No. 4,613,484, which is
herein fully incorporated by reference.
[0080] In an embodiment the reactor used in the slurry process of
the invention is capable of and the process of the invention is
producing greater than 2000 lbs of polymer per hour (907 Kg/hr),
more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most
preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another
embodiment the slurry reactor used in the process of the invention
is producing greater than 15,000 lbs of polymer per hour (6804
Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to
about 100,000 lbs/hr (45,500 Kg/hr).
[0081] Examples of solution processes are described in U.S. Pat.
Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are fully
incorporated herein by reference
[0082] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated in the
presence of a bulky ligand metallocene-type catalyst system of the
invention and in the absence of or essentially free of any
scavengers, such as triethylaluminum, trimethylaluminum,
tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum
chloride, dibutyl zinc and the like. This preferred process is
described in PCT publication WO 96/08520 and U.S. Pat. No.
5,712,352 and 5,763,543, which are herein fully incorporated by
reference. In another preferred embodiment of the process of the
invention, the process is operated by introducing a benzil compound
into the reactor and/or contacting a benzil compound with the bulky
ligand metallocene-type catalyst system of the invention prior to
its introduction into the reactor.
[0083] Polymer Product of the Invention
[0084] The polymers produced by the process of the invention can be
used in a wide variety of products and end-use applications. The
polymers produced by the process of the invention include linear
low density polyethylene, elastomers, plastomers, high density
polyethylenes, low density polyethylenes, polypropylene and
polypropylene copolymers.
[0085] The polymers, typically ethylene based polymers, have a
density in the range of from 0.86g/cc to 0.97 g/cc, preferably in
the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the
range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the
range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in
the range from 0.910 g/cc to 0.940 g/cc, and most preferably
greater than 0.915 g/cc to about 0.930 g/cc.
[0086] The melt strength of the polymers produced using the
catalyst of the invention are greater than 4 cN, preferably greater
than 5 cN. For purposes of this patent application and appended
claims melt strength is measured with an Instron capillary
rheometer in conjunction with the Goettfert Rheotens melt strength
apparatus. A polymer melt strand extruded from the capillary die is
gripped between two counter-rotating wheels on the apparatus. The
take-up speed is increased at a constant acceleration of 24
mm/sec.sup.2, which is controlled by the Acceleration Programmer
(Model 45917, at a setting of 12). The maximum pulling force (in
the unit of cN) achieved before the strand breaks or starts to show
draw-resonance is determined as the melt strength. The temperature
of the rheometer is set at 190.degree. C. The capillary die has a
length of one inch (2.54 cm) and a diameter of 0.06" (0.15cm). The
polymer melt is extruded from the die at a speed of 3 inch/min
(7.62 cm/min). The distance between the die exit and the wheel
contact point should be 3.94 inches (100 mm).
[0087] The polymers produced by the process of the invention
typically have a molecular weight distribution, a weight average
molecular weight to number average molecular weight
(M.sub.w/M.sub.n) of greater than 1.5 to about 15, particularly
greater than 2 to about 10, more preferably greater than about 2.5
to less than about 8, and most preferably from 3.0 to 8.
[0088] In one preferred embodiment, the polymers of the present
invention have a M,/M, of greater than or equal to 3, preferably
greater than 3. M. is the z-average molecular weight. In another
preferred embodiment, the polymers of the invention have a
M.sub.Z/M.sub.W of greater than or equal to 3.0 to about 4. In yet
another preferred embodiment, the M)M, is in the range greater than
3 to less than 4.
[0089] Also, the polymers of the invention typically have a narrow
composition distribution as measured by Composition Distribution
Breadth Index (CDBI). Further details of determining the CDBI of a
copolymer are known to those skilled in the art. See, for example,
PCT Patent Application WO 93/03093, published Feb. 18, 1993, which
is fully incorporated herein by reference.
[0090] The bulky ligand metallocene-type catalyzed polymers of the
invention in one embodiment have CDBI's generally in the range of
greater than 50% to 100%, preferably 99%, preferably in the range
of 55% to 85%, and more preferably 60% to 80%, even more preferably
greater than 60%, still even more preferably greater than 65%. In
another embodiment, polymers produced using a bulky ligand
metallocene-type catalyst system of the invention have a CDBI less
than 50%, more preferably less than 40%, and most preferably less
than 30%.
[0091] The polymers of the present invention in one embodiment have
a melt index (MI) or (I.sub.2) as measured by ASTM-D-1238-E in the
range from 0.01 dg/min to 1000 dg/min, more preferably from about
0.01 dg/min to about 100 dg/min, even more preferably from about
0.1 dg/min to about 50 dg/min, and most preferably from about 0.1
dg/min to about 10 dg/min.
[0092] The polymers of the invention in an embodiment have a melt
index ratio (121/I.sub.2) ( 121 is measured by ASTM-D-1238-F) of
from 30 to less than 200, more preferably from about 35 to less
than 100, and most preferably from 40 to 95.
[0093] The polymers of the invention in a preferred embodiment have
a melt index ratio (I.sub.21/I.sub.2) (I.sub.21 is measured by
ASTM-D-1238-F) of from preferably greater than 30, more preferably
greater than 35, even more preferably greater that 40, still even
more preferably greater than 50 and most preferably greater than
65.
[0094] The polymers of the invention may be blended and/or
coextruded with any other polymer. Non-limiting examples of other
polymers include linear low density polyethylenes produced via
conventional Ziegler-Natta and/or bulky ligand metallocene-type
catalysis, elastomers, plastomers, high pressure low density
polyethylene, high density polyethylenes, polypropylenes and the
like.
[0095] Polymers produced by the process of the invention and blends
thereof are useful in such forming operations as film, sheet, and
fiber extrusion and co-extrusion as well as blow molding, injection
molding and rotary molding. Films include blown or cast films
formed by coextrusion or by lamination useful as shrink film, cling
film, stretch film, sealing films, oriented films, snack packaging,
heavy duty bags, grocery sacks, baked and frozen food packaging,
medical packaging, industrial liners, membranes, etc. in
food-contact and non-food contact applications. Fibers include melt
spinning, solution spinning and melt blown fiber operations for use
in woven or non-woven form to make filters, diaper fabrics, medical
garments, geotextiles, etc. Extruded articles include medical
tubing, wire and cable coatings, geomembranes, and pond liners.
Molded articles include single and multi-layered constructions in
the form of bottles, tanks, large hollow articles, rigid food
containers and toys, etc.
EXAMPLES
[0096] In order to provide a better understanding of the present
invention including representative advantages thereof, the
following examples are offered.
[0097] For the following examples, the following was utilized. In
all the Examples below the methylalumoxane (MAO) used was a 30
weight percent MAO solution in toluene (typically 13.5 wt %
Aluminum and 28.2 wt % MAO by NMR) available from Albemarle
Corporation, Baton Rouge, La., the Davison 948 silica dehydrated to
600.degree. C. (silica gel) available from W.R. Grace, Davison
Chemical Division, Baltimore, Maryland. Toluene was anhydrous from
Aldrich, and used without further purification. The compounds
(C.sub.3H.sub.6)SiCl.sub.2 and (C.sub.4H.sub.8)SiCl.sub.2 were
purchased from Gelest and Lancaster.
[0098] The synthesis of the metallocene compounds of the invention
are well known. Example 1 illustrates the typical synthesis route
to producing the compounds of the invention including those used in
the following examples.
Example 1
Synthesis of
(C.sub.3H.sub.6)Si(C.sub.5Me.sub.4).sub.2ZrCl.sub.2
[0099] To a slurry of C.sub.5Me.sub.4HLi (5.2 g, 40.6 mmol) in THF
(100 ml) was added (C.sub.3H.sub.6)SiCl.sub.2 (2.84 g, 20.3 mmol).
The reaction mixture was stirred for 1 h and reacted with 1
equivalent NaCp (sodium cylopentadiene) (2.0 M, THF). After
stirring for one hour the volatiles were removed and the reaction
extracted with pentane and filtered through a glass frit. The
filtrate was treated with 2.1 equiv. nBuLi (10.0 M, hexanes), based
on (C.sub.3H.sub.6)SiCl.sub.2 and stirred for 2 h. The volatiles
were removed in vacuo and the crude white dianion washed with
pentane and collected on a glass frit. One half of the dianion was
dissolved in Et.sub.2O (80 ml) and reacted with solid ZrCl4 (2.2 g,
9.4 mmol). The volatiles were removed in vacuo from the greenish
reaction mixture and the remaining solid extracted with
CH.sub.2Cl.sub.2 (60 ml). The extract's volatiles were slowly
removed to induce precipitation of the product. A yellow solid was
filtered from the solution (1.82 g, 41.0% yield).
Example 2
Catalyst Preparation for
(C.sub.3H.sub.6)Si(C.sub.5Me.sub.4).sub.2ZrCl.sub- .2
[0100] (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4).sub.2ZrCl.sub.2 (0.63 g,
1.33 mmol) was weighed into a beaker and reacted with 32.0 g 30%
MAO in toluene (available from Albemarle Corporation, Baton Rouge,
La.) and 32.0 g toluene and stirred until dissolution (10 min). To
the reaction mixture was added 24.0 g silica gel (Davison 948,
600.degree. C., available from W.R. Grace, Davison Chemical
Division, Baltimore, Md.,) and mixed with a spatula. The resulting
mud was dried in vacuo at room temperature for 15 h and transferred
into a bomb for screening in a continuous gas phase pilot
plant.
Example 3
Catalyst Preparation
Catalyst Preparation for (C.sub.3H.sub.6)Si(2-methylC.sub.9H.sub.5)
(C.sub.5Me.sub.4)ZrCl.sub.2
[0101] (C.sub.3H.sub.6)Si(2-methylC.sub.9H.sub.5)
(C.sub.5Me.sub.4)ZrCl.su- b.2 (0.40 g, 0.83 mmol) was weighed into
a beaker and reacted with 53.5 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.) and 53.5 g toluene and
stirred until dissolution (10 min). To the reaction mixture was
added 40.0 g silica gel (Davison 948, 600.degree. C., available
from W.R. Grace, Davison Chemical Division, Baltimore, Md.,) and
mixed with a spatula. The resulting mud was dried in vacuo at room
temperature for 15 h and transferred into a bomb for screening in a
continuous gas phase pilot plant. After drying this catalyst, it
was dry-coated with 1.4 g Al Stearate which had been dried in vacuo
at 85.degree. C. for 18 hr.
Example 4
Catalyst Preparation for (C.sub.3H.sub.6)Si(C.sub.5H.sub.4)
(C.sub.5Me.sub.4)ZrCl.sub.2
[0102] (C.sub.3H.sub.6)Si(2-methylC.sub.9H.sub.5)
(C.sub.5Me.sub.4)ZrCl.su- b.2 (0.39 g, 0.93 mmol) was weighed into
a beaker and reacted with 53.5 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.) and 53.5 g toluene and
stirred until dissolution (10 min). To the reaction mixture was
added 40.0 g silica gel (Davison 948, 600.degree. C., available
from W.R. Grace, Davison Chemical Division, Baltimore, Md.,) and
mixed with a spatula. The resulting mud was dried in vacuo at room
temperature for 15 h and transferred into a bomb for screening in a
continuous gas phase pilot plant.
Example 5
Catalyst Preparation for (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4)
(3MeC.sub.5H.sub.3)ZrCl.sub.2
[0103] (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4)
(3MeC.sub.5H.sub.3)ZrCl.sub.2 (0.71 g, 1.65 mmol) was weighed into
a beaker and reacted with 53.5 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.) and 53.5 g toluene and
stirred until dissolution (10 min). To the reaction mixture was
added 40.0 g silica gel (Davison 948, 600.degree. C., available
from W.R. Grace, Davison Chemical Division, Baltimore, Md.,) and
mixed with a spatula. The resulting mud was dried in vacuo at room
temperature for 15 h and transferred into a bomb for screening in a
continuous gas phase pilot plant.
Example 6
Catalyst Preparation for (C.sub.4H.sub.8)Si(C.sub.5Me.sub.4)
(C.sub.5H.sub.4)ZrCl.sub.2
[0104] (C.sub.4H.sub.8)Si(C.sub.5Me.sub.4)
(C.sub.5H.sub.4)ZrCl.sub.2 (0.71 g, 1.65 mmol) was weighed into a
beaker and reacted with 53.5 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.) and 53.5 g toluene and
stirred until dissolution (10 min). To the reaction mixture was
added 40.0 g silica gel (Davison 948, 600.degree. C., available
from W.R. Grace, Davison Chemical Division, Baltimore, Md.,) and
mixed with a spatula. The resulting mud was dried in vacuo at room
temperature for 15 h and transferred into a bomb for screening in a
continuous gas phase pilot plant.
Example 7
Catalyst Preparation for 50/50 racemic/meso of
(C.sub.3H.sub.6)Si(2-methyl- C.sub.9H.sub.5).sub.2ZrCl.sub.2
[0105] A 50/50 rac-/meso mixture of
(C.sub.3H.sub.6)Si(2-methylC.sub.9H.su- b.5).sub.2ZrCl.sub.2 (0.81
g, 1.65 mmol) was weighed into a beaker and reacted with 53.5 g 30%
MAO in toluene (available from Albemarle Corporation, Baton Rouge,
La.) and 53.5 g toluene and stirred until dissolution (10 min). To
the reaction mixture was added 40.0 g silica gel (Davison 948,
600.degree. C., available from W.R. Grace, Davison Chemical
Division, Baltimore, Md.,) and mixed with a spatula. The resulting
mud was dried in vacuo at room temperature for 15 h and transferred
into a bomb for screening in a continuous gas phase pilot
plant.
Example 8
Catalyst Preparation for (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4)
(C.sub.5Me.sub.3)ZrCl.sub.2
[0106] (C.sub.3H.sub.6)Si(C.sub.5Me.sub.4)
(C.sub.5Me.sub.3)ZrCl.sub.2 (0.48 g, 1.05 mmol) was weighed into a
beaker and reacted with 33.5 g 30% MAO in toluene (available from
Albemarle Corporation, Baton Rouge, La.) and 33.5 g toluene and
stirred until dissolution (10 min). To the reaction mixture was
added 25.0 g silica gel (Davison 948, 600.degree. C., available
from W.R. Grace, Davison Chemical Division, Baltimore, Md.,) and
mixed with a spatula. The resulting mud was dried in vacuo at room
temperature for 15 h and transferred into a bomb for screening in a
continuous gas phase pilot plant.
Example 9
Polymerization for Examples 2 through 8
[0107] All the catalysts prepared in Examples 2 through 8 were
screened in a fluidized bed reactor equipped with devices for
temperature control, catalyst feeding or injection equipment, GC
analyzer for monitoring and controlling monomer and gas feeds and
equipment for polymer sampling and collecting. The reactor consists
of a 6 inch (15.24 cm) diameter bed section increasing to, 10
inches (25.4 cm) at the reactor top. Gas comes in through a
perforated distributor plate allowing fluidization of the bed
contents and polymer sample is discharged at the reactor top.
1TABLE 1 Example Example 2 Example 3 Example 4 Example 5 Example 6
Example 7 Example 8 Temperature (.degree. F.) 170 (76.7) 175 175
175 (79.4) 175 (79.4) 175 (79.4) 175 (79.4) (.degree. C.) (79.4)
(79.4) Pressure (psi) 300 (2067) 300 300 300 300 300 300 (kPa)
(2067) (2067) (2067) (2067) (2067) (2067) Ethylene (mole %) 30.4
35.2 35 35.2 35.1 35 35 Hydrogen (mole 498 816 1024 812 904 971 686
ppm) Hydrogen/Ethylene 16.4 23.2 29.3 23.1 25.7 27.8 19.6
Concentration ratio Hexene (mole %) 0.57 0.29 0.33 0.52 0.63 0.23
0.24 Hexene/Ethylene 0.019 0.008 0.009 0.015 0.018 0.007 0.01
Concentration Bed Weight (g) 642 1773 1874 1948 1868 1757 1918
Residence Time 3.4 4.8 2.6 4.5 8.1 4.9 4.4 (hrs) Productivity.sup.1
(g/g) 1617 1493 959 1406 444 416 1297 Gas Velocity 0.547 (16.7)
1.54 (47) 1.6 (49) 1.49 1.6 (49) 1.6 (49) 1.59 (ft/sec) (cm/sec)
(45.4) (48.5) Production Rate 188 370 713 437 231 416 440 (g/h)
Bulk Density 0.4168 0.4748 0.4798 Not Meas. Not Meas. 0.4748 0.4503
(g/cc) .sup.1Productivity is number of grams of product per gram of
catalyst.
Example 10
Catalyst preparation for (C.sub.3H.sub.6)Si(2-methylC.sub.9H.sub.5)
(C.sub.5Me.sub.4)ZrCl.sub.2
[0108] 1341 ml of 30% MAO in toluene (available from Albemarle
Corporation, Baton Rouge, La.) was added to a 2 gallon glass
reactor vessel with a heating/cooling jacket and a helical ribbon
blender having a central auger-type shaft. 2200 ml toluene was
added to the reaction vessel. A suspension of 22.0 g
(C.sub.3H.sub.6)Si(2-methylC.sub.9H.sub.5)
(C.sub.5Me.sub.4)ZrCl.sub.2 in 250 ml toluene was transferred to
the reaction vessel via cannula. An additional 150 ml toluene was
used to rinse the bottle containing the metallocene compound
suspension. The reaction mixture was heated to 155.degree. F.
(68.30.degree. C.) and stirred for 1 hr. The reaction mixture was
transferred to a large glass flask and 500 g silica gel was added
with mixing. Two additional increments of silica gel (250 g each)
were added to the mixture. The supported catalyst was added back to
the original reactor vessel with stirring and 28.6 g AS-990 in 286
ml of toluene was added. (AS-990 is (N,N-bis
(2-hydroxylethyl)octadecylamine (C.sub.18H.sub.37N(CH.sub.2CH.su-
b.2OH).sub.2)) available as Kemamine AS-990 from ICI Specialties,
Wilmington, Del.). The catalyst was dried by N.sub.2 purge at
120.degree. F. (49.degree. C.) until free flowing. The dried
catalyst was dry-mixed with 3.0 wt % of Aluminum Stearate #22 in a
dry box, (AlSt #22 is (CH.sub.3(CH.sub.2).sub.16COO).sub.2Al--OH
and is available from Witco Corporation, Memphis, Tenn.), then
transferred to a catalyst bomb for testing.
Example 11
Catalyst Preparation for (C.sub.3H.sub.6)Si(C.sub.5H.sub.4)
(C.sub.5Me.sub.4)ZrF.sub.2
[0109] 1609 ml of 30% MAO in toluene (available from Albemarle
Corporation, Baton Rouge, La.) was added to a 2 gallon glass
reactor vessel with a heating/cooling jacket and a helical ribbon
blender having a central auger-type shaft. 2200 ml toluene was
added to the reaction vessel. A suspension of 19.4 g
(C.sub.3H.sub.6)Si(C.sub.5H.sub.4) (C.sub.5Me.sub.4)ZrF.sub.2 in
250 ml toluene was transferred to the reaction vessel via cannula.
An additional 200 ml toluene was used to rinse the bottle
containing the metallocene compound suspension. The reaction
mixture was heated to 155.degree. F. (68.3.degree. C.) and stirred
for 1 hr. The reaction mixture was transferred to a large glass
flask and 500 g silica gel was added with mixing. Two additional
increments of silica gel (250 g each) were added to the mixture.
The supported catalyst was added back to the original reactor
vessel with stirring and 30.2 g AS-990 in 286 ml of toluene was
added. (AS-990 is (N,N-bis (2-hydroxylethyl) octadecylamine
(C.sub.18H.sub.37N(CH.sub.2CH.s- ub.2OH).sub.2)) available as
Kemamine AS-990 from ICI Specialties, Wilmington, Del.). The
catalyst was dried by N.sub.2 purge at 120.degree. F. (49.degree.
C.) until free flowing. The dried catalyst was dry-mixed with 2.5
wt % of Aluminum Stearate #22 in a dry box, (AlSt #22 is
(CH.sub.3(CH.sub.2).sub.16COO).sub.2Al--OH and is available from
Witco Corporation, Memphis, Tenn.), then transferred to a catalyst
bomb for testing.
Example 12
Catalyst Preparation for (C.sub.4H.sub.8)Si(C.sub.5Me.sub.4)
(C.sub.5H.sub.4)ZrCl.sub.2
[0110] 1609 ml of 30% MAO in toluene (available from Albemarle
Corporation, Baton Rouge, La.) was added to a 2 gallon glass
reactor vessel with a heating/cooling jacket and a helical ribbon
blender having a central auger-type shaft. 2200 ml toluene was
added to the reaction vessel. A suspension of 22.04 g
(C.sub.4H.sub.8)Si(C.sub.5Me.sub.4) (C.sub.5H.sub.4)ZrCl.sub.2 in
250 ml toluene was transferred to the reaction vessel via cannula.
An additional 200 ml toluene was used to rinse the bottle
containing the metallocene compound suspension. The reaction
mixture was heated to 1550 F (68.3.degree. C.) and stirred for 1
hr. The reaction mixture was transferred to a large glass flask and
500 g silica gel was added with mixing. Two additional increments
of silica gel (250 g each) were added to the mixture. The supported
catalyst was added back to the original reactor vessel with
stirring and 30.2 g AS-990 in 286 ml of toluene was added. (AS-990
is (N,N-bis (2-hydroxylethyl) octadecylamine
(C.sub.18H.sub.37N(CH.sub.2CH.sub.2OH).sub.2)) available as
Kemamine AS-990 from ICI Specialties, Wilmington, Del.). The
catalyst was dried by N.sub.2 purge at 120.degree. F. (49.degree.
C.) until free flowing. The dried catalyst was dry-mixed with 2.5
wt % of Aluminum Stearate #22 in a dry box, (AlSt #22 is
(CH.sub.3(CH.sub.2).sub.16COO).su- b.2Al--OH and is available from
Witco Corporation, Memphis, Tenn.), then transferred to a catalyst
bomb for testing.
Example 14
Polymerizations for Examples 10 through 13
[0111] The catalyst systems of the Examples above were then tested
in a continuous gas phase fluidized bed reactor which comprised a
nominal 18 inch (45.7cm), schedule 60 reactor having an internal
diameter of 16.5 inches (41.9 cm). The fluidized bed is made up of
polymer granules. The gaseous feed streams of ethylene and hydrogen
together with liquid comonomer were mixed together in a mixing tee
arrangement and introduced below the reactor bed into the recycle
gas line. Hexene-1 was used as the comonomer. The individual flow
rates of ethylene, hydrogen and comonomer were controlled to
maintain fixed composition targets. The ethylene concentration was
controlled to maintain a constant ethylene partial pressure. The
hydrogen was controlled to maintain a constant hydrogen to ethylene
mole ratio. The concentration of all the gases were measured by an
on-line gas chromatograph to ensure relatively constant composition
in the recycle gas stream. The catalyst system was injected
directly into the fluidized bed using purified nitrogen as a
carrier. Its rate was adjusted to maintain a constant production
rate. The reacting bed of growing polymer particles is maintained
in a fluidized state by the continuous flow of the make up feed and
recycle gas through the reaction zone. A superficial gas velocity
of 1-3 ft/sec (31-91 cm/sec) was used to achieve this. The reactor
was operated at a total pressure of 300 psig (2069 kPa). To
maintain a constant reactor temperature, the temperature of the
recycle gas is continuously adjusted up or down to accommodate any
changes in the rate of heat generation due to the polymerization.
The fluidized bed was maintained at a constant height by
withdrawing a portion of the bed at a rate equal to the rate of
formation of particulate product. The product is removed
semi-continuously via a series of valves into a fixed volume
chamber, which is simultaneously vented back to the reactor. This
allows for highly efficient removal of the product, while at the
same time recycling a large portion of the unreacted gases back to
the reactor. This product is purged to remove entrained
hydrocarbons and treated with a small steam of humidified nitrogen
to deactivate any trace quantities of residual catalyst.
[0112] The polymerization conditions for each polymerization
utilizing the catalyst systems of the Examples above and results
are set forth in Table 1. The catalyst systems of Examples 11 and
13 were run twice as Examples 11A and Example 13A.
2TABLE 2 VARI- Example Example Example Example Example ABLES 11 11A
12 13 13A Temperature 185 (85) 185 (85) 185 (85) 185 (85) 185 (85)
(.degree. F.) (.degree. C.) Pressure 300 300 300 300 300 (psi)
(kPa) (2069) (2069) (2069) (2069) (2069) C.sub.2 Partial 220.4
220.3 219.5 220.5 220.7 Pressure (1520) (1520) (1514) (1521) (1522)
(psia) (kPa) Ethylene 70 70 69.8 70.1 70.1 (mole %) Hydrogen 874.1
1628.6 1508.3 1671.7 1429.4 (mole ppm) Hydrogen/ 12.48 23.3 21.6
23.86 20.38 Ethylene Concentra- tion ratio Hexene 0.77 0.81 1.43
1.68 1.73 (mole %) Hexene/ 0.0111 0.0115 0.0205 0.0240 0.0247
Ethylene Concentra- tion ratio Bed Weight 297.3 296.9 272.2 294.6
270.8 (lbs) (Kg) (135) (135) (124) (134) (123) Residence 3.39 4.39
4.61 4.55 5.24 Time (hrs) Gas Velocity 2.25 2.25 2.25 2.25 2.25
(ft/sec) (68.6) (68.6) (68.6) (68.6) (68.6) (cm/sec) Production
88.2 (40) 67.8 (31) 59.7 (27) 64.7 (29) 52.8 (24) Rate (lbs/hr)
(Kg/Hr) Bulk Density 0.4658 0.4608 0.4528 0.3879 0.4060 (g/cc)
Productivity 3613 2834 2061 2428 2083 (g/g).sup.1 Melt Index 0.79
1.65 0.47 1.18 0.7 (dg/min) (I.sub.2) Melt Index 40.7 44.4 112.6
83.1 112.58 Ratio (I.sub.2/I.sub.2) Density 0.9223 0.9229 0.9184
0.9216 0.9188 (g/cc) .sup.1Productivity is number of grams of
product per gram of catalyst
[0113] Polymer Data
[0114] The properties of the polymer were determined by the
following test methods:
3 Property Units Procedure Melt Indices, Melt Flow Ratios dg/min
ASTM D-1238 Density g/cc ASTM D-1505 Haze % ASTM D-1003 Gloss @
45.degree. % ASTM D-2457 Tensile @ Yield mPa ASTM D-882 Elongation
@ Yield % ASTM D-882 Tensile @ Break mPa ASTM D-882 Elongation @
Break % ASTM D-882 1% Secant Modulus mPa ASTM D-882 Dart Drop
Impact g/.mu.m ASTM D-1709 (A) Elmendorf Tear Resistance g/.mu.m
ASTM D-1922 Melt Strength cN As described in Specification
Composition Distribution % As described in Specification Breadth
Index
[0115] Property Units Procedure
[0116] The polymers and the films produced therefrom of the present
invention were produced using the cyclic bridged metallocene-type
catalyst systems of the invention. The cyclic bridged metallocene
catalyst compounds used were as follows: Catalyst A is
cyclotrimethylenesilyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride, Catalyst B is
cyclotetramethylenesilyl(tetramethyl cyclopentadienyl)
(cyclopentadienyl) zirconium dichloride, and Catalyst C is
cyclotrimethylenesilyl (tetramethyl cyclopentadienyl) (2-methyl
indenyl) zirconium dichloride, Catalyst D is
cyclotrimethylenesilyl(tetra- methyl- cyclopentadienyl) (3-methyl
cyclopentadienyl) zirconium dichloride, Catalyst E is
cyclotrimethylenesilyl bis(2-methyl indenyl) zirconium dichloride,
Catalyst F is cyclotrimethylenesilyl(tetramethyl cyclopentadienyl)
(2,3,5-trimethyl cyclopentadienyl) zirconium dichloride; and they
all were prepared as described in Example 2. Catalysts A-F were
then polymerized similarly as described in Examples 9 and 14 in a
gas phase polymerization process producing ethylene/hexene-l
copolymers.
[0117] Table 3 includes the data generated using a catalyst of the
invention in a gas phase polymerization process similar to that
described in Example 14 to produce an ethylene/hexene-1 copolymer.
Table 3A below gives film data for the polymers described in Table
3 in Examples 14 through 18.
[0118] Table 4 includes the data generated using a catalyst of the
invention in a gas phase polymerization process similar to that
described in Example 9 to produce an ethylene/hexene-1
copolymer.
4TABLE 3 Example 14 15 16 17 18 19 20 Catalyst Used C C A A B B B
Density (g/cc) 0.9196 0.9219 0.9221 0.9175 0.9178 0.9186 0.9250
Melt Index (g/10 0.90 2.06 0.74 0.86 0.92 2.16 1.27 min) Melt Index
Ratio 36 46 100 77 70 58 68 (I.sub.21/I.sub.2) Melt Strng. (cN) 6.5
4.4 6.2 5.9 4.0 4.3 4.4 Melting Peaks 1.sup.st M.P. (.degree. C.)
119.5 119.7 109.70 106.2 118.7 120.03 121.20 2nd. M.P. (.degree.
C.) 108.0 107.4 120.93 117.3 104.8 110.96 110.75 Mn 23,600 15,500
20,500 23,300 23,000 19,500 23,300 Mw 128,400 127,200 104,400
124,100 116,800 91,700 117,700 Mz 401,900 449,900 335,900 400,500
414,200 308,400 407,300 Mw/Mn 5.4 8.2 5.1 5.3 5.1 4.7 5.1 Mz/Mw 3.1
3.5 3.2 3.2 3.5 3.4 3.5 CDBI 75.5 69.0 73.9 78.4 62.6 57.2 76.3 SCB
(/1000 .degree. C.) 13.4 15.8 15.2 15.8 16.3 17.3 12.1
[0119]
5TABLE 3A BLOWN FILM PROPERTIES (2.5 BUR, DIE GAP AND DIE TEMP
SETTING VARIED) EXAMPLES 14A 15A 16A 17A 18A Gauge(mil) 2.2 1.1 2.1
2.1 4.2 1% SECMOD -MD 38100 38520 36800 32150 34980 (psi) -TD 45760
48030 45060 39700 38800 TNSL@YLD(psi) -MD 1515 1698 1550 1394 1401
-TD 1748 2023 1635 1519 1453 ELNG@YLD(%) -MD 5.9 5.7 5.9 6.2 6.4
-TD 5.9 5.8 5.7 6.1 6.2 TNSL@BRK(psi) -MD 6268 5196 4586 4863 4258
-TD 6420 5286 3884 4748 4276 ELNG@BRK -MD 594 508 507 543 592 (%)
-TD 652 615 576 620 650 ELM TEAR -MD 123 40 59 98 182 (g/mil) -TD
338 326 347 281 317 26" Dart (g/mil) 172 112 98 145 132 HAZE (%)
21.6 32.1 15.3 16.3 8.9 GLOSS (%) 26 18 40 36 62
[0120]
6TABLE 4 1st 2nd. Catalyst Density MI MIR M.S. Tm Tm SCB Example
Used (g/cm3) (g/10 min) (I-21/I-2) (cN) Mn Mw Mz Mw/Mn Mz/Mw
(.degree. C.) (.degree. C.) CDBI (/1000 C.) 21 A 0.9232 1.45 76 5.5
15,200 92,100 303,500 6.1 3.3 112.8 120.8 81.7 14.9 22 A 0.9211
1.58 76 4.9 13,100 86,100 325,500 6.57 3.78 108.4 118.2 82.1 16.6
23 A 0.9215 0.89 84 8.5 19,000 104,100 358,700 5.48 3.45 105.8
120.0 80.7 16.0 24 A 0.9189 0.52 119 7.0 21,900 107,500 321,200
4.91 2.99 119.9 109.0 61.2 17.5 25 A 0.9122 0.38 120 7.8 22,700
114,500 353,400 5.04 3.09 119.2 107.7 49.9 20.9 26 A 0.9249 1.69 56
5.7 24,400 96,600 329,300 3.96 3.41 113.7 s 58.5 12.3 27 D 0.9221
0.92 79 5.7 5,140 118,500 433,100 23.05 3.65 117.4 103.4 74.3 17.5
28 B 0.9209 0.98 95 5.8 12,300 101,400 395,500 8.24 3.90 107.3
118.1 81.7 16.2 29 B 0.9126 1.51 63 5.5 15,900 91,700 319,300 5.77
3.48 101.2 110.4 82.0 18.6 30 B 0.9206 0.82 77 7.7 20,700 112,800
383,800 5.45 3.40 107.4 119.4 82.1 15.4 31 E 0.9220 1.04 44 17.3
5,570 140,500 2,072,000 25.22 14.75 121.0 104.7 58.1 17.0 32 F
0.9228 0.54 174 -- -- -- -- -- -- -- -- -- --
[0121] While the present invention has been described and
illustrated by reference to particular embodiments, those of
ordinary skill in the art will appreciate that the invention lends
itself to variations not necessarily illustrated herein. For
example, it is contemplated that a the cyclic bridged
metallocene-type catalyst compound of the invention can be combined
with one or more non-cyclic bridged metallocene-type catalyst
compounds. It is also contemplated that the process of the
invention may be used in a series reactor polymerization process.
For example, a supported cyclic bridged bulky ligand
metallocene-type catalyst compound is used in one reactor and a
non-cyclic bridged or unbridged, bulky ligand metallocene-type
catalyst compound being used in another or vice-versa. For this
reason, then, reference should be made solely to the appended
claims for purposes of determining the true scope of the present
invention.
* * * * *