U.S. patent application number 09/248147 was filed with the patent office on 2001-10-18 for olefin polymerization catalysts, their production and use.
Invention is credited to SMITH, JACK A., WHITEKER, GREGORY T..
Application Number | 20010031843 09/248147 |
Document ID | / |
Family ID | 26911144 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031843 |
Kind Code |
A1 |
WHITEKER, GREGORY T. ; et
al. |
October 18, 2001 |
OLEFIN POLYMERIZATION CATALYSTS, THEIR PRODUCTION AND USE
Abstract
This invention relates to a catalyst system comprising an
activator and one or more heteroatom substituted phenoxide group 3
to 10 transition metal or lanthanide metal compounds wherein the
metal is bound to the oxygen of the phenoxide group and provided
that: a) if more than one heteroatom substituted phenoxide is
present it is not bridged to the other heteroatom substituted
phenoxide, b) if the metal is a group 4 metal then the carbon
adjacent to the carbon bound to the oxygen of the phenoxide may not
be bound to an aldehyde or an ester, c) the carbon ortho to the
carbon bound to the oxygen of the phenoxide may not be bound to the
C.sup.1 carbon in a group represented by the formula: 1 wherein
R.sup.6 and R.sup.7 are independently hydrogen, halogen, a
hydrocarbon group, a heterocyclic compound residue, an oxygen
containing group, a nitrogen containing group, a boron containing
group, an sulfur containing group, a phosphorus containing group, a
silicon containing group, a germanium containing group, or a tin
containing group, and R.sup.1 and R.sup.2 may be bonded to each
other to form a ring. The activator may be an aluminum alkyl, an
alumoxane, a modified alumoxane, a non-coordinating anion, a
borane, a borate or a mixture thereof.
Inventors: |
WHITEKER, GREGORY T.;
(CHARLESTON, WV) ; SMITH, JACK A.; (CHARLESTON,
WV) |
Correspondence
Address: |
UNIVATION TECHNOLOGIES
5555 SAN FELIPE
SUITE 1950
HOUSTON
TX
770562723
|
Family ID: |
26911144 |
Appl. No.: |
09/248147 |
Filed: |
February 10, 1999 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09248147 |
Feb 10, 1999 |
|
|
|
09216594 |
Dec 18, 1998 |
|
|
|
Current U.S.
Class: |
526/161 ;
502/117; 502/155; 502/156; 502/158; 502/162; 526/111; 526/135;
526/172 |
Current CPC
Class: |
C08F 10/02 20130101;
C08F 4/659 20130101; C08F 4/64048 20130101; C08F 210/14 20130101;
C08F 4/65916 20130101; C08F 10/02 20130101; C08F 4/65912 20130101;
C08F 210/16 20130101; C08F 10/02 20130101; C08F 4/65908 20130101;
C08F 110/02 20130101; C08F 210/16 20130101 |
Class at
Publication: |
526/161 ;
526/111; 526/135; 526/172; 502/117; 502/155; 502/158; 502/162;
502/156 |
International
Class: |
C08F 004/44 |
Claims
We claim:
1. A catalyst system comprising an activator and one or more
heteroatom substituted phenoxide group 3 to 10 transition or
lanthanide metal compounds wherein the metal is bound to the oxygen
of the phenoxide group and provided that: a) if more than one
heteroatom substituted phenoxide is present it is not bridged to
the other heteroatom substituted phenoxide, b) if the metal is a
group 4 metal then the carbon ortho to the carbon bound to the
oxygen of the phenoxide may not be bound to an aldehyde or an
ester, and c) the carbon ortho to the carbon bound to the oxygen of
the phenoxide may not be bound to the C.sup.1 carbon in a group
represented by the formula: 12 wherein R.sup.6 and R.sup.7 are
independently hydrogen, halogen, a hydrocarbon group, a
heterocyclic compound residue, an oxygen containing group, a
nitrogen containing group, a boron containing group, an sulfur
containing group, a phosphorus containing group, a silicon
containing group, a germanium containing group, or a tin containing
group, and R.sup.1 and R.sup.2 may be bonded to each other to form
a ring.
2. The catalyst system of claim 1 wherein the activator is an
aluminum alkyl, an alumoxane, a modified alumoxane, a borane, a
borate or a non-coordinating anion.
3. The catalyst system of claim 1 wherein the transition metal is a
group 4 metal.
4. The catalyst system of claim 1 wherein the transition metal is
zirconium.
5. The catalyst system of claim 1 wherein the heteroatom
substituted phenoxide transition metal compound is selected from
the group consisting of:
bis(N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine)
zirconium(IV) dibenzyl;
bis(N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine)
zirconium(IV) dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylpheno- xide)zirconium(IV)
dibenzyl; bis(N-benzylidene-2-hydroxy-3,5,di-t-butylben- zylamine)
titanium(IV) dibenzyl; bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amy-
lphenoxide)zirconium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-a- mylphenoxide)zirconium(IV)
dichloride; bis(2-(2H-benzotriazol-2-yl)-4,6-di-
-t-amylphenoxide)zirconium(IV) di(bis(dimethylamide));
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide)zirco-
nium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)tit- anium(IV)
dibenzyl; bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylben-
zyl)phenoxide)titanium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(-
1',1'-dimethylbenzyl)phenoxide)titanium(IV) dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide)hafni-
um(IV) dibenzyl; and
(N-phenyl-3,5-di-(1',1'-dimethylbenzyl)salicylimino)z- irconium(IV)
tribenzyl.
6. The catalyst system of claim 5 further comprising an activator
comprising one or more of an aluminum alkyl, an alumoxane, a
modified alumoxane, a borane, a borate or a non-coordinating
anion.
7. The catalyst system of claim 1 wherein either the transition
metal compound or the activator or both are placed on a
support.
8. The catalyst system of claim 1 further comprising a
Ziegler-Natta catalyst.
9. The catalyst system of claim 1 further comprising a mono-or
bis-cyclopentadienyl group 4, 5 and 6 transition metal compound and
an optional second activator.
10. The catalyst system of claim 1 further comprising a second
activator.
11. The catalyst system of claim 1 wherein the activator is one or
more of alumoxane, tris (2,2',2"-nonafluorobiphenyl)
fluoroaluminate, triphenyl boron, triethyl boron, tri-n-butyl
ammonium tetraethylborate, triaryl borane, tri (n-butyl) ammonium
tetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron,
or diethylaluminum chloride.
12. A catalyst system comprising the reaction product of an
activator and one or more heteroatom substituted phenoxide
transition metal compounds represented by the following formulae:
13wherein: R.sup.1 to R.sup.5 may be independently hydrogen, a
heteroatom containing group or a C.sub.1 to C.sub.100 group
provided that at least one of R.sup.2 to R.sup.5 is a group
containing a heteroatom, any of R.sup.1 to R.sup.5 may or may not
be bound to the metal M, O is oxygen, M is a group 3 to 10
transition metal or a lanthanide metal, n is the valence state of
M, Q is an anionic ligand or a bond to an R group containing a
heteroatom which may be any of R.sup.1 to R.sup.5, and further
provided that: a) if M is a group 4 metal then R.sup.5 may not be
an aldehyde or an ester; b) the R.sup.4 and R.sup.5 groups do not
form pyridine in the first formula if M is a group 4 metal; c) the
R.sup.4 and R.sup.5 groups do not form pyridine in at least one
ring of the second formula if M is a group 4 metal; and d) neither
R.sup.1 nor R.sup.5 may be a group represented by the formula: 14
wherein R.sup.6 and R.sup.7 are independently hydrogen, halogen, a
hydrocarbon group, a heterocyclic compound residue, an oxygen
containing group, a nitrogen containing group, a boron containing
group, an sulfur containing group, a phosphorus containing group, a
silicon containing group, a germanium containing group, or a tin
containing group, and R.sup.6 and R.sup.7 may be bonded to each
other to form a ring.
14. The catalyst system of claim 13 wherein the activator is an
aluminum alkyl, an alumoxane, a modified alumoxane, a borane, a
borate, a non-coordinating anion or a mixture thereof.
15. The catalyst system of claim 13 wherein Q is a bond to any of
R.sup.2 to R.sup.5 and the R group that Q is bound to is a
heteroatom containing group.
16. The catalyst system of claim 13 wherein the heteroatom
containing group is a triazole or an oxyzole.
17. The catalyst system of claim 13 wherein the heteroatom in the
heteroatom containing group is nitrogen and/or oxygen.
18. The catalyst system of claim 13 wherein the R.sup.1 group is a
C.sub.4 to C.sub.20 alkyl group.
19. The catalyst system of claim 13 wherein R.sup.1 is a tertiary
alkyl group.
20. The catalyst system of claim 13 wherein R.sup.5 is bound to the
metal.
21. The catalyst system of claim 13 wherein the R.sup.2 group is a
butyl, isobutyl, tertiary butyl, pentyl hexyl, heptyl, isohexyl,
octyl, isooctyl, decyl, nonyl, or dodecyl group.
22. The catalyst system of claim 13 wherein two or more R groups
have formed a five or six membered ring.
23. The catalyst system of claim 13 wherein two or more R groups
have formed a multi-ring system.
24. The catalyst system of claim 13 wherein M is zirconium,
titanium or hafnium.
25. The catalyst system of claim 13 wherein n is 4.
26. The catalyst system of claim 13 wherein n is 3.
27. The catalyst system of claim 13 wherein Q is a halogen or an
alkyl group.
28. The catalyst system of claim 13 wherein Q is an amide,
carboxylate, carbamate, thiolate, hydride or alkoxide group.
29. The catalyst system of claim 13 further comprising a
support.
30. The catalyst system of claim 13 wherein either the transition
metal compound or the activator or the reaction product thereof are
placed on a support selected from the group consisting of talc;
silica, magnesium chloride, alumina, silica-alumina; polyethylene,
polypropylene, polystyrene; or a mixture thereof.
31. The catalyst system of claim 13 wherein prior to being combined
with the transition metal compound and/or the activator and/or the
reaction product thereof the support is partially or completely
dehydrated.
32. The catalyst system of claim 13 wherein the transition metal
compound and the activator are combined in ratios of about 1000:1
to about 0.5:1.
33. The catalyst system of claim 13 wherein the transition metal
compound and the activator are combined in ratios of about 300:1 to
about 1:1.
34. The catalyst system of claim 13 wherein the activator is a
borane and the transition metal compound and the borane are
combined in ratios of about 1:1 to about 10:1
35. The catalyst system of claim 13 wherein the activator is an
alkyl aluminum compound and the transition metal compound and the
alkyl aluminum compound are combined in ratios of about 0.5:1 to
about 10:1
36. The catalyst system of claim 13 wherein two or more R groups do
not form a five membered ring.
37. The catalyst system of claim 13 wherein M is zirconium.
38. A process for polymerizing olefins comprising combining one or
more olefins with a catalyst system comprising the reaction product
of one or more activators and one or more heteroatom substituted
phenoxide group 4 to 10 transition metal or lanthanide metal
compounds wherein the metal is bound to the oxygen of the phenoxide
group and provided that: a) if more than one heteroatom substituted
phenoxide is present it is not bridged to the other heteroatom
substituted phenoxide, b) if the metal is a group 4 metal then the
carbon ortho to the carbon bound to the oxygen of the phenoxide may
not be bound to an aldehyde or an ester, and c) the carbon ortho to
the carbon bound to the oxygen of the phenoxide may not be bound to
the C.sup.1 carbon in a group represented by the formula: 15
wherein R.sup.6 and R.sup.7 are independently hydrogen, halogen, a
hydrocarbon group, a heterocyclic compound residue, an oxygen
containing group, a nitrogen containing group, a boron containing
group, an sulfur containing group, a phosphorus containing group, a
silicon containing group, a germanium containing group, or a tin
containing group, and R.sup.1 and R.sup.2 may be bonded to each
other to form a ring.
39. The process of claim 38 wherein the heteroatom substituted
phenoxide transition metal compound is represented by the of the
following formulae: 16wherein: R.sup.1 to R.sup.5 may be
independently hydrogen, a heteroatom containing group or a C.sub.1
to C.sub.100 group provided that at least one of R.sup.2 to R.sup.5
is a group containing a heteroatom, any of R.sup.1 to R.sup.5 may
or may not be bound to the metal M, O is oxygen, M is a group 3 to
10 transition metal or a lanthanide metal, n is the valence state
of M, Q is an anionic ligand or a bond to an R group containing a
heteroatom which may be any of R.sup.1 to R.sup.5, and further
provided that: a) if M is a group 4 metal then R.sup.5 may not be
an aldehyde or an ester; and b) the R.sup.4 and R.sup.5 groups do
not form pyridine in the first formula if M is a group 4 metal; and
c) neither R.sup.1 nor R.sup.5 may be a group represented by the
formula: 17 wherein R.sup.6 and R.sup.7 are independently hydrogen,
halogen, a hydrocarbon group, a heterocyclic compound residue, an
oxygen containing group, a nitrogen containing group, a boron
containing group, an sulfur containing group, a phosphorus
containing group, a silicon containing group, a germanium
containing group, or a tin containing group, and R.sup.6 and
R.sup.7 may be bonded to each other to form a ring.
40. The process of claim 38 wherein the activator is an aluminum
alkyl, an alumoxane, a modified alumoxane, a borane, a borate, a
non-coordinating anion or a mixture thereof.
41. The process of claim 38 wherein Q is a bond to any of R.sup.2
to R.sup.5 and the R group that Q is bound to is a heteroatom
containing group.
42. The process of claim 38 wherein the heteroatom containing group
is an imime, triazole, or oxyzole.
43. The process of claim 38 wherein the heteroatom in the
heteroatom containing group is nitrogen and/or oxygen.
44. The process of claim 38 wherein the R.sup.1 group is a C.sub.4
to C.sub.20 alkyl group.
45. The process of claim 38 wherein the R.sup.1 group is a butyl,
isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl,
nonyl, or dodecyl group.
46. The process of claim 38 wherein two or more R groups have
formed a five or six membered ring.
47. The process of claim 38 wherein two or more R groups have
formed a multi ring system.
48. The process of claim 38 wherein M is zirconium, titanium or
hafnium.
49. The process of claim 38 wherein n is 3 or 4.
50. The process of claim 38 wherein Q is a halogen or an alkyl
group.
51. The process of claim 38 wherein Q is an amide, carboxylate,
carbamate, thiolate, hydride or alkoxide group.
52. The process of claim 38 wherein the catalyst system and the
olefin are reacted in the gas phase.
53. The process of claim 38 wherein the catalyst system and the
olefin are reacted in the slurry phase.
54. The process of claim 38 wherein the catalyst system and the
olefin are reacted in the slurry phase solution phase.
55. The process of claim 38 wherein the catalyst system and the
olefin are reacted under high pressure.
Description
STATEMENT OF RELATED APPLICATIONS
[0001] This application is a continuation in part of U.S. Ser. No.
09/216,594, filed Dec. 18, 1998 and claims priority therefrom.
FIELD OF THE INVENTION
[0002] This invention relates to a new family of olefin
polymerization catalysts based upon phenoxide complexes of
transition metals.
BACKGROUND OF THE INVENTION
[0003] The intense commercialization of metallocene polyolefin
catalysts (metallocene being cyclopentadienyl based transition
metal catalyst compounds) has led to widespread interest in the
design of non-metallocene, homogeneous catalysts. This field is
more than an academic curiosity as new, non-metallocene catalysts
may provide an easier pathway to currently available products and
may also provide product and process opportunities which are beyond
the capability of metallocene catalysts. In addition, certain
non-cyclopentadienyl ligands will be more economical due to the
relative ease of synthesis of a variety of substituted analogs.
[0004] Anionic, multidentate heteroatom ligands have received the
most attention in non-metallocene polyolefins catalysis. Notable
classes of bidentate anionic ligands which form active
polymerization catalysts include N--N.sup.- and N--O.sup.- ligand
sets. Examples of these types of non-metallocene catalysts include
amidopyridines (Kempe, R., "Aminopyridinato Ligands--New Directions
and Limitations", 80.sup.th Canadian Society for Chemistry Meeting,
Windsor, Ontario, Canada, Jun. 1-4, 1997. Kempe, R. et al, Inorg.
Chem. 1996 vol 35 6742.) Likewise, recent reports by Jordan et al.
of polyolefin catalysts based on hydroxyquinolines (Bei, X.;
Swenson, D. C.; Jordan, R. F., Organometallics 1997, 16, 3282) have
been interesting even though the catalytic activities of Jordan's
hydroxyquinoline catalysts is low.
[0005] European Patent Application 0 803 520 discloses
polymerization catalysts containing beta-diketiminate ligands.
Other recent non-metallocene olefin polymerization catalysts
include U.S. Pat. No. 4,057,565 which discloses
2-dialkylaminobenzyl and 2-dialkylaminomethylphenyl derivatives of
selected transition metals and WO 96/08498 which discloses group 4
metal complexes containing a bridged non-aromatic, anionic dienyl
ligand group.
[0006] U.S. Pat. No. 5,637,660 discloses bidentate pyridine based
transition metal catalysts.
[0007] Further Grubbs et al in Organometallics, Vol 17, 1988 page
3149-3151 disclose that nickel (II) salicylaldiminato complexes
combined with B(C.sub.6F.sub.5).sub.3 polymerized ethylene. (49,500
Mw, Mw/Mn 6.8, and 35 branches per 1000 C's).
[0008] Ethylenebis(salicylideneiminato)zirconium dichloride
combined with methyl alumoxane deposited on a support and
unsupported versions were used to polymerize ethylene by Repo et al
in Macromolecules 1997, 30, 171-175.
[0009] Further EP 241,560 A1 discloses alkoxide ligands in
transition metal catalyst systems.
[0010] EP 0 874 005 A1 discloses phenoxide compounds with an imine
substituent for use as a polymerization catalyst.
[0011] Thus there is a need in the art for new novel olefin
polymerization catalysts.
SUMMARY OF THE INVENTION
[0012] This invention relates to a catalyst system comprising an
activator and one or more heteroatom substituted phenoxide group 3
to 10 or lanthanide transition metal compounds wherein the metal is
bound to the oxygen of the phenoxide group and provided that:
[0013] a) if more than one heteroatom substituted phenoxide is
present it is not bridged to the other heteroatom substituted
phenoxide,
[0014] b) if the metal is a group 4 metal then the carbon ortho to
the carbon bound to the oxygen of the phenoxide may not be bound to
an aldehyde or an ester, and
[0015] c) the carbon ortho to the carbon bound to the oxygen of the
phenoxide may not be bound to the C.sup.1 carbon in a group
represented by the formula: 2
[0016] wherein R.sup.6 and R.sup.7 are independently hydrogen,
halogen, a hydrocarbon group, a heterocyclic compound residue, an
oxygen containing group, a nitrogen containing group, a boron
containing group, an sulfur containing group, a phosphorus
containing group, a silicon containing group, a germanium
containing group, or a tin containing group, and R.sup.1 and
R.sup.2 may be bonded to each other to form a ring.
[0017] The activator is preferably one or more of aluminum alkyl,
an alumoxane, a modified alumoxane, a non-coordinating anion, or a
borane.
[0018] This invention further relates to a novel olefin
polymerization systems comprising an activator and one or more
catalysts represented by the of the following formulae: 3
[0019] wherein R.sup.1 to R.sup.5 may be independently hydrogen, a
heteroatom containing group or a C.sub.1 to C.sub.100 group
provided that one of R.sup.2 to R.sup.5 is a group containing a
heteroatom (R.sup.5 and/or R.sup.1 also may or may not be bound to
the metal M, and further provided that the R.sup.4 and R.sup.5
groups do not form pyridine in the first formula if M is a group 4
metal and the R.sup.4 and R.sup.5 groups do not form pyridine in at
least one ring of the second formula if M is a group 4 metal, O is
oxygen, M is a group 3 to 10 transition metal or anthanide metal, n
is the valence state of M, Q is an anionic ligand or a bond to an R
group containing a heteroatom which may be any of R.sup.1 to
R.sup.5, and further provided that if M is a group 4 metal then
R.sup.1 may not be an aldehyde or an ester, and further provided
that if M is nickel then R.sup.5 may not be an imine. Any two or
more R groups may form a ring structure. Provided however that
neither R.sup.1 nor R.sup.5 may be a group represented by the
formula 4
[0020] wherein R.sup.6 and R.sup.7 are independently hydrogen,
halogen, a hydrocarbon group, a heterocyclic compound residue, an
oxygen containing group, a nitrogen containing group, a boron
containing group, an sulfur containing group, a phosphorus
containing group, a silicon containing group, a germanium
containing group, or a tin containing group, and R.sup.6 and
R.sup.7 may be bonded to each other to form a ring.
[0021] The activator is preferably an aluminum alkyl, an alumoxane,
a modified alumoxane, a non-coordinating anion, a borane or a
combination thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0022] This invention relates to a novel olefin polymerization
system comprising an activator and one or more catalysts
represented by the following formulae: 5
[0023] wherein R.sup.1 is hydrogen or a C.sub.4 to C.sub.100 group,
preferably a tertiary alkyl group, preferably a C.sub.4 to C.sub.20
alkyl group, preferably a C.sub.4 to C.sub.20 tertiary alkyl group,
preferably a neutral C.sub.4 to C.sub.100 group and may or may not
also be bound to M, and at least one of R.sup.2 to R.sup.5 is a
group containing a heteroatom, the rest of R.sup.2 to R.sup.5 are
independently hydrogen or a C.sub.1 to C.sub.100 group, preferably
a C.sub.4 to C.sub.20 alkyl group (preferably butyl, isobutyl,
pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl,
dodecyl) and any of R.sup.2 to R.sup.5 also may or may not be bound
to M provided that in the first formula if M is a group 4 metal
then the R.sup.4 and R.sup.5 groups do not form pyridine and in the
second formula if M is a group 4 metal the R.sup.4 and R.sup.5
groups do not form pyridine in at least one ring, and further
provided that if M is a group 4 metal then R.sup.5 may not be an
aldehyde or an ester, and further provided that if M is nickel then
R.sup.5 may not be an imine, further provided that neither R.sup.1
nor R.sup.5 may be a group represented by the formula 6
[0024] wherein R.sup.6 and R.sup.7 are independently hydrogen,
halogen, a hydrocarbon group, a heterocyclic compound residue, an
oxygen containing group, a nitrogen containing group, a boron
containing group, an sulfur containing group, a phosphorus
containing group, a silicon containing group, a germanium
containing group, or a tin containing group, and R.sup.6 and
R.sup.7 may be bonded to each other to form a ring; O is oxygen, M
is a group 3 to group 10 transition metal or lanthanide metal,
preferably a group 4 metal, preferably Ti, Zr or Hf, n is the
valence state of the metal M, preferably 2, 3, 4, or 5, Q is an
alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate,
hydride or alkoxide group, or a bond to an R group containing a
heteroatom which may be any of R.sup.1 to R.sup.5. A heteroatom
containing group may be any heteroatom or a heteroatom bound to
carbon silica or another heteroatom. Preferred heteroatoms include
boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead,
antimony, oxygen, selenium, tellurium. Particularly preferred
heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even
more particularly preferred heteroatoms include oxygen and
nitrogen. The heteroatom itself may be directly bound to the
phenoxide ring or it may be bound to another atom or atoms that are
bound to the phenoxide ring. The heteroatom containing group may
contain one or more of the same or different heteroatoms. Preferred
heteroatom groups include imines, amines, oxides, phosphines,
ethers, ketenes, oxoazolines heterocyclics, oxazolines, thioethers,
and the like. Particularly preferred heteroatom groups include
imines. Any two adjacent R groups may form a ring structure,
preferably a 5 or 6 membered ring. Likewise the R groups may form
multi-ring structures. In one embodiment any two or more R groups
do not form a 5 membered ring.
[0025] Preferred catalyst systems of this invention include those
comprising catalysts represented by the following formulae: 7
[0026] wherein
[0027] R.sup.5=aldimino, ketimino, alkoxy, .alpha.-alkoxymethyl,
thioalkoxy, .alpha.-thioalkoxymethyl, amino, .alpha.-aminomethyl,
azo, phosphino, .alpha.-phosphinomethyl, keto or cyclic
substituents such as pyrrole, furan, thiophene, imidazole,
pyrazole, tetrazole, oxazoline, isoazole, thiazole.
[0028] R.sup.o=preferably tertiary alkyl or silyl group, such as
--CMe.sub.3, --CMe.sub.2Et, CEt.sub.3, --CMe.sub.2Ph, --CPh.sub.3,
--SiMe.sub.3, --SiEt.sub.3, --SiPh.sub.3.
[0029] R=is hydrogen or an alkyl, aryl, silyl group or --OT where O
is oxygen and T is hydrogen or an alkyl, aryl or silyl group.
[0030] M.sup.n is a group 3 to 10 transition metal or a lanthanide
metal, preferably a group 4 metal, n is the valence of M and
M.sup.n is also bound to Q.sub.n-1, where Q is as defined above or
any of the phenoxide groups in the above formulae.
[0031] The synthesis of desired ligands can be accomplished using
techniques described in the literature. For example,
N-benzylidene-2-hydroxybenzylamines can be prepared by condensation
of an aldehyde or ketone with the prequisite 2-hydroxybenzylamine.
In some instances, such as those involving less-reactive amines or
aldehydes, addition of a catalytic amount of formic acid or 3 .ANG.
molecular sieves may be required. Phenols with heterocyclic
substituents can also be prepared by standard techniques. For
example, ortho-cyanophenols can be converted to oxazolines via
reaction with .alpha.-aminoalcohols. Certain ligands, such as
ortho-benzotriazole-substituted phenols are commercially
available.
[0032] Metallation of these acidic functionalized phenols can be
accomplished by reaction with basic reagents such as
Zr(CH.sub.2Ph).sub.4, Ti(NMe.sub.2).sub.4. Reaction of phenolic
ligands with Zr(CH.sub.2Ph).sub.4 occurs with elimination of
toluene, whereas reaction with Ti(NMe.sub.2).sub.4 proceeds via
amine elimination. In both cases simple alkoxide complexes are
formed, as determined by .sup.1H NMR spectroscopy. Alternatively,
ligands can be deprotonated with reagents such as BuLi, KH or Na
metal and then reacted with metal halides, such as ZrCl.sub.4 or
TiCl.sub.4.
[0033] Preferred transition metal compounds for use in this
invention include:
[0034] bis(N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine)
zirconium(IV) dibenzyl;
[0035] bis(N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine)
zirconium(IV) dichloride;
[0036]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)
dibenzyl;
[0037] bis(N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine)
titanium(IV) dibenzyl;
[0038]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)
dibenzyl;
[0039]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)
dichloride;
[0040]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)
di(bis(dimethylamide));
[0041]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide-
)zirconium(IV) dibenzyl;
[0042]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)
dibenzyl;
[0043]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide-
)titanium(IV) dibenzyl;
[0044]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide-
)titanium(IV) dichloride; and
[0045]
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1',1'-dimethylbenzyl)phenoxide-
)hafnium(IV) dibenzyl.
[0046] In a preferred embodiment one or more of the transition
metal compounds named above is combined with an aluminum alkyl, an
alumoxane, a modified alumoxane, a non-coordinating anion, a
borane, a borate or a mixture thereof.
[0047] The catalysts described herein are preferably combined with
an activator to form an olefin polymerization catalyst system.
Preferred activators include alkyl aluminum compounds (such as
diethylaluminum chloride), alumoxanes, modified alumoxanes,
non-coordinating anions, boranes and the like. 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 which
ionize the neutral metallocene compound. Boranes appear to perform
better than borates, however this may be an experimental artifact
and should not be construed as limiting this invention. Other
useful compounds include triphenyl boron, triethyl boron,
tri-n-butyl ammonium tetraethylborate, triaryl borane and the like.
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 and 5,731,451 and European publications EP-A-0
561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publication WO
94/10180, all of which are herein fully incorporated by
reference.
[0048] 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-0 426 637,
EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos.
5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568,
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. Other activators include those described
in PCT publication WO 98/07515 such as tris (2, 2',
2"-nonafluorobiphenyl) fluoroaluminate, which 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. Also,
methods of activation such as using radiation and the like are also
contemplated as activators for the purposes of this invention.
[0049] In general the transition metal compound and the activator
are combined in ratios of about 1000:1 to about 0.5:1. In a
preferred embodiment the transition metal compound and the
activator are combined in a ratio of about 300:1 to about 1:1,
preferably about 10:1 to about 1:1, for boranes the ratio is
preferably about 1:1 to about 10:1 and for alkyl aluminum compounds
(such as diethylaluminum chloride combined with water) the ratio is
preferably about 0.5:1 to about 10:1.
[0050] In one embodiment the catalysts systems described above can
further include other classes of catalysts, such as for example one
or more Ziegler-Natta catalysts and/or one or more metallocene
catalyst and/or one or more vanadium catalysts and/or one or more
chromium catalysts. In a preferred embodiment a Ziegler-Natta
catalyst as described in Ziegler-Natta Catalysts and
Polymerizations. John Boor, Academic Press, New York, 1979 (with or
without a separate activator) is combined with a catalyst system of
this invention and used to polymerize one or more olefins. In
another embodiment a metallocene catalyst (such as a
cyclopentadienyl transition metal compound) with or without a
separate activator is combined with a catalyst system of this
invention and used to polymerize one or more olefins. Preferred
cyclopentadienyl transition metal compounds are those mono-and
bis-cyclopentadienyl group 4, 5 and 6 compounds described in U.S.
Pat. Nos. 4,530,914, 4,805,561, 4,937,299, 5,124,418, 5,017,714,
5,057,475, 5,064,802, 5,278,264, 5,278,119, 5,304,614, 5,324,800,
5,347,025, 5,350,723, 5,391,790 5,391,789, EP-A-0 591 756, EP-A-0
520 732, EP-A-0 578,838, EP-A-0 638,595, EP-A-0 420 436, WO
91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO
94/07928, WO 94/03506 and WO 95/07140, all of which are fully
incorporated by reference herein.
[0051] The catalysts and catalyst systems described above can be
used in any known olefin polymerization process including gas
phase, solution, slurry and high pressure. The catalysts and
catalyst systems described above are particularly suitable for use
a solution, gas or slurry polymerization process or a combination
thereof, most preferably a gas or slurry phase polymerization
process.
[0052] In one embodiment, this invention is directed toward the
solution, slurry or gas phase polymerization reactions involving
the polymerization of one or more of monomers having from 2 to 30
carbon atoms, preferably 2-12 carbon atoms, and more preferably 2
to 8 carbon atoms. Preferred monomers include one or more of
ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1,
3,5,5,-trimethyl-hexene-1, hexene-1, octene-1, decene-1,
3-methyl-pentene-1, and cyclic olefins or a combination thereof.
Other monomers can include vinyl monomers, diolefins such as
dienes, polyenes, norbornene, norbornadiene monomers. In one
embodiment, a homopolymer of ethylene is produced.
[0053] 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.)
[0054] 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).
[0055] The reactor temperature in the gas phase process may vary
from about 30.degree. C. to about 120.degree. C., preferably from
about 60.degree. C. to about 1 15.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.
[0056] The productivity of the catalyst or catalyst system in a gas
phase system is influenced by the main monomer partial pressure.
The preferred mole percent of the main monomer, ethylene or
propylene, preferably ethylene, is from about 25 to 90 mole percent
and the monomer partial pressure is in the range of from about 75
psia (517 kPa) to about 300 psia (2069 kPa), which are typical
conditions in a gas phase polymerization process.
[0057] 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).
[0058] 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.
[0059] 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 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.
[0060] In one embodiment, 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. The
preferred temperature in the particle form process is within the
range of about 185.degree. C. (85.degree. C.) to about 230.degree.
C. (110.degree. C.). Two preferred polymerization methods for the
slurry process are 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.
[0061] In another embodiment, the slurry process is carried out
continuously in a loop reactor. The catalyst as a slurry in
isobutane or as a dry free flowing powder is injected regularly to
the reactor loop, which is itself filled with circulating slurry of
growing polymer particles in a diluent of isobutane containing
monomer and comonomer. Hydrogen, optionally, may be added as a
molecular weight control. The reactor is maintained at pressure of
about 525 psig to 625 psig (3620 kPa to 4309 kPa) and at a
temperature in the range of about 140.degree. F. to about
220.degree. F. (about 60.degree. C. to about 104.degree. C.)
depending on the desired polymer density. Reaction heat is removed
through the loop wall since much of the reactor is in the form of a
double-jacketed pipe. The slurry is allowed to exit the reactor at
regular intervals or continuously to a heated low pressure flash
vessel, rotary dryer and a nitrogen purge column in sequence for
removal of the isobutane diluent and all unreacted monomer and
comonomers. The resulting hydrocarbon free powder is then
compounded for use in various applications.
[0062] In another 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).
[0063] In another embodiment in the slurry process of the invention
the total reactor pressure is in the range of from 400 psig (2758
kPa) to 800 psig (5516 kPa), preferably 450 psig (3103 kPa) to
about 700 psig (4827 kPa), more preferably 500 psig (3448 kPa) to
about 650 psig (4482 lda), most preferably from about 525 psig
(3620 kPa) to 625 psig (4309 kPa).
[0064] In yet another embodiment in the slurry process of the
invention the concentration of ethylene in the reactor liquid
medium is in the range of from about 1 to 10 weight percent,
preferably from about 2 to about 7 weight percent, more preferably
from about 2.5 to about 6 weight percent, most preferably from
about 3 to about 6 weight percent.
[0065] A preferred process of the invention is where the process,
preferably a slurry or gas phase process is operated 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, which are herein fully incorporated by
reference.
[0066] In another preferred embodiment the one or all of the
catalysts are tumbled with up to 6 weight % of a metal stearate,
(preferably a aluminum stearate, more preferably aluminum
distearate) based upon the weight of the catalyst, any support and
the stearate, preferably 2 to 3 weight %. In an alternate
embodiment a solution of the metal stearate is fed into the
reactor. These agents may be dry tumbled with the catalyst or may
be fed into the reactor in a solution with or without the catalyst
system or its components.
[0067] The catalyst and/or the activator may be placed on a
support. Typically the support can be of any of the solid, porous
supports. Typical support materials include talc; inorganic oxides
such as silica, magnesium chloride, alumina, silica-alumina;
polymeric supports such as polyethylene, polypropylene,
polystyrene; and the like. Preferably the support is used in finely
divided form. Prior to use the support is preferably partially or
completely dehydrated. The dehydration may be done physically by
calcining or by chemically converting all or part of the active
hydroxyls. For more information on how to support catalysts please
see U.S. Pat. No. 4,808,561 which teaches how to support a
metallocene catalyst system. The techniques used therein are
generally applicable for this invention.
[0068] The catalyst system, the catalyst and or the activator may
also be introduced into the reactor in solution. In one embodiment
a solution of the activated catalyst in an alkane such as pentane,
hexane, isopentane or the like is feed into a gas phase
reactor.
[0069] In a preferred embodiment, the polyolefin recovered
typically has a melt index as measured by ASTM D-1238, Condition E,
at 190.degree. C. of 100 g/10 min or less. In a preferred
embodiment the polyolefin is ethylene homopolymer.
[0070] In a preferred embodiment the catalyst system described
above is used to make a polyethylene having a density of between
0.89 and 0.960 g/cm.sup.3 (as measured by ASTM 2839), a melt index
of 1.0 or less g/10 min or less (as measured by ASTM D-1238,
Condition E, at 190.degree. C.). Polyethylene having a melt index
of between 0.01 to 10 dg/min is preferably produced. In some
embodiments, a density of 0.915 to 0.940g/cm.sup.3 would be
preferred, in other embodiments densities of 0.930 to
0.960g/cm.sup.3 are preferred.
[0071] The polyolefins then can be made into films, molded
articles, sheets and the like. The films may be formed by any of
the conventional technique known in the art including extrusion,
co-extrusion, lamination, blowing and casting. The film may be
obtained by the flat film or tubular process which may be followed
by orientation in an uniaxial direction or in two mutually
perpendicular directions in the plane of the film to the same or
different extents. Orientation may be to the same extent in both
directions or may be to different extents. Particularly preferred
methods to form the polymers into films include extrusion or
coextrusion on a blown or cast film line.
[0072] The films produced may further contain additives such as
slip, antiblock, antioxidants, pigments, fillers, antifog, UV
stabilizers, antistats, polymer processing aids, neutralizers,
lubricants, surfactants, pigments, dyes and nucleating agents.
Preferred additives include silicon dioxide, synthetic silica,
titanium dioxide, polydimethylsiloxane, calcium carbonate, metal
stearates, calcium stearate, zinc stearate, talc, BaSO.sub.4,
diatomaceous earth, wax, carbon black, flame retarding additives,
low molecular weight resins, hydrocarbon resins, glass beads and
the like.
[0073] The additives may be present in the typically effective
amounts well known in the art, such as 0.001 weight % to 10 weight
%.
[0074] This invention further relates to a library of a plurality
of heteroatom substituted phenoxide group 3 to 10 transition metal
or lanthanide metal compounds wherein the metal is bound to the
oxygen of the phenoxide group and provided that:
[0075] a) if more than one heteroatom substituted phenoxide is
present it is not bridged to the other heteroatom substituted
phenoxide,
[0076] b) if the metal is a group 4 metal then the carbon ortho to
the carbon bound to the oxygen of the phenoxide may not be bound to
an aldehyde or an ester, and
[0077] c) the carbon ortho to the carbon bound to the oxygen of the
phenoxide may not be bound to the C.sup.1 carbon in a group
represented by the formula: 8
[0078] wherein R.sup.6 and R.sup.7 are independently hydrogen,
halogen, a hydrocarbon group, a heterocyclic compound residue, an
oxygen containing group, a nitrogen containing group, a boron
containing group, an sulfur containing group, a phosphorus
containing group, a silicon containing group, a germanium
containing group, or a tin containing group, and R.sup.1 and
R.sup.2 may be bonded to each other to form a ring.
[0079] In a preferred embodiment the heteroatom substituted
phenoxide group 4 to 10 transition metal or lanthanide metal
compounds are represented by the formulae above. These libraries
may then be used for the simultaneous parallel screening of
catalysts, activators and or monomers by combining the library with
one or more activators and or olefins.
EXAMPLES
[0080] MMAO is modified methylalumoxane (type 3 in hexane)
commercially available from Akzo Chemicals, Inc. under the trade
name Modified Methylalumoxane type 3A , covered under patent number
U.S. Pat. No. 5,041,584)
Example 1
[0081] 9
[0082] Synthesis of
N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine.
[0083] A solution of 2-hydroxy-3,5,di-t-butylbenzylamine (prepared
by the procedure described by G. E. Stokker, et al.; J Med. Chem.
1980, 23, 1414; 2.35 g, 10.0 mmol) is prepared in 50 mL methanol.
Benzaldehyde (1.06 g, 10.0 mmol) is added, and the resulting
solution is stirred for 30 minutes. Product crystallizes upon
cooling the solution to -40.degree. C.
Example 2
[0084] 10
[0085] Ethylene Polymerization using Catalyst 1.
[0086] A solution of
N-benzylidene-2-hydroxy-3,5,di-t-butylbenzylamine is prepared in 50
mL toluene. BZ.sub.4Zr is added (0.5 equiv), and the resulting
solution is stirred for 30 minutes. A 1 .mu.mol aliquot of the
solution is withdrawn and added to 300 equiv of MMAO (Type 3A,
Akzo). The resulting solution is stirred for 5 minutes and is
injected into a 1 L slurry reactor, containing 600 mL hexane, 43 mL
hexene and 100 .mu.mol isoBu.sub.3AI. The reactor is then
pressurized to 85 psi (586 kPa) with ethylene and heated to
75.degree. C. After 30 minutes, the reactor is cooled to ambient
temperature and vented. Solid polyethylene is obtained.
Example 3
[0087] 11
[0088] Ethylene Polymerization using catalyst 2.
[0089] A solution of
2-(21H-Benzotriazol-2-yl)-4,6-di-t-pentylphenol (Aldrich) was
prepared in 50 mL toluene. Bz.sub.4Zr was added (0.5 equiv), and
the resulting solution was stirred for 30 minutes. The resulting
solution wa added to 300 equiv of MMAO (Type 3A, Akzo). The
resulting solution was stirred for 5 minutes, a 0.25 .mu.mol (Zr)
aliquot of the solution was withdrawn and injected into a 1 L
slurry reactor, containing 600 mL hexane, 43 mL hexene and 100
.mu.mol isoBu.sub.3Al. The reactor was then pressurized to 85 psi
(586 kPa) with ethylene and heated to 75.degree. C. After 30
minutes, the reactor was cooled to ambient temperature and vented.
Solid polyethylene was obtained (0.98 g) which corresponds to an
activity of 9200 g PE/mmol Zr.multidot.100 psi
C.sub.2H.sub.4.multidot.hr.
[0090] The catalysts described herein are expected to produce HDPE
under ethylene-hexene copolymerization conditions.
[0091] All documents described herein are incorporated by reference
herein, including any priority documents and/or testing procedures.
As is apparent form the foregoing general description and the
specific embodiments, while forms of the invention have been
illustrated and described, various modifications can be made
without departing from the spirit and scope of the invention.
Accordingly it is not intended that the invention be limited
thereby.
* * * * *