U.S. patent application number 10/113761 was filed with the patent office on 2003-05-22 for coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation.
This patent application is currently assigned to W. R. Grace & Co.-Conn.. Invention is credited to Carney, Michael John, Denton, Dean Alexander, Shih, Keng-Yu.
Application Number | 20030096698 10/113761 |
Document ID | / |
Family ID | 23713360 |
Filed Date | 2003-05-22 |
United States Patent
Application |
20030096698 |
Kind Code |
A1 |
Shih, Keng-Yu ; et
al. |
May 22, 2003 |
Coordination catalyst systems employing agglomerated metal
oxide/clay support-activator and method of their preparation
Abstract
The present invention is directed to a coordinating catalyst
system comprising at least one bidentate or tridentate pre-catalyst
transition metal compound, (e.g., 2,6-bis
(2,4,6-trimethylarylamino) pyridyl iron dichloride), at least one
support-activator (e.g., spray dried silica/clay agglomerate), and
optionally at least one organometallic compound (e.g., triisobutyl
aluminum), in controlled amounts, and methods for preparing the
same. The resulting catalyst system exhibits enhanced activity for
polymerizing olefins and yields polymer having very good
morphology.
Inventors: |
Shih, Keng-Yu; (Columbia,
MD) ; Carney, Michael John; (Eldersburg, MD) ;
Denton, Dean Alexander; (Baltimore, MD) |
Correspondence
Address: |
Robert A. Maggio
W. R. Grace & Co.-Conn.
Patent Dept.
7500 Grace Drive
Columbia
MD
21044-4098
US
|
Assignee: |
W. R. Grace & Co.-Conn.
|
Family ID: |
23713360 |
Appl. No.: |
10/113761 |
Filed: |
April 1, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10113761 |
Apr 1, 2002 |
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09431771 |
Nov 1, 1999 |
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6399535 |
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Current U.S.
Class: |
502/150 ;
502/152; 502/154 |
Current CPC
Class: |
C08F 10/02 20130101;
C08F 4/7006 20130101; C08F 4/7042 20130101; C08F 4/025 20130101;
C08F 10/00 20130101; C08F 10/02 20130101; C08F 10/00 20130101; C08F
10/00 20130101 |
Class at
Publication: |
502/150 ;
502/152; 502/154 |
International
Class: |
B01J 031/00 |
Claims
What is claimed is:
1. A coordinating catalyst system capable of polymerizing olefins
comprising: (I) as a pre-catalyst, at least one non-metallocene,
non-constrained geometry, bidentate transition metal compound or
tridentate transition metal compound capable of (A) being activated
upon contact with the support-activator of (II)(B) or (B) being
converted, upon contact with an organometallic compound, to an
intermediate capable of being activated upon contact with the
support-activator of (II)(B), wherein the transition metal is at
least one member selected from Groups 3 to 10 of the Periodic
table; in intimate contact with (II) catalyst support-activator
agglomerate comprising a composite of (A) at least one inorganic
oxide component selected from SiO.sub.2, Al.sub.2O.sub.3, MgO,
AlPO.sub.4, TiO.sub.2, ZrO2, Cr.sub.2O.sub.3 and (B) at least one
ion containing layered material having interspaces between the
layers and sufficient Lewis acidity, when present within the
support-activator, to activate the pre-catalyst when the
pre-catalyst is in contact with the support-activator, said layered
material having a cationic component and an anionic component,
wherein said an anionic component is present within the interspace
of the layered material, said layered material being intimately
dispersed with said inorganic oxide component within the
agglomerate in an amount sufficient to improve the activity of the
coordinating catalyst system for polymerizing ethylene monomer,
expressed as Kg of polyethylene per gram of catalyst system per
hour, relative to the activity of a corresponding catalyst system
employing the same pre-catalyst but in the absence of either
Component A or B of the support-activator; wherein the amount of
the pre-catalyst and support-activator which is in intimate contact
is sufficient to provide a ratio of micromoles of pre-catalyst to
grams of support-activator of from about 5:1 to about 500:1.
2. The catalyst system of claim 1 which additionally comprises as a
third component, at least one organometallic compound represented
by the structural formula: M(R.sup.12).sub.s wherein M represents
at least one element of Group 1, 2, or 13 or the Periodic Table,
tin or zinc, and each R.sup.2 independently represents at least one
of hydrogen, halogen, or hydrocarbon-based group, and "s" is a
number corresponding to the oxidation number of M; said
organometallic compound being in intimate contact with said
pre-catalyst in an amount sufficient to provide a molar ratio of
organometallic compound to pre-catalyst from about 0.001:1 to about
10,000:1.
3. The catalyst system of claim 1 wherein the pre-catalyst is a
bidentate transition metal compound represented by the formula:
7wherein: (I) each A independently represents oxygen, sulfur,
phosphorus or nitrogen; (II) Z represents a transition metal
selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd,
Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and
Hf in the +2, +3 or +4 oxidation state: (III) each L and L'
independently represents a ligand group selected from at least one
of hydrogen, halogen, hydrocarbon based radical, or two L groups,
together represent a hydrocarbon based radical, which, together
with Z, constitute a heterocyclic ring structure; (IV) "a" is an
integer of 0 or 1 and represents the number of L' groups bound to
Z, the lines joining each A to each other A represent a hydrocarbon
based radical joined to A by a double or single bond, the lines
joining each A to Z represent a covalent or dative bond.
4. The catalyst system of claim 1 wherein the transition metal
compound is a tridentate transition metal compound represented by
the formula: 8wherein: (I) each A independently represents oxygen,
sulfur, phosphorous or nitrogen; (II) Z represents a transition
metal selected from at least one of the group of Fe, Co, Ni, Ru,
Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr, Mn,
Zr, and Hf in the +2, +3 or +4 oxidation state; (III) each L and L'
independently represents a ligand group selected from at least one
of hydrogen, halogen and hydrocarbon based radical, or two L groups
together represent a hydrocarbon based radical, which together with
Z, constitute a heterocyclic ring structure; and (IV) "a" is an
integer of 0, 1, or 2 and represents the number of L' groups bound
to Z, the lines joining each A to each other A represent a
hydrocarbon based radical joined to A by a double or single bond,
and the lines joining each A to Z represent a covalent or dative
bond.
5. The catalyst system of any one of claims 3 and 4 wherein each A
represents a nitrogen atom, each L and L' is independently selected
from halogen, hydrocarbyl or mixtures thereof, or two L groups
together represent hydrocarbylene which together with Z constitute
a 3 to 7 member heterocyclic ring structure.
6. The catalyst system of any one of claims 3 and 4 wherein at
least one L of the pre-catalyst is selected from hydrocarbyl.
7. The catalyst system of claim 6 wherein Z is selected from Ni,
Pd, Fe or Co.
8. The catalyst system of claim 3 wherein Z is selected from Ni or
Pd and each L is independently selected from chlorine, bromine,
iodine, or C.sub.1-C.sub.8 alkyl.
9. The catalyst system of claim 4 wherein Z is selected from iron
or cobalt and each L is independently selected from chlorine,
bromine, iodine, or C.sub.1-C.sub.8 alkyl.
10. The catalyst system of any one of claims 3 and 4 wherein L is
selected from halogen or hydrogen, and the catalyst system further
comprises at least one organometallic compound represented by the
formula: M(R.sup.12).sub.s wherein M is aluminum R.sup.12 is
hydrocarbyl, and "s" is 3, intimately associated with the
pre-catalyst in an amount sufficient to provide a molar ratio of
organometallic compound to transition metal in the pre-catalyst of
from about 0.001:1 to about 250:1.
11. The catalyst system of claim 1 wherein the layered material of
the support-activator is at least one of clay or clay minerals
having a negative charge of below 0.
12. The catalyst system of claim 11 wherein the layered material is
a smectite clay, the weight ratio of inorganic oxide to clay in the
support activator agglomerate is from about 0.25:1 to about 99:1,
and the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 10:1 to about 250:1.
13. The catalyst system of claim 12 wherein the smectite clay is at
least one of montmorillonite and hectorite, the weight ratio of
inorganic oxide to clay in the support-activator agglomerate is
from about 0.5:1 to about 20:1, and the ratio of micromoles of
pre-catalyst to grams of support-activator is from about 30:1 to
about 100:1.
14. The catalyst system of claim 1 wherein the inorganic oxide
component is SiO.sub.2, the weight ratio of SiO.sub.2 to layered
material in the support-activator agglomerate is from about 1:1 to
about 10:1, and the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 80:1 to about 100:1.
15. The catalyst system of anyone of claims 1 and 2 wherein the
support-activator comprises spray dried agglomerate particles
comprising constituent particles of at least one of said inorganic
oxides and at least one of said layered materials wherein: (I) at
least 80% of the volume of the agglomerated particles smaller than
D.sub.90 of the entire agglomerate particle size distribution
possesses a microspheroidal morphology; (II) the support-activator
agglomerate particles possess: (A) an average particle size of from
about 4 to about 250 microns, and (B) a surface area of from 20 to
about 800 m.sup.2/gm; and (III) the constituent inorganic oxide
particles from which the agglomerate particles are derived have an
average particle size, prior to spray drying of from about 2 to
about 10 microns, and the constituent layered material particles
have an average particle size, prior to spray drying of from about
0.01 to about 50 microns.
16. The catalyst system of claim 15 wherein the constituent
inorganic oxide particles from which the agglomerate particles are
derived, prior to spray drying, have: (I) an average particle size
of from about 4 to about 9 microns, (II) a particle size
Distribution Span of from about 0.5 to about 3.0 microns, and (III)
a colloidal particle size content of from about 2 to about 60 wt.
%, based on the constituent inorganic oxide particle weight.
17. A coordinating catalyst system formed by the process
comprising: (I) agglomerating to form a support-activator: (A) at
least one inorganic oxide component selected from SiO.sub.2,
Al.sub.2O.sub.3, MgO, AlPO.sub.4, TiO.sub.2, ZrO.sub.2,
Cr.sub.2O.sub.3 with (B) at least one ion containing layered
material having interspaces between the layers and sufficient Lewis
acidity, when present within the support-activator, to activate the
transition metal of the pre-catalyst of II when the pre-catalyst is
in contact with the support-activator, said layered material,
having a cationic component and an anionic component, wherein said
anionic component is present within the interspace of the layered
material, said layered material being intimately dispersed with
said inorganic oxide component within said agglomerate in an amount
sufficient to improve the activity of the coordinating catalyst
system for polymerizing ethylene monomer, expressed as Kg of
polyethylene per gram of catalyst system per hour, relative to the
activity of a corresponding catalyst system employing the same
pre-catalyst but in the absence of either Component A or B of the
support-activator; (II) providing as a pre-catalyst, at least one
non-metallocene, non-constrained geometry, transition metal
compound selected from bidentate transition metal compound, and
tridentate transition metal compound capable of (A) being activated
upon contact with the support-activator of (I), or (B) being
converted, upon contact with an organometallic compound, to an
intermediate capable of being activated upon contact with the
support-activator, wherein the transition metal is at least one
element selected from Groups 3 to 10 of the Periodic Table; (III)
contacting the support-activator and pre-catalyst in the presence
of at least one inert liquid hydrocarbon in a manner sufficient to
provide a ratio of micromoles of pre-catalyst to grams of
support-activator of from about 5:1 to about 500:1.
18. The catalyst system of claim 17 prepared by the additional step
of including at least one organometallic compound in the liquid
hydrocarbon of step III, said organometallic compound being
represented by the structure formula: M(R.sup.12).sub.s wherein M
represents at least one element of Groups 1, 2, or 13 of the
Periodic Table, tin or zinc, and each R.sup.12 independently
represents at least one of hydrogen, halogen, or hydrocarbon-based
group, and "s" is a number corresponding to the oxidation number of
M, said organometallic compound being in intimate contact with said
pre-catalyst, wherein the amount of organometallic compound present
is sufficient to provide a molar ratio of organometallic compound
to pre-catalyst of from about 0.001:1 to about 250:1.
19. The catalyst system of claim 17 wherein the transition metal
compound is a bidentate transition metal compound represented by
the formula: 9wherein: (I) each A independently represents oxygen,
sulfur, phosphorus or nitrogen; (II) Z represents a transition
metal selected from at least one of the group of Fe, Co, Ni, Ru,
Rh, Pd, Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn,
Zr, and Hf in the +2, +3 or +4 oxidation state; (III) each L and L'
independently represents a ligand group selected from at least one
of hydrogen, halogen, and hydrocarbon based radical, or two L
groups together represent a hydrocarbon based radical which,
together with Z, constitute a heterocyclic ring structure; and (IV)
"a" is an integer of 0 or 1 and represents the number of L' groups
bound to Z, the lines joining each A to each other A represent a
hydrocarbon based radical joined to A by a double or single bond,
and the lines joining each A to Z represent a covalent or dative
bond.
20. The catalyst system of claim 17 wherein the transition metal
compound is a tridentate transition metal compound represented by
the formula: 10wherein: (I) each A independently represents oxygen,
sulfur, phosphorous or nitrogen; (II) Z represents a transition
metal selected from at least one member of the group of Fe, Co, Ni,
Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr,
Mn, Zr, and Hf in the +2, +3 or +4 oxidation state; (III) each L
and L' independently represents a ligand group selected from at
least one of hydrogen, halogen, and hydrocarbon based radical, or
two L groups together represent a hydrocarbon based radical which,
together with Z, constitute a heterocyclic ring structure; and (IV)
"a" is an integer of 0, 1 or 2 and represents the number of L'
groups bound to Z, the lines joining each A to each other A
represent a hydrocarbon based radical joined to A by a double or
single bond, and the lines joining each A to Z represent a covalent
or dative bond.
21. The catalyst system of any one of claims 19 and 20 wherein each
A represents nitrogen, each L and L' is independently halogen,
hydrocarbyl, or mixtures thereof, or two L groups together
represent a hydrocarbylene group which, together with Z, constitute
a 3 to 7 member heterocyclic ring structure.
22. The catalyst system of claim 18 wherein M is aluminum, "s" is
3, and R.sup.12 is C.sub.1 to C.sub.24 alkyl, and each L of the
pre-catalyst is selected from halogen.
23. The catalyst composition of any one of claims 19 and 20 wherein
at least one L of the pre-catalyst is hydrocarbyl.
24. The catalyst system of any one of claims 19 and 20 wherein Z is
selected from at least one of Ni, Pd, Fe, or Co.
25. The catalyst system of claim 19 wherein Z is selected from Ni
or Pd and each L is independently selected from chlorine, bromine,
iodine, and C.sub.1-C.sub.8 alkyl.
26. The catalyst system of claim 20 wherein Z is selected from iron
and cobalt and each L is independently selected from chlorine,
bromine, iodine, and C.sub.1-C.sub.8 alkyl.
27. The catalyst system of claim 19 prepared by the additional step
of including in the inert hydrocarbon liquid of step III, at least
one organometallic compound represented by the structural formula:
M(R.sup.12).sub.s wherein M represents at least one element of
Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each
R.sup.12 independently represents at least one of hydrogen,
halogen, or hydrocarbyl group, and "s" is the oxidation number of
M; said organometallic compound being in intimate contact with said
pre-catalyst in an amount sufficient to provide a molar ratio of
organometallic compound to pre-catalyst of from about 0.01:1 to
about 125:1.
28. The catalyst system of claim 20 prepared by the additional
steps of including in the inert hydrocarbon liquid of step III, at
least one organometallic compound represented by the structural
formula: M(R.sup.12).sub.s wherein M represents at least one
element of Group 1, 2, or 13 or the Periodic Table, tin or zinc,
and each R.sup.12 independently represents at least one of
hydrogen, halogen, or hydrocarbyl group, and "s" is the oxidation
number of M; said organometallic compound being in intimate contact
with said pre-catalyst in an amount sufficient to provide a molar
ratio of organometallic compound to pre-catalyst of from about
0.1:1 to about 10:1.
29. The catalyst system of claim 27 wherein M is aluminum, R.sup.12
is alkyl or alkoxy, "s" is 3, Z is selected from at least one of Ni
and Pd, and L is halogen.
30. The catalyst system of claim 28 wherein M is aluminum, R.sup.12
is alkyl or alkoxy, "s" is 3, Z is selected from at least one of Fe
or Co, and L is halogen.
31. The catalyst system of claim 17 wherein the support-activator
is at least one of clay or clay mineral having a negative charge
below 0.
32. The catalyst system of claim 31 wherein the layered material is
a smectite clay, the weight ratio of inorganic oxide to clay in the
support activator agglomerate is from about 0.25:1 to about 99:1,
and the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 10:1 to about 250:1.
33. The catalyst system of claim 32 wherein the smectite clay is at
least one of montmorillonite and hectorite, the weight ratio of
inorganic oxide to clay in the support-activator agglomerate is
from about 0.5:1 to about 20:1, and the ratio of micromoles of
pre-catalyst to grams of support-activator is from about 30:1 to
about 100:1.
34. The catalyst system of claim 17 wherein the inorganic oxide
component is SiO.sub.2, the weight ration of SiO.sub.2 to layered
material in the support-activator agglomerate is from about 1:1 to
about 10:1, and the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 80:1 to about 100:1.
35. The catalyst system of any one of claims 17 and 18 wherein the
support-activator comprises spray dried agglomerate particles
comprising constituent particles of at least one of said inorganic
oxides and at least one of said layered materials wherein: (I) at
least 80% of the volume of the agglomerated particles smaller than
D.sub.90 of the entire agglomerate particle size distribution
possesses a microspheroidal morphology; (II) the support-activator
agglomerate particles possess: (A) an average particle size of from
about 4 to about 250 microns, and (B) a surface area of from 20 to
about 800 m.sup.2/gm; (III) the constituent inorganic oxide
particles from which the agglomerate particles are derived have an
average particle size, prior to spray drying, of from about 2 to
about 10 microns, and the constituent layered material particles
have an average particle size, prior to spray drying, of from about
0.01 to about 50 microns.
36. The catalyst system of claim 35 wherein the constituent
inorganic oxide particles from which the agglomerate particles are
derived, prior to spray drying, have: (I) an average particle size
of from about 4 to about 9 microns, (II) a particle size
Distribution Span of from about 0.5 to about 3.0 microns, and (III)
and a colloidal particle size content of from about 2 to about 60
wt. %, based on the constituent inorganic oxide particle
weight.
37. A process for preparing a catalyst system for polymerizing
olefins. comprising: (I) agglomerating to form a support-activator:
(A) at least one inorganic oxide component selected from SiO.sub.2,
Al.sub.2O.sub.3, MgO, AlPO.sub.4, TiO.sub.2, ZrO.sub.2,
Cr.sub.2O.sub.3 with (B) at least one ion containing layered
material having interspaces between the layers and sufficient Lewis
acidity, when present within the support-activator, to activate the
pre-catalyst compound of (II) when the pre-catalyst is in contact
with the support-activator, said layered material having a cationic
component and an anionic component, wherein said anionic component
is present within the interspace of the layered material, said
layered material being intimately dispersed with said inorganic
oxide component within the agglomerate in amounts sufficient to
improve the activity of the coordinating catalyst system for
polymerizing ethylene monomer, expressed as Kg of polyethylene per
gram of catalyst system per hour, relative to the activity of a
corresponding catalyst system employing the same pre-catalyst but
in the absence of either Component A or B of the support-activator;
(II) providing as a pre-catalyst, at least one non-metallocene,
non-constrained geometry transition metal compound selected from
bidentate transition metal compound, and tridentate transition
metal compound, capable of (A) being activated upon contact with
the support-activator, or (B) being converted, upon contact with an
organometallic compound, to an intermediate capable of being
activated upon contact with the support-activator, wherein the
transition metal is at least one member selected from Groups 3 to
10 of the Periodic Table; (III) contacting the support-activator
and pre-catalyst in the presence of at least one inert liquid
hydrocarbon in a manner sufficient to provide in the liquid
hydrocarbon, a ratio of micromoles of pre-catalyst to grams of
support-activator of from about 5:1 or to about 500:1, and to cause
at least one of absorption and adsorption of the pre-catalyst by
the support-activator.
38. The process of claim 37 further comprising including at least
one organometallic compound in the inert liquid hydrocarbon of step
III represented by the structure formula: M(R.sup.12).sub.s wherein
M represents at least one element of Groups 1, 2, or 13 of the
Periodic Table, tin or zinc, and each R.sup.12 independently
represents at least one of hydrogen, halogen, or hydrocarbon-based
group, and "s" is the oxidation number of M, said organometallic
compound being in intimate contact with said pre-catalyst, wherein
the amount of organometallic compound present in the liquid
hydrocarbon is sufficient to provide a molar ratio of
organometallic compound to pre-catalyst of from about 0.001:1 to
about 250:1.
39. The process of claim 37 wherein the transition metal compound
is a bidentate transition metal compound represented by the
formula: 11wherein: (I) each A independently represents oxygen,
sulfur, phosphorus nitrogen; (II) Z represents a transition metal
selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd,
Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and
Hf in the +2, +3 or +4 oxidation state; (III) each L and L'
independently represents a ligand group selected from at least one
of hydrogen, halogen, and hydrocarbon based radical, or two L
groups together represent a hydrocarbon based radical, which
together with Z, constitute a heterocyclic ring structure; and (IV)
"a" is an integer of 0 or 1 and represents the number of L' groups
bound to Z, the lines joining each A to each other A represent a
hydrocarbon based radical joined to A by a double or single bond,
and the lines joining each A to Z represent a covalent or dative
bond.
40. The process of claim 37 wherein the transition metal compound
is a tridentate transition metal compound represented by the
formula: 12wherein: (I) each A independently represents oxygen,
sulfur, phosphorous or nitrogen; (II) Z represents a transition
metal selected from at least one of the group of Fe, Co, Ni, Ru,
Rh, Pd, Os, Ir and Pt in the +2 oxidation state and Ti, V, Cr, Mn,
Zr, and Hf in the +2, +3 or +4 oxidation state; (III) each L and L'
independently represents a ligand group selected from at least one
of hydrogen, halogen, and hydrocarbon based radical, or two L
groups together represent a hydrocarbon based radical which,
together with Z, constitute, a heterocyclic ring structure; and
(IV) "a" is an integer of 0, 1 or 2 and represents the number of L'
groups bound to Z, the lines joining each A to each other A
represent a hydrocarbon based radical joined to A by a double or
single bond, and the lines joining each A to Z represent a covalent
or dative bond.
41. The process of any one of claims 39 and 40 wherein each A
represents nitrogen, each L and L' is independently selected from
halogen, hydrocarbyl or mixtures thereof, or two L groups together
represent a hydrocarbylene group which, together with Z, constitute
a 3 to 7 member heterocyclic ring structure.
42. The process of claim 38 wherein M is aluminum, "s" is 3, and
R.sup.12 is C.sub.1 to C.sub.24 alkyl, and each L of the
pre-catalyst is halogen.
43. The process of any one of claims 39 and 40 wherein at least one
L of the pre-catalyst is hydrocarbyl.
44. The process of any one of claims 39 and 40 wherein Z is
selected from at least one of Ni, Pd, Fe, or Co.
45. The process of claim 39 wherein Z is selected from Ni or Pd and
each L is independently selected from chlorine, bromine, iodine,
and C.sub.1-C.sub.8 alkyl.
46. The process of claim 40 wherein Z is selected from iron or
cobalt and each L is independently selected from chlorine ,
bromine, iodine, and C.sub.1-C.sub.8 alkyl.
47. The process of claim 39 prepared by the additional step of
including in the inert liquid hydrocarbon of step III, at least one
organometallic compound represented by the structure formula:
M(R.sup.12).sub.s wherein M represents at least one element of
Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each
R.sup.12 independently re presents at least one of hydrogen,
halogen, or hydrocarbyl group, and "s" is the oxidation number of
M; said organometallic compound being in intimate contact with said
pre-catalyst in an amount sufficient to provide a molar ratio of
pre-catalyst to organometallic compound from about 0.01:1 to about
125:1.
48. The process of claim 40 prepared by the additional step of
including at least one organometallic compound in the inert liquid
hydrocarbon of step III represented by the structure formula:
M(R.sup.12).sub.s wherein M represents at least one element of
Group 1, 2, or 13 or the Periodic Table, tin or zinc, and each
R.sup.12 independently represents at least one of hydrogen, halogen
or hydrocarbyl group, and "s" is the oxidation number of M; said
organometallic compound being in intimate contact with said
pre-catalyst in an amount sufficient to provide a molar ratio of
pre-catalyst to organometallic compound in the hydrocarbon liquid
from about 0.1:1 to about 10:1.
49. The process of claim 47 wherein M is aluminum, R.sup.12 is
alkyl or alkoxy, "s" is 3, Z is selected from at least one of Ni,
Pd, and L is halogen.
50. The process of claim 48 wherein M is aluminum, R.sup.12 is
alkyl or alkoxy, "s" is 3, Z is selected from at least one of Fe or
Co, and L is halogen.
51. The process of claim 37 wherein the support-activator is at
least one of clay or clay mineral having a negative charge below
0.
52. The process of claim 51 wherein the layered material is a
smectite clay, the weight ratio of inorganic oxide to clay in the
support activator agglomerate is from about 0.25:1 to about 99:1,
and the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 10:1 to about 250:1.
53. The process of claim 52 wherein the smectite clay is at least
one of montmorillonite and hectorite, the weight ratio of inorganic
oxide to clay in the support-activator agglomerate is from about
0.5:1 to about 20:1, and the ratio of micromoles of transition
metal in the pre-catalyst to grams of support-activator is from
about 30:1 to about 100:1.
54. The process of claim 37 wherein the inorganic oxide is
SiO.sub.2, the weight ratio of SiO.sub.2 to layered material in the
support-activator agglomerate is from about 1:1 to about 10:1, and
the ratio of micromoles of pre-catalyst to grams of
support-activator is from about 30:1 to about 100:1.
55. The process of any one of claims 37 and 38 wherein the
support-activator comprises spray dried agglomerate particles
comprising constituent particles of at least one of said inorganic
oxides and at least one of said layered materials wherein: (I) at
least 80% of the volume of the agglomerated particles smaller than
D.sub.90 of the entire agglomerate particle size distribution
possesses a microspheroidal morphology; (II) the support-activator
agglomerate particles possess (A) an average particle size of from
about 5 to about 250 microns, and (B) a surface area of from 20 to
about 800 m.sup.2/gm; (III) the constituent inorganic oxide
particles from which the agglomerate particles are derived have an
average particle size, prior to spray drying, of from about 2 to
about 10 microns and the constituent layered material particles
have an average particle size, prior to spray drying, of from about
0.01 to about 50 microns.
56. The process of claim 55 wherein the constituent inorganic oxide
particles from which the agglomerate particles are derived, prior
to spray drying, have: (I) an average particle size of from about 4
to about 9 microns; (II) a particle size Distribution Span of from
about 0.5 to about 3.0 microns; and (III) a colloidal particle size
content of from about 2 to about 60 wt. %, based on the constituent
inorganic oxide weight.
57. The process of claim 37 wherein the support-activator and
pre-catalyst are agitated in the liquid hydrocarbon at a
temperature of from about 0 to about 80.degree. C. for a period of
from about 0.5 to about 1440 minutes.
58. The process of claim 37 wherein the liquid hydrocarbon is
separated from the mixture of support-activator and
pre-catalyst.
59. The process of claim 38 wherein the liquid hydrocarbon is
separated from the mixture of support-activator, pre-catalyst and
organometallic compound.
60. The process of claim 38 wherein the organometallic compound is
contacted with pre-catalyst prior to contract with the
support-activator.
61. The process of claim 37 further comprising including in the
inert liquid hydrocarbon of step III, at least one organometallic
compound represented by the structural formula: M(R.sup.12).sub.s
wherein M represents at least one element of Groups 1, 2, or 13 or
the Periodic Table, tin or zinc, and each R.sup.12 independently
represents at least one of hydrogen, halogen, or hydrocarbyl group,
and "s" is the oxidation number of M, said organometallic compound
being in intimate contact with said pre-catalyst, wherein the
amount of organometallic compound present is sufficient to provide
a ratio of millimoles of organometallic compound to grams of
support-activator of from about 0.001:1 to about 2:1.
62. The process of claim 61 wherein said ratio is from about 0.1:1
to about 0.8:1.
63. The process of claim 37 further comprising calcining the
support-activator at a temperature of from about 100 to about
800.degree. C. for a period of from about 1 to about 600
minutes.
64. The process of claim 37 further comprising recovering the
support-activator having the pre-catalyst impregnated therein from
the liquid hydrocarbon.
Description
FIELD OF THE INVENTION
[0001] The invention relates to coordination catalyst systems,
which comprise a support-activator in agglomerate form and a
coordination catalyst component and methods of their
preparation.
BACKGROUND OF THE INVENTION
[0002] Coordination catalyst systems, which are usually based on
transition metal compounds of Groups 3 to 10 and organometallic
compounds of Group 13 of the Periodic Table of the Elements, are
exceptionally diverse catalysts which are employed in chemical
reactions of and with olefinically unsaturated compounds. Such
reactions are embodied in processes for the preparation of olefin
polymers by coordination polymerization.
[0003] The preparation of polyethylene of increased density
(high-density polyethylene, HDPE) and of polymers and copolymers of
ethylene, propylene or other 1-alkenes is of considerable
industrial importance.
[0004] The prevailing belief on the reaction mechanism of
coordination catalysts is that a transition metal compound forms a
catalytically active center to which the olefinically unsaturated
compound bonds by coordination in a first step. Olefin
polymerization takes place via coordination of the monomers and a
subsequent insertion reaction into a transition metal-carbon or a
transition metal-hydrogen bond.
[0005] The presence of organometallic compounds (e.g.,
organoaluminum compounds such as methylalumoxane) in the
coordination catalyst systems or during the catalyzed reaction is
thought to be necessary in order to activate the catalyst, or
maintain its activity, by reduction and, where appropriate,
alkylation or formation of a complex system. These compounds were
therefore also called cocatalysts. The compound containing the
transition metal atom, which is eventually activated, is typically
called the pre-catalyst and after activation, the primary
catalyst.
[0006] The best known industrially used catalyst systems for
coordination polymerization are those of the "Ziegler-Natta
catalyst" type and the "Phillips catalyst" type. The former
comprise the reaction product of a metal alkyl or hydride of
elements of the first three main groups of the Periodic Table and a
reducible compound of a transition metal element of Groups 4 to 7
the combination used most frequently comprising an aluminum alkyl,
such as diethylaluminum chloride, and titanium (IV) chloride. More
recent highly active Ziegler-Natta catalysts are systems in which
the titanium compound is fixed chemically to the surface of
magnesium compounds, such as, in particular, magnesium
chloride.
[0007] More recent developments have focused on single-site
catalyst systems. Such systems are characterized by the fact that
their metal centers behave alike during polymerization thus making
very uniform polymers.
[0008] Catalysts are judged to behave in a single-site manner when
the polymer they make meets some basic criteria (e.g., narrow
molecular weight distribution, or uniform comonomer distribution).
Thus, the metal can have any ligand set around it and be classified
as "single-site" as long as the polymer that it produces has
certain properties.
[0009] Includable within single-site catalyst systems are
metallocene catalysts and constrained geometry catalysts.
[0010] A "metallocene" is conventionally understood to mean a metal
(e.g., Zr, Ti, Hf, Sc, Y, Vi or La) complex that is bound to two
cyclopentadienyl (Cp) rings, or derivatives thereof, such as
indenyl, tetrahydroindenyl, fluorenyl and mixtures. In addition to
the two Cp ligands, other groups can be attached to the metal
center, most commonly halides and alkyls. The Cp rings can be
linked together (so-called "bridged metallocene" structure), as in
most polypropylene catalysts, or they can be independent and freely
rotating, as in most (but not all) metallocene-based polyethylene
catalysts. The defining feature is the presence of two Cp ligands
or derivatives.
[0011] Metallocene catalysts can be employed either as so-called
"neutral metallocenes" in which case an alumoxane, such as
methylalumoxane, is used as a co-catalyst, or they can be employed
as so-called "cationic metallocenes" which incorporate a stable and
loosely bound non-coordinating anion as a counter ion to a cationic
metal metallocene center. Cationic metallocenes are disclosed in
U.S. Pat. Nos. 5,064,802; 5,225,500; 5,243,002; 5,321,106;
5,427,991; and U.S. Pat. No. 5,643,847; and EP 426 637 and EP 426
638.
[0012] "Constrained geometry" is a term that refers to a particular
class of organometallic complexes in which the metal center is
bound by only one modified Cp ring or derivative. The Cp ring is
modified by bridging to a heteroatom such as nitrogen, phosphorus,
oxygen, or sulfur, and this heteroatom also binds to the metal
site. The bridged structure forms a fairly rigid system, thus the
term "constrained geometry". By virtue of its open structure, the
constrained geometry catalyst can produce resins (long chain
branching) that are not possible with normal metallocene
catalysts.
[0013] Still more recently, late transitional metal (e.g., Fe, Co,
Ni, or Pd) bidentate and tridentate catalyst systems have been
developed. Representative disclosures of such late transition metal
catalysts are found in U.S. Pat. No. 5,880,241 and its divisional
counterparts U.S. Pat. Nos. 5,880,323; 5,866,663; 5,886,224; and
U.S. Pat. No. 5,891,963, and PCT International Application Nos.
PCT/US98/00316; PCT/US97/23556; PCT/GB99/00714; PCT/GB99/00715; and
PCT/GB99/00716.
[0014] Both the single site and late transition metal pre-catalysts
typically require activation to form a cationic metal center by an
organometal Lewis acid (e.g., methyl alumoxane (MAO))
(characterized as operating through a hydrocarbyl abstraction
mechanism). Such activators or cocatalysts are pyrophoric (or
require pyrophoric reagents to make the same), and are typically
employed in quantities which are multiples of the catalyst.
Attempts to avoid such disadvantages have led to the development of
borane (e.g., trispentaflurophenylborane) and borate (e.g.,
ammonium tetrakispentaflurophenylborate) activators which are
non-pyrophoric but more expensive to manufacture. These factors
complicate the development of heterogeneous versions of such
catalyst systems in terms of meeting cost and performance
targets.
[0015] Use of these catalysts and related types in various
polymerization processes can give products with sometimes extremely
different properties. In the case of olefin polymers, which are
generally known to be important as materials, the suitability for
particular applications depends, on the one hand, on the nature of
the monomers on which they are based and on the choice and ratio of
comonomers and the typical physical parameters which characterize
the polymer, such as average molecular weight, molecular weight
distribution, degree of branching, degree of crosslinking,
crystallinity, density, presence of functional groups in the
polymer and the like, and on the other hand, on properties
resulting from the process, such as content of low molecular weight
impurities and presence of catalyst residues, and last but not
least on costs.
[0016] In addition to realization of the desired product
properties, other factors are decisive for evaluating the
efficiency of a coordination catalyst system, such as the activity
of the catalyst system, that is to say the amount of catalyst
required for economic conversion of a given amount of olefin, the
product conversion per unit time and the product yield. Catalyst
systems such as the Fe or Co catalysts described herein, which
exhibit high productivity and high specificity in favor of a low
degree of branching of the polymer, are sought for certain
applications. Catalyst systems utilizing the Ni and Pd catalysts
described herein seek to achieve highly branched polymers with
reasonable productivity.
[0017] The stability and ease of handling of the catalyst or its
components is another factor which affects the choice of commercial
embodiments thereof. Practically all known coordination catalysts
are extremely sensitive to air and moisture to varying degrees.
Coordination catalysts are typically reduced in their activity or
irreversibly destroyed by access to (atmospheric) oxygen and/or
water. Most Ziegler-Natta and metallocene catalysts, for example,
deactivate spontaneously on access to air and become unusable. Most
coordination catalysts must therefore typically be protected from
access of air and moisture during preparation, storage and use,
which of course makes handling difficult and increases the
expenditure required. The bi-end tri-dentate catalysts described
herein are known to be more tolerant toward oxygen.
[0018] A still further factor to be considered is the ability to
utilize the coordination catalyst as a heterogeneous catalyst
system. The advantages of a heterogeneous catalyst system are more
fully realized in a slurry polymerization process. More
specifically, slurry polymerizations are often conducted in a
reactor wherein monomer, catalysts, and diluent are continuously
fed into the reactor. The solid polymer that is produced is not
dissolved in the diluent and is allowed to settle out before being
periodically withdrawn form the reactor. In this kind of
polymerization, factors other than activity and selectivity, which
are always present in solution processes, become of paramount
importance.
[0019] For example, in the slurry process it is desired to have a
supported catalyst which produces relatively high bulk density
polymer. If the bulk density is too low, the handling of the solid
polymer becomes impractical. It is also an advantage to have the
polymer formed as uniform, spherical particles that are relatively
free of fines. Although fines can have a high bulk density, they
also do not settle as well as larger particles and they present
additional handling problems with the later processing of the
polymer fluff.
[0020] Furthermore, slurry polymerization processes differ in other
fundamental ways from the typical solution polymerization
processes. The latter requires higher reaction temperatures
(>130.degree. C.) and pressures (>450 psi) and often results
in lower molecular weight polymers. The lower molecular weight is
attributed to the rapid chain-termination rates under such reaction
conditions. Although lowering the reaction temperature and/or
pressure, or changing molecular structure of the metallocene
catalyst can produce higher molecular weight polymer in a solution
process, it becomes impractical to process the resulting high
molecular weight polymers in the downstream equipment due to the
high viscosity.
[0021] In contrast, a slurry reaction process overcomes many of the
above disadvantages by simply operating at lower temperature
(<100.degree. C.). As a result, a higher molecular weight
polymer with a uniform particle size and morphology can be
routinely obtained. It is also advantageous to carry out slurry
reactions with sufficiently high polymerization efficiencies such
that residues from the polymerization catalysts do not have to be
removed from the resulting polymers. The above-discussed advantages
of slurry polymerization processes provides incentive for
developing coordination catalysts in heterogeneous form. Thus far,
gas phase polymerization processes are only practical with a
heterogeneous catalyst system.
[0022] Finally, evaluation of a coordination catalyst system must
include process considerations which influence the morphology
(e.g., bulk density) of the resulting polymer, the environmental
friendliness of the process, and avoidance of reactor fouling.
[0023] Thus, there has been a continuing search to develop a
coordination catalyst system, preferably a heterogeneous
coordination catalyst system, which demonstrates high catalyst
activity, is free of reactor fouling, produces polymer products
having good resin morphology while simultaneously being very
process friendly (e.g., easy to make) and inexpensive to make.
[0024] There has also been a particular need to discover compounds
which are less sensitive to deactivation and/or less hazardous and
still suitable as activating components in coordination catalyst
systems.
[0025] The present invention was developed in response to these
searches.
[0026] International application No. PCT/US97/11953 (International
Publication No. WO 97/48743) is directed to frangible, spray dried
agglomerate catalyst supports of silica gel, which possess a
controlled morphology of microspheroidal shape, rough scabrous
appearance, and interstitial void spaces which penetrate the
agglomerate surface and are of substantially uniform size and
distribution. The agglomerates also possess a 1-250 micron particle
size, 1-1000 m.sup.2/g surface area, and an Attrition Quality Index
(AQI) of at least 10. The agglomerates are derived from a mixture
of dry milled inorganic oxide particles, e.g., silica gel and
optionally but preferably wet milled inorganic oxide particles,
e.g., silica gel particles (which preferably contain a colloidal
content of less than 1 micron particle), slurried in water for
spray drying. The high AQI assures that the agglomerates are
frangible and that the polymerization performance is improved. The
controlled morphology is believed to permit the constituent
particles of the agglomerates to be more uniformly impregnated or
coated with conventional olefin polymerization catalysts. Clay is
not disclosed as suitable metal oxide.
[0027] U.S. Pat. No. 5,633,419 discloses the use of spray dried
silica gel agglomerates as supports for Ziegler-Natta catalyst
systems.
[0028] U.S. Pat. No. 5,395,808 discloses bodies made by preparing a
mixture of ultimate particles of bound clay, with one or more
optional ingredients such as inorganic binders, extrusion or
forming aids, burnout agents or forming liquid, such as water.
Preferably the ultimate particles are formed by spray drying.
Suitable binders include silica when Kaolin clay is used as the
inorganic oxide. The bodies are made from the ultimate particles
and useful methods for forming the bodies include extrusion,
pelletization, balling, and granulating. Porosity is introduced
into the bodies during their assembly from the ultimate particles,
and results primarily from spaces between the starting particles.
The porous bodies are disclosed to be useful as catalyst supports.
See also U.S. Pat. Nos. 5,569,634; 5,403,799; and U.S. Pat. No.
5,403,809; and EP 490 226 for similar disclosures.
[0029] U.S. Pat. No. 5,362,825 discloses olefin polymerization
catalysts produced by contacting a pillared clay with a
Ziegler-Natta catalyst, i.e., a soluble complex produced from the
mixture of a metal dihalide with at least one transition metal
compound in the presence of a liquid diluent. The resulting mixture
is in turn contacted with an organoaluminum halide to produce the
catalyst.
[0030] U.S. Pat. No. 5,807,800 is directed to a supported
metallocene catalyst comprising a particulate catalyst support,
such as a molecular sieve zeolite, and a stereospecific
metallocene, supported on the particulate support and incorporating
a metallocene ligand structure having two sterically dissimilar
cyclopentadienyl ring structures coordinated with a central
transition metal atom. At column 4 of the background discussion, it
is disclosed that cationic metallocenes which incorporate a stable
non-coordinating anion normally do not require the use of
alumoxane.
[0031] U.S. Pat. No. 5,238,892 discloses the use of undehydrated
silica as a support for metallocene and trialkylaluminum
compounds.
[0032] U.S. Pat. No. 5,308,811 discloses an olefin polymerization
catalyst obtained by contacting (a) a metallocene-type transition
metal compound, (b) at least one member selected from the group
consisting of clay, clay minerals, ion exchanging layered
compounds, diatomaceous earth, silicates and zeolites, and (c) an
organoaluminum compound. Component (b) may be subjected to chemical
treatment, which, for example, utilizes ion exchangeability to
substitute interlaminar exchangeable ions of the clay with other
large bulky ions to obtain a layered substance having the
interlaminar distance enlarged. Such bulky ions play the role of
pillars, supporting the layered structure, and are therefore called
pillars. Guest compounds, which can be intercalated, include
cationic inorganic compounds derived from such materials as
titanium tetrachloride and zirconium tetrachloride. SiO.sub.2 may
be present during such intercalation of guest compounds. The
preferred clay is montmorillonite. Silica gel is not disclosed as a
suitable component (b).
[0033] U.S. Pat. No. 5,753,577 discloses a polymerization catalyst
comprising a metallocene compound, a co-catalyst such as proton
acids, ionized compounds, Lewis acids and Lewis acidic compounds,
as well as clay mineral. The clay can be modified by treatment with
acid or alkali to remove impurities from the mineral and possibly
to elute part of the metallic cations from the crystalline
structure of the clay. Examples of acids which can effect such
modification include Bronsted acids such as hydrochloric, sulfuric,
nitric and acetic acids. The preferred modification of the clay is
accomplished by exchanging metallic ions originally present in the
clay with specific organic cations such as aliphatic ammonium
cations, oxonium ions, and onium compounds such as aliphatic amine
hydrochloride salts. Such polymerization catalysts may optionally
be supported by fine particles of SiO.sub.2, Al.sub.2O.sub.3,
ZrO.sub.2, B.sub.2O.sub.3, CaO, ZnO, MgCl.sub.2, CaCl.sub.2, and
mixtures thereof. (Col. 3, line 48; Col. 21, line 10 et seq.). The
fine particle support may be of any shape preferably having a
particle size in the range of 5-200 microns, and pore size ranges
of from 20-100.ANG.. Use of metal oxide support is not described in
the examples.
[0034] U.S. Pat. No. 5,399,636 discloses a composition comprising a
bridged metallocene which is chemically bonded to an inorganic
moiety such as clay or silica. Silica is illustrated in the working
examples as a suitable support, but not clay.
[0035] EP 849 292 discloses an olefin polymerization catalyst
consisting essentially of a metallocene compound, a modified clay
compound, and an organoaluminum compound. The modification of the
clay is accomplished by reaction with specific amine salts such as
a proton acid salt obtained by the reaction of an amine with a
proton acid (hydrochloric acid). The specifically disclosed proton
acid amine salt is hexylamine hydrochloride. The modification of
the clay results in exchange of the ammonium cation component of
the proton acid amine salt with the cations originally present in
the clay to form the mineral/organic ion complex.
[0036] U.S. Pat. No. 5,807,938 discloses an olefin polymerization
catalyst obtained by contacting a metallocene compound, an
organometallic compound, and a solid catalyst component comprising
a carrier and an ionized ionic compound capable of forming a stable
anion on reaction with the metallocene compound. Suitable carriers
disclosed include inorganic compounds or organic polymeric
compounds. The inorganic compounds include inorganic oxides, such
as alumina, silica, silica-alumina, silica magnesia; clay minerals;
and inorganic halides. The ionized ionic compound contains an
anionic component and a cationic component. The cationic component
preferably comprises a Lewis Base functional group containing an
element of the Group 15 or 16 of the Periodic Table such as
ammonium, oxionium, sulfonium, and phosphonium, cations. The cation
component may also contain a functional group other than Lewis Base
function groups, such as carbonium, tropinium, and a metal cation.
The anion component includes those containing a boron, aluminum,
phosphorous or antimony atom, such as an organoboron,
organoaluminum, organophosphorous, and organoantimony anions. The
cationic component is fixed on the surface of the carrier. Only
silica or chlorinated silica are employed in the working examples
as a carrier. In many examples, the silica surface is modified with
a silane.
[0037] U.S. Pat. No. 5,830,820 discloses an olefin polymerization
catalyst comprising a modified clay mineral, a metallocene
compound, and an organoaluminum compound. The clay inneral is
modified with a compound capable of introducing a cation into the
layer interspaces of the clay mineral. Suitable cations which are
inserted into the clay include those having a proton, namely,
Bronsted acids such trimethylammonium, as well as carbonium ions,
oxonium ions, and sulfonium ions. Representative anions include
chlorine ion, bromide ion, and iodide ion.
[0038] EP 881 232 is similar to U.S. Pat. No. 5,830,820, except
that the average particle size of the clay is disclosed as being
less than 10 microns.
[0039] EP 849 288 discloses an olefin polymerization catalyst
consisting essentially of a metallocene compound, an organoaluminum
compound, and a modified clay compound. The clay is modified by
contact with a proton acid salt of certain specific amine
compounds; such as hexylamine chloride.
[0040] JP Kokai Patent HEI 10-338516 discloses a method for
producing a metallic oxide intercalated in a clay mineral which
comprises swelling and diluting the clay mineral, having a laminar
structure, with water to form a sol; adding an organometallic
compound to an aqueous solution containing organic acid to form a
sol that contains the metallic compound; mixing the swelling clay
mineral sol with the metallic compound containing sol and agitating
to intercalate the metallic compound between the layers in the
swollen clay mineral; and washing, dehydrating, drying and roasting
the clay mineral that has the metallic compound intercalated
therein. Suitable metallic oxides include those of titanium, zinc,
iron, and tin.
[0041] U.S. Pat. No. 4,981,825 is directed to a dried solid
composition comprising clay particles and inorganic metal oxide
particles substantially segregated from the clay particles. More
specifically, the metal oxide particles are sol particles which
tend to fuse upon sintering. Consequently, by segregating the sol
particles with smectite-type clay particles, fusion of the sol
particles is reduced under sintering conditions thereby preventing
a loss of surface area. The preferred metal oxide is colloidal
silica having an average particle size between 40 and 800 angstroms
(0.004 and 0.08 microns), preferably 40 and 80 angstroms. The ratio
of the metal oxide to clay is between about 1:1 to 20:1, preferably
4:1 to 10:1. The end product is described at Column 3, line 50 et
seq. as sol particle-clay composites in which the clay platelets
inhibit aggregation of the sol particles. Such products are made up
entirely of irregular sol-clay networks in which the clay platelets
are placed between the sol particles. The result is a composite
with very high surface area, and ability to retain such high
surface area at elevated temperatures. This arrangement is also
distinguished from intercalation of the clay by the silica. The
subject compositions are disclosed in the abstract to be useful for
catalytic gaseous reactions and removal of impurities from gas
streams. Specific catalysts systems are not disclosed.
[0042] U.S. Pat. No. 4,761,391 discloses delaminated clays whose
x-ray defraction patterns do not contain a distinct first order
reflection. Such clays are made by reacting synthetic or natural
swelling clays with a pillaring agent selected from the group
consisting of polyoxymetal cations, mixtures of polyoxymetal
cations, colloidal particles comprising alumina, silica, titania,
chromia, tin oxide, antimony oxide or mixtures thereof, and
cationic metal clusters comprising nickel, molybdenum, cobalt, or
tungsten. The resulting reaction product is dried in a gaseous
medium, preferable by spray drying. The resulting acidic
delaminated clays may be used as the active component of cracking
and hydroprocessing catalysts. The ratio of clay to pillaring agent
is disclosed to be between about 0.1 and about 10. To obtain the
delaminated clay, a suspension of swelling clay, having the proper
morphology, e.g., colloidal particle size, is mixed with a solution
or a suspension of the pillaring agent at the aforedescribed
ratios. As the reactants are mixed, the platelets of clay rapidly
sorb the pillaring agent producing a flocculated mass comprised of
randomly oriented pillared platelet aggregates. The flocculated
reaction product or gel is then separated from any remaining liquid
by techniques such as centrifugation filtration and the like. The
gel is then washed in warm water to remove excess reactants and
then preferably spray dried. The pillaring agent upon heating is
converted to metal oxide clusters which prop apart the platelets of
the clay and impart the acidity which is responsible for the
catalytic activity of the resultant delaminated clay. The x-ray
defraction pattern of such materials contains no distinct first
order of reflection which is indicative of platelets randomly
oriented in the sense that, in addition to face-to-face linkages of
platelets, there are also face-to-edge and edge-to-edge linkages.
The utilities described at Column 8, Lines 55 et seq. include use
as components of catalyst, particularly hydrocarbon conversion
catalysts, and most preferably as components of cracking and
hydrocracking catalysts. This stems from the fact that the because
the clay contains macropores as well as micropores, large molecules
that normally cannot enter the pores of zeolites will have access
to the acid sites in the delaminated clays making such materials
more efficient in cracking of high molecular weight hydrocarbon
constituents. (See also U.S. Pat. No. 5,360,775.)
[0043] U.S. Pat. No. 4,375,406 discloses compositions containing
fibrous clays and precalcined oxides prepared by forming a fluid
suspension of the clay with the precalcined oxide particles,
agitating the suspension to form a co-dispersion, and shaping and
drying the co-dispersion. Suitable fibrous clays include
aluminosilicates, magnesium silicates, and aluminomagnesium
silicates. Examples of suitable fibrous clays are attapulgite,
playgorskite, sepiolite, haloysite, endellite, chrysotile asbestos,
and imogolite. Suitable oxides include silica. The ratio of fibrous
clay to precalcined oxide is disclosed to vary from 20:1 to 1:5 by
weight. In contrast, the presently claimed invention does not
employ fibrous clays.
[0044] Additional patents which disclose intercalated clays are
U.S. Pat. No. 4,629,712 and U.S. Pat. No. 4,637,992. Additional
patents which disclose pillared clays include U.S. Pat. No.
4,995,964 and U.S. Pat. No. 5,250,277.
[0045] A paper presented at the MetCon '99 Polymers in Transition
Conference in Houston, Tex., on Jun. 9-10, 1999, entitled "Novel
Clay Mineral-Supported Metallocene Catalysts for Olefin
Polymerization" by Yoshinor Suga, Eiji Isobe, Toru Suzuki,
Kiyotoshi Fujioka, Takashi Fujita, Yoshiyuki Ishihama, Takehiro
Sagae, Shigeo Go, and Yumito Uehara discloses olefin polymerization
catalysts comprising metallocene compounds supported on dehydrated
clay minerals optionally in the presence of organoaluminum
compounds. At page 5 it is disclosed that catalysts prepared with
fine clay mineral particles has had operational difficulties such
as fouling which make them unsuitable for slurry and gas phase
processes. Thus, a granulation method was developed to give the
clay minerals a uniform spherical shape. The method for producing
this spherical shape is not disclosed.
[0046] PCT International Application No. PCT/US96/17140,
corresponding to U.S. Pat. No. 562,922, discloses a support for
metallocene olefin polymerizations comprising the reaction product
of an inorganic oxide comprising a solid matrix having reactive
hydroxyl groups or reactive silane functionalized derivatives of
hydroxyl groups on the surface thereof, and an activator compound.
The activator compound comprises a cation which is capable of
reacting with the metallocene compound to form a catalytically
active transition metal complex and a compatible anion containing
at least one substituent able to react with the inorganic oxide
matrix through residual hydroxyl functionalities or through the
reactive silane moiety on the surface thereof. The representative
example of a suitable anion activator is tris
(pentafluorophenyl)(4-hydroxyphenyl- )borate. Suitable inorganic
oxides disclosed include silica, alumina, and aluminosilicates.
[0047] U.S. Pat. No. 5,880,241 discloses various late transition
metal bidentate catalyst compositions. At column 52, lines 18 et
seq., it is disclosed that the catalyst can be heterogenized
through a variety of means including the use of heterogeneous
inorganic materials as non-coordinating counter ions. Suitable
inorganic materials disclosed include aluminas, silicas,
silica/aluminas, cordierites, clays, and MgCl.sub.2 but mixtures
are not disclosed. Spray drying the catalyst with its associated
non-coordinating anion onto a polymeric support is also
contemplated. Examples 433 and 434 employ montmorillonite clay as a
support but polymer morphology is not disclosed for these
examples.
[0048] PCT International Application No. PCT/US97/23556 discloses a
process for polymerizing ethylene by contact with Fe or Co
tridentate ionic complex formed either through alkylation or
abstraction of the metal alkyl by a strong Lewis acid compound,
e.g., MAO, or by alkylation with a weak Lewis acid, e.g.,
triethylaluminum and, subsequent abstraction of the resulting alkyl
group on the metal center with a stronger Lewis acid, e.g.,
B(C.sub.6F.sub.5).sub.3. The Fe or Co tridentate compound may be
supported by silica or alumina and activated with a Lewis or
Bronsted acid such as an alkyl aluminum compound (pg. 19, line 1 et
seq.). Acidic clay (e.g., montmorillonite) may function as the
support and replace the Lewis or Bronsted acid. Examples 43-45 use
silica supported MAO, and Example 56 employs dehydrated silica as a
support for the Co complex. Polymer morphology is not
discussed.
[0049] PCT International Application No. PCT/US98/00316 discloses a
process for polymerizing propylene using catalysts similar to the
above discussed PCT-23556 application.
[0050] U.S. Ser. No. 09/166,545, filed Oct. 5, 1998, by Keng-Yu
Shih, an inventor of the present application, discloses a supported
late transition metal bidentate or tridentate catalyst system
containing anion and cation components wherein the anion component
contains boron, aluminum, gallium, indium, tellurium and mixtures
thereof covalently bonded to an inorganic support (e.g. SiO.sub.2)
through silane derived intermediates such as a silica-tethered
anilinium borate.
[0051] U.S. Ser. No. ______ (Docket W-9459-01) filed on an even
date herewith by Keng-Yu Shih discloses the use of silica
agglomerates as a support for transition metal catalyst systems
employing specifically controlled (e.g., very low) amounts of
non-abstracting aluminum alkyl activators.
SUMMARY OF THE INVENTION
[0052] The present invention relies on the discovery that certain
agglomerate composite particles of an inorganic oxide (e.g.,
silica) and an ion exchanging layered compound (e.g., clay) are
believed to possess enhanced Lewis acidity dispersion and
accessibility which renders them extremely proficient
support-activators for certain non-metallocene and non-constrained
geometry bi- and tridentate transition metal compound
pre-catalysts. More specifically, it is believed that the
agglomerate particles incorporate the ionizable clay particles in
such a way that their known Lewis acidity is more uniformly
dispersed throughout the particle while simultaneously being made
more accessible for interaction with the pre-catalyst. It is
believed that this permits the support-activator to effectively and
simultaneously activate, e.g., ionize, the pre-catalyst when in a
pre-activated (e.g., ionizable) state as well as support the active
catalyst during polymerization. This eliminates the need to use
additional ionizing agents which are expensive, and introduce added
complexity to the system. In contrast, the support-activator is
inexpensive, environmentally friendly, and easy to manufacture.
[0053] The present invention relies on the further discovery that
pre-activation of the pre-catalyst is very sensitive to the level
of certain organometallic compounds and is induced by extremely low
amounts of the same. This further reduces the catalyst system
costs, and eliminates the need for expensive MAO or borate
activators of the prior art while simultaneously achieving
extremely high activity.
[0054] A still further aspect of the discovery of the present
invention is that the support-activator apparently immobilizes the
pre-catalyst by adsorption and/or absorption, preferably by
chemadsorption and/or chemabsorption from a slurry of the same
without any special impregnation steps, which slurry can actually
be used directly for the slurry polymerization of olefins. The
resulting polymer morphology is indicative of a heterogeneous
polymerization which is consistent with the observation (based on
x-ray powder diffraction, cross-section microprobe elemental
analysis and the color induced in the support-activator) that the
support-activator is readily impregnated by the pre-catalyst such
that it is believed to react with the same. Moreover, the
microspheroidal morphology of the catalyst system coupled with the
immobilization of the active catalyst therein is believed to
contribute to the extremely desirable observed polymer morphology
because it prevents reactor fouling, eliminates polymer fines and
exhibits a high bulk density. The catalyst system can be employed
as a slurry or dry powder.
[0055] A still even further aspect of the discovery of the present
invention is the functional interrelationship which exists between
the inorganic oxide: layered material weight ratio, the calcination
temperature, and the amount of organoaluminum compound on the one
hand, and the catalyst activity on the other hand, such that these
variables can be controlled to exceed the activity of the same
pre-catalyst supported and/or activated by the inorganic oxide
alone, or the layered material (e.g., clay) alone, while
simultaneously producing good polymer morphology.
[0056] Accordingly, in one aspect of the invention there is
provided a coordinating catalyst system, preferably a heterogeneous
coordinating catalyst system, capable of polymerizing olefins
comprising:
[0057] (I) as a pre-catalyst, at least one non-metallocene,
non-constrained geometry, bidentate transition metal compound or
tridentate transition metal compound capable of (A) being activated
upon contact with the support-activator, or (B) being converted,
upon contact with an organometallic compound, to an intermediate
capable of being activated upon contact with the support-activator,
wherein the transition metal is at least one member selected from
Groups 3 to 10 of the Periodic table; in intimate contact with
[0058] (II) support-activator agglomerate comprising a composite of
(A) at least one inorganic oxide component selected from SiO.sub.2,
Al.sub.2O.sub.3, MgO, AlPO.sub.4, TiO.sub.2, ZrO.sub.2,
Cr.sub.2O.sub.3 and (B) at least one ion containing layered
material having interspaces between the layers and sufficient Lewis
acidity, when present within the support-activator, to activate the
pre-catalyst when the pre-catalyst is in contact with the
support-activator, said layered material having a cationic
component and an anionic component, wherein said anionic component
is present within the interspace of the layered material, said
layered material being intimately dispersed with said inorganic
oxide component within the agglomerate in an amount sufficient to
improve the activity of the coordinating catalyst system for the
polymerization of ethylene monomer, expressed as Kg polyethylene/g
of catalyst system/hour, relative to the activity of a
corresponding coordination catalyst system employing the same
pre-catalyst but in the absence of either component A (inorganic
oxide) or B (layered material) of the support activator, wherein
the amount of the pre-catalyst and support-activator which is in
intimate contact is sufficient to provide a ratio of micromoles of
pre-catalyst to grams of support-activator of from about 5:1 to
about 500:1.
[0059] In another aspect of the present invention, there is
provided a process for making the above catalyst system which
comprises:
[0060] (I) agglomerating to form a support-activator:
[0061] (A) at least one inorganic oxide component selected from
SiO.sub.2, Al.sub.2O.sub.3, MgO, AlPO.sub.4, TiO.sub.2, ZrO.sub.2,
Cr.sub.2O.sub.3 with
[0062] (B) at least one ion containing layered material having
interspaces between the layers and sufficient Lewis acidity, when
present within the support-activator, to activate the transition
metal of the pre-catalyst compound of (II) when in contact with the
support-activator, said layered material having a cationic
component and an anionic component, wherein said anionic component
is present within the interspace of the layered material, said
layered material being intimately dispersed with said inorganic
oxide component within said agglomerate in an amount sufficient to
improve the activity of the coordinating catalyst system for the
polymerization of ethylene monomer, expressed as Kg polyethylene
per gram of catalyst system per hour, relative to the activity of a
corresponding coordination catalyst system employing the same
pre-catalyst but in the absence of either component A or B of the
support-activator;
[0063] (II) providing as a pre-catalyst at least one
non-metallocene, non-constrained geometry pre-catalyst transition
metal compound selected from bidentate transition metal compound,
and tridentate transition metal compound, capable of (A) being
activated upon contact with the support-activator, or (B) being
converted, upon contact with an organometallic compound, to an
intermediate capable of being activated upon contact with the
support-activator, wherein the transition metal is at least one
member selected from Groups 3 to 10 of the Periodic Table;
[0064] (III) contacting the support-activator and pre-catalyst in
the presence of at least one inert liquid hydrocarbon in a manner
sufficient to provide in the liquid hydrocarbon, a ratio of
micromoles of pre-catalyst to grams of support-activator of from
about 5:1 to about 500:1 and to cause at least one of absorption
and adsorption of the pre-catalyst by the support-activator.
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] FIG. 1 is a scanning electron micrograph of a cross-section
of an agglomerate particle prepared in accordance with Example 1,
Run No. 4. The photograph was taken with a scanning electron
microscope and represents a 1000-fold magnification of the actual
agglomerate particle.
[0066] FIG. 2 is a scanning electron micrograph of a cross-section
of an agglomerate particle prepared in accordance with Example 1,
Run No. 4. The photograph was taken with a scanning electron
microscope and represents 2000-fold magnification of the actual
agglomerate particle.
[0067] FIGS. 3 to 14 are contour maps of the activity (KgPE/g of
catalyst system per hour) of coordination catalyst systems prepared
and tested in accordance with Example 8. Each individual plot line
of each Figure is associated with a number which expresses the
expected catalyst activity at the coordinate conditions of wt. %
clay in the support-activator (based on the weight of silica+clay)
(y-axis) and the millimoles of triisobutyl aluminum per gram of
support-activator x-axis).
DESCRIPTION OF PREFERRED EMBODIMENTS
[0068] As indicated above, the present invention employs a
non-metallocene non-constrained geometry neutral transition metal
compound as a pre-catalyst which can be activated by contact with
the support-activator and optionally an organometallic compound
described hereinafter. An activated transition metal compound is
one (a) in which the central transition metal atom such as that,
represented by Z in the following formulas, is changed, such as by
transforming into a state of full or partial positive charge, that
is, the transition metal compound becomes a cation or cation-like,
in its association with a stable anion or anion-like moiety and (b)
that is capable of catalyzing the polymerization of olefins under
polymerization conditions.
[0069] More specifically, the transition metal pre-catalyst can be
at least one bidentate transition metal compound, at least one
tridentate transition metal compound or mixtures thereof capable of
(A) being activated upon contact with the support-activator or (B)
being converted upon contact with an organometallic compound, to an
intermediate which is capable of being activated upon contact with
the support-activator.
[0070] The bidentate pre-catalyst compounds can be generically
represented by the formula: 1
[0071] and the tridentate pre-catalyst compounds can be generically
represented by the formula: 2
[0072] wherein in each of formulas I and II above:
[0073] each A independently represents an at least one of oxygen,
sulfur, phosphorous or nitrogen, and preferably represents oxygen
or nitrogen or a combination thereof, and most preferably each A in
I and at least two A's of II represent nitrogen;
[0074] "a" is an integer of 0, 1 or 2 which represents the number
of (L') groups bound to Z, the value of "a" being dependent on the
oxidation state of Z and whether a particular A-Z bond is dative or
covalent, and if covalent whether it is a single or double
bond;
[0075] Z represents at least one of Group 3 to 10 transition metals
of the Periodic Table, preferably transition metals selected from
Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt in the +2 (a=0) or +3 (a=1)
oxidation state or Ti, V, Cr, Mn, Zr, Hf in the +2 (a=0), +3 (a=1)
or +4 (a=2) oxidation states, more preferably a Group 4 to 7 late
transition metal selected from iron, cobalt, nickel or palladium
and most preferably iron or cobalt; and each L and L' (when
present) independently represents a ligand selected from the group
of hydrogen, halo, and hydrocarbon based radical or group
associated through a covalent or dative bond to Z, or both L groups
together represent a hydrocarbon based radical, preferably a
C.sub.3 to C.sub.24 hydrocarbylene group, associated through a
covalent or dative bond to Z, and which, together with Z.
constitute a ring or fused ring structure, typically a 3 to 7,
preferably 4 to 7 member heterocyclic ring structure when the line
joining A to Z represents a covalent bond.
[0076] As used herein, the term "hydrocarbon-based radical or
group" denotes a radical or group having a carbon atom directly
attached to the remainder of the molecule and having a
predominantly hydrocarbon character within the context of this
invention. Moreover, in this context the terms "group" and
"radical" are used interchangeably. Such radicals include the
following:
[0077] (1) Hydrocarbon radicals; that is, aliphatic radicals,
aromatic- and alicyclic-substituted radicals, and the like, of the
type known to those skilled in art.
[0078] (2) Substituted hydrocarbon radicals; that is, radicals
containing pendant non-hydrocarbon substituents, that in the
context of this invention, do not alter the predominantly
hydrocarbon character of the radical or constitute a poison for the
pre-catalyst. Those skilled in the art will be aware of suitable
substituents; examples are halo, nitro, hydroxy, alkoxy,
carbalkoxy, and alkythio.
[0079] (3) Hetero radicals; that is, radicals which, while
predominantly hydrocarbon in character within the context of this
invention, contain atoms other than carbon present as a member of
the linear structure of a chain or ring otherwise composed of
carbon atoms. Suitable hetero atoms will be apparent to those
skilled in the art and include, for example, nitrogen, oxygen and
sulfur.
[0080] In general, no more than three substituents or hetero atoms,
and preferably no more than one, will be present for each 10 carbon
atoms in the hydrocarbon based radical.
[0081] More specifically, the hydrocarbon based radical or group of
L and L' can be substituted or unsubstituted, cyclic or non-cyclic,
linear or branched, aliphatic, aromatic, or mixed aliphatic and
aromatic including hydrocarbylene, hydrocarbyloxy,
hydrocarbylsilyl, hydrocarbylamino, and hydrocarbylsiloxy radicals
having up to 50 non-hydrogen atoms. The preferred L and L' groups
are independently selected from halo, hydrocarbyl, and substituted
hydrocarbyl radicals. The hydrocarbon based radical may typically
contain from 1 to about 24 carbon atoms, preferably from 1 to about
12 carbon atoms and the substituent group is preferably a halogen
atom.
[0082] The lines joining each A to each other A represent a
hydrocarbon based radical, (typically a C.sub.2 to C.sub.90 (e.g.,
C.sub.2 to C.sub.20) preferably C.sub.3 to C.sub.30 (e.g., C.sub.3
to C.sub.12) hydrocarbon based radical, such as a hydrocarbylene
radical providing a ring or fused ring hydrocarbylene structure or
substituted hydrocarbylene structure. Portions of the structure may
be comprised of carbon-carbon double bonds, carbon-carbon single
bonds, carbon-A atom double bonds and carbon-A atom single
bonds.
[0083] Typically, for the bidentate and tridentate transition metal
compounds, A, Z and the carbons includable in the lines connecting
the (A) groups collectively can be joined to typically make a 4 to
7, preferably 5 to 7 member ring structures.
[0084] The bonds between each A atom of the pre-catalyst and the
transition metal Z and between L and Z can be either dative or
covalent. Dative bonds merely represent a relationship between an
electron rich A atom and the metal Z whereby the electron density
of the metal is increased by providing electrons to the empty
orbitals of the metal and do not induce any change in the oxidation
state of the metal Z. Similar considerations apply to the
relationship between Z and L.
[0085] The above described bidentate and tridentate pre-catalyst
compounds from which the subject catalyst is derived are known. The
disclosure of such components and the methods of forming the same
have been described in various publications, including PCT Pub.
Nos. WO 96/23010; WO 99/46302; WO 99/46303; and WO 99/46304; U.S.
Pat. Nos. 5,880,241; 5,880,323; 5,866,663; 5,886,224; and U.S. Pat.
No. 5,891,963; Journal of the American Chemical Society (JACS)
1998, 120, 6037-6046, JACS 1995, 117, 6414-6415 and Supplemental
Teachings; JACS 1996, 118, 1518; Macromol. Rapid Commun. 19, 31-34
(1998); Caltech Highlights 1997, 65-66; Chem Week 4/29/98, 72;
C&EN 4/13/98 11-12; JACS 1998, 120, 4049-4050; Japanese Patent
Application 02-078,663, and Angew. Chem. Int. Ed. 1999, vol 38, pp
428-447, The Search for New-Generation Olefin Polymerization
Catalysts: Life Beyond Metallocenes. The teaching of each of the
above cited references are incorporated herein in its entirety by
reference.
[0086] In formulas I and II, each L and L' group is preferably a
halogen atom, an unsubstituted hydrocarbyl or a hydrocarbyloxy
group. The most preferred compounds are those having each L being
halogen.
[0087] Preferred bidentate pre-catalyst compounds may, for example
be represented as compounds of the formula: 3
[0088] wherein
[0089] n is an integer which can vary from 0 to 3, preferably 0 or
1;
[0090] a, b, c, and d each independently represents a 1 or 0 to
indicate whether its associated R group is present (1) or not
(0);
[0091] R.sup.1 and R.sup.4 are each independently selected from an
unsubstituted or substituted C.sub.1-C.sub.20, preferably
C.sub.3-C.sub.20 hydrocarbyl, such as alkyl, aryl, alkaryl or
aralkyl group, as for example, i-propyl; t-butyl;
2,4,6-trimethylphenyl; 2-methylphenyl; 2,6-diisopropylphenyl; their
fluorinated derivatives and the like; or with adjacent groups,
together, may represent a C.sub.3-C.sub.20 hydrocarbylene
group;
[0092] R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are
each independently selected from hydrogen, an unsubstituted or
substituted C.sub.1-C.sub.20 hydrocarbyl group such as an alkyl,
aryl, alkaryl or aralkyl group, as for example, methyl, ethyl,
i-propyl, butyl (all isomers), phenyl, toluyl,
2,6-diisopropylphenyl and the like; or any R groups and adjacent
carbon atoms, such as R.sup.2 and R.sup.3, taken together can
provide an unsubstituted or substituted C.sub.3-C.sub.20 ring
forming hydrocarbylene group, such as hexylene, 1,8-naphthylene and
the like.
[0093] Z, A and each L and L' are as defined above in connection
with Formula I. It is preferred that Z be selected from nickel or
palladium and that each L and L' be independently selected from
chlorine, bromine, iodine or a C.sub.1-C.sub.8 (more preferably
C.sub.1-C.sub.4) alkyl. The bonds depicted by a dotted line signify
the possibility that the atoms bridged by said dotted line may be
bridged by a single or double bond.
[0094] It will be understood that the particular identity of b, c,
and d in Formula I will be dependent on (i) the identity of Z, (ii)
the identity of heteroatom A, (iii) whether the bond between
heteroatom A and its adjacent ring carbon is single or double, and
(iv) whether the bond between heteroatom A and Z is dative or
covalent.
[0095] More specifically, when A.sup.1 in Formula Ia is nitrogen it
will always have at least 3 available vacancies for bonding. If the
bond between such N and its adjacent ring carbon is a double
covalent bond, the b for R.sup.5 will be zero, and only one further
vacancy will be available in the N for either a covalent bond with
Z, in which case c and d are zero, or if the bond with Z is dative,
the N can covalently bond with its associated R.sup.1 or R.sup.7
group in which case either d or c is 1. Similarly, if the bonds
between the N and the adjacent ring carbon and between N and Z are
single covalent, the b of R.sup.5 can be 1, and either d or the c
of R.sup.7 will be 1. Alternatively if the bond between N and Z is
dative in this scenario, both d, and the c of R.sup.7 can be 1.
[0096] The above rules are modified when A.sup.1 in Formula Ia is
oxygen because oxygen has only 2 available vacancies rather than
the 3 vacancies for N. Thus, when Al is oxygen and is double
covalently bonded to the adjacent ring carbon, the bond between Al
and Z will be dative and b of R.sup.5, c of R.sup.7 and d will be
0. If such double bond is replaced by a single bond, the b of
R.sup.5 can be 1 and either the bond between A.sup.1 and Z is
single covalent, in which case c of R.sup.2 and d are both 0, or if
dative, either c of R.sup.7 or d can be 1.
[0097] The vacancy rules when A.sup.1 is sulfur are the same as for
A.sup.1 being oxygen. Phosphorous typically has 3 available
vacancies for 3 single covalent bonds or 1 double covalent bond and
1 single covalent bond. Phosphorous will typically not covalently
bond with Z, its association with Z being that of a dative
bond.
[0098] Similar considerations to those described above for A.sup.1
apply in respect to A.sup.2 of Formula Ia and in respect to all A
groups and a, b, c, of Formula Ia discussed hereinafter.
[0099] Illustrative of bidentate pre-catalyst compounds which are
useful in providing the catalyst composition of the present
invention are compounds of Ia having the following combination of
groups:
1TABLE I Ia 4 # n R.sup.1/R.sup.4 R.sup.2/R.sup.3 R.sup.5/R.sup.6
A.sup.1 A.sup.2 L.sup.1 L.sup.2 a b c d Z 1 0 2,6-iPr.sub.2Ph Me
N/A N N Me e 0 0 0 1 Pd 2 0 2,6-iPr.sub.2Ph Me N/A N N Me Me 0 0 0
1 Pd 3 0 2,6-iPr.sub.2Ph Me N/A N N Me Br 0 0 0 1 Pd 4 0
2,6-iPr.sub.2Ph Me N/A N N Me Cl 0 0 0 1 Pd 5 0 2,6-iPr.sub.2Ph Me
N/A N N Br Br 0 0 0 1 Pd 6 0 2,6-iPr.sub.2Ph Me N/A N N Cl Cl 0 0 0
1 Pd 7 0 2,6-iPr.sub.2Ph Me N/A N N Br Br 0 0 0 1 Ni 8 0
2,6-iPr.sub.2Ph Me N/A N N Cl Cl 0 0 0 1 Ni 9 0 2,6-iPr.sub.2Ph Me
N/A N N Me Me 0 0 0 1 Ni 10 0 2,6-iPr.sub.2Ph Me N/A N N Me Br 0 0
0 1 Ni 11 0 2,6-iPr.sub.2Ph Me N/A N N Me Cl 0 0 0 1 Ni 12 0
2,6-Me.sub.2Ph Me N/A N N Me e 0 0 0 1 Pd 13 0 2,6-Me.sub.2Ph Me
N/A N N Me Me 0 0 0 1 Pd 14 0 2,6-Me.sub.2Ph Me N/A N N Me Br 0 0 0
1 Pd 15 0 2,6-Me.sub.2Ph Me N/A N N Me Cl 0 0 0 1 Pd 16 0
2,6-Me.sub.2Ph Me N/A N N Br Br 0 0 0 1 Pd 17 0 2,6-Me.sub.2Ph Me
N/A N N Cl Cl 0 0 0 1 Pd 18 0 2,6-iPr.sub.2Ph H N/A N N Me e 0 0 0
1 Pd 19 0 2,6-iPr.sub.2Ph H N/A N N Me Me 0 0 0 1 Pd 20 0
2,6-iPr.sub.2Ph H N/A N N Me Br 0 0 0 1 Pd 21 0 2,6-iPr.sub.2Ph H
N/A N N Me Cl 0 0 0 1 Pd 22 0 2,6-iPr.sub.2Ph H N/A N N Br Br 0 0 0
1 Pd 23 0 2,6-iPr.sub.2Ph H N/A N N Cl Cl 0 0 0 1 Pd 24 0
2,6-iPr.sub.2Ph H N/A N N Br Br 0 0 0 1 Ni 25 0 2,6-iPr.sub.2Ph H
N/A N N Cl Cl 0 0 0 1 Ni 26 0 2,6-iPr.sub.2Ph H N/A N N Me Me 0 0 0
1 Ni 27 0 2,6-iPr.sub.2Ph H N/A N N Me Br 0 0 0 1 Ni 28 0
2,6-iPr.sub.2Ph H N/A N N Me Cl 0 0 0 1 Ni 29 0 2,6-iPr.sub.2Ph An
N/A N N Me e 0 0 0 1 Pd 30 0 2,6-iPr.sub.2Ph An N/A N N Me Me 0 0 0
1 Pd 31 0 2,6-iPr.sub.2Ph An N/A N N Me Br 0 0 0 1 Pd 32 0
2,6-iPr.sub.2Ph An N/A N N Me Cl 0 0 0 1 Pd 33 0 2,6-iPr.sub.2Ph An
N/A N N Br Br 0 0 0 1 Pd 34 0 2,6-iPr.sub.2Ph An N/A N N Cl Cl 0 0
0 1 Pd 35 0 2,6-iPr.sub.2Ph An N/A N N Br Br 0 0 0 1 Ni 36 0
2,6-iPr.sub.2Ph An N/A N N Cl Cl 0 0 0 1 Ni 37 0 2,6-iPr.sub.2Ph An
N/A N N Me Me 0 0 0 1 Ni 38 0 2,6-iPr.sub.2Ph An N/A N N Me Br 0 0
0 1 Ni 39 0 2,6-iPr.sub.2Ph An N/A N N Me Cl 0 0 0 1 Ni 40 0
2,6-Me.sub.2Ph An N/A N N Me e 0 0 0 1 Pd 41 0 2,6-Me.sub.2Ph An
N/A N N Me Me 0 0 0 1 Pd 42 0 2,6-Me.sub.2Ph An N/A N N Me Br 0 0 0
1 Pd 43 0 2,6-Me.sub.2Ph An N/A N N Me Cl 0 0 0 1 Pd 44 0
2,6-Me.sub.2Ph An N/A N N Br Br 0 0 0 1 Pd 45 0 2,6-Me.sub.2Ph An
N/A N N Cl Cl 0 0 0 1 Pd 46 0 2,6-Me.sub.2Ph H N/A N N Me e 0 0 0 1
Pd 47 0 2,6-Me.sub.2Ph H N/A N N Me Me 0 0 0 1 Pd 48 0
2,6-Me.sub.2Ph H N/A N N Me Br 0 0 0 1 Pd 49 0 2,6-Me.sub.2Ph H N/A
N N Me Cl 0 0 0 1 Pd 50 0 2,6-Me.sub.2Ph H N/A N N Br Br 0 0 0 1 Pd
51 0 2,6-Me.sub.2Ph H N/A N N Cl Cl 0 0 0 1 Pd 52 0 2,6-Me.sub.2Ph
Me N/A N N Br Br 0 0 0 1 Ni 53 0 2,6-Me.sub.2Ph Me N/A N N Cl Cl 0
0 0 1 Ni 54 0 2,6-Me.sub.2Ph Me N/A N N Me Me 0 0 0 1 Ni 55 0
2,6-Me.sub.2Ph Me N/A N N Me Br 0 0 0 1 Ni 56 0 2,6-Me.sub.2Ph Me
N/A N N Me Cl 0 0 0 1 Ni 57 0 2,4,6-Me.sub.3Ph Me N/A N N Me e 0 0
0 1 Pd 58 0 2,4,6-Me.sub.3Ph Me N/A N N Me Me 0 0 0 1 Pd 59 0
2,4,6-Me.sub.3Ph Me N/A N N Me Br 0 0 0 1 Pd 60 0 2,4,6-Me.sub.3Ph
Me N/A N N Me Cl 0 0 0 1 Pd 61 0 2,4,6-Me.sub.3Ph Me N/A N N Br Br
0 0 0 1 Pd 62 0 2,4,6-Me.sub.3Ph Me N/A N N Cl Cl 0 0 0 1 Pd 63 0
2,4,6-Me.sub.3Ph Me N/A N N Br Br 0 0 0 1 Ni 64 0 2,4,6-Me.sub.3Ph
Me N/A N N Cl Cl 0 0 0 1 Ni 65 0 2,4,6-Me.sub.3Ph Me N/A N N Me Me
0 0 0 1 Ni 66 0 2,4,6-Me.sub.3Ph Me N/A N N Me Br 0 0 0 1 Ni 67 0
2,4,6-Me.sub.3Ph Me N/A N N Me Cl 0 0 0 1 Ni 68 0 2,4,6-Me.sub.3Ph
H N/A N N Me e 0 0 0 1 Pd 69 0 2,4,6-Me.sub.3Ph H N/A N N Me Me 0 0
0 1 Pd 70 0 2,4,6-Me.sub.3Ph H N/A N N Me Br 0 0 0 1 Pd 71 0
2,4,6-Me.sub.3Ph H N/A N N Me Cl 0 0 0 1 Pd 72 0 2,4,6-Me.sub.3Ph H
N/A N N Br Br 0 0 0 1 Pd 73 0 2,4,6-Me.sub.3Ph H N/A N N Cl Cl 0 0
0 1 Pd 74 0 2,4,6-Me.sub.3Ph H N/A N N Br Br 0 0 0 1 Ni 75 0
2,4,6-Me.sub.3Ph H N/A N N Cl Cl 0 0 0 1 Ni 76 0 2,4,6-Me.sub.3Ph H
N/A N N Me Me 0 0 0 1 Ni 77 0 2,4,6-Me.sub.3Ph H N/A N N Me Br 0 0
0 1 Ni 78 0 2,4,6-Me.sub.3Ph H N/A N N Me Cl 0 0 0 1 Ni 79 0
2,4,6-Me.sub.3Ph An N/A N N Me e 0 0 0 1 Pd 80 0 2,4,6-Me.sub.3Ph
An N/A N N Me Me 0 0 0 1 Pd 81 0 2,4,6-Me.sub.3Ph An N/A N N Me Br
0 0 0 1 Pd 82 0 2,4,6-Me.sub.3Ph An N/A N N Me Cl 0 0 0 1 Pd 83 0
2,4,6-Me.sub.3Ph An N/A N N Br Br 0 0 0 1 Pd 84 0 2,4,6-Me.sub.3Ph
An N/A N N Cl Cl 0 0 0 1 Pd 85 0 2,4,6-Me.sub.3Ph An N/A N N Br Br
0 0 0 1 Ni 86 0 2,4,6-Me.sub.3Ph An N/A N N Cl Cl 0 0 0 1 Ni 87 0
2,4,6-Me.sub.3Ph An N/A N N Me Me 0 0 0 1 Ni 88 0 2,4,6-Me.sub.3Ph
An N/A N N Me Br 0 0 0 1 Ni 89 0 2,4,6-Me.sub.3Ph An N/A N N Me Cl
0 0 0 1 Ni 90 0 Ph j N/A N N Me Me 0 0 0 1 Pd 91 0 Ph Me N/A N N Me
Me 0 0 0 1 Pd 92 0 Ph H N/A N N Me Me 0 0 0 1 Pd 93 0 Ph An N/A N N
Me Me 0 0 0 1 Pd 94 0 Ph j N/A N N Me Cl 0 0 0 1 Pd 95 0 Ph Me N/A
N N Me Cl 0 0 0 1 Pd 96 0 Ph H N/A N N Me Cl 0 0 0 1 Pd 97 0 Ph An
N/A N N Me Cl 0 0 0 1 Pd 98 0 2-PhPh j N/A N N Me Me 0 0 0 1 Pd 99
0 2-PhPh Me N/A N N Me Me 0 0 0 1 Pd 100 0 2-PhPh H N/A N N Me Me 0
0 0 1 Pd 101 0 2-PhPh An N/A N N Me Me 0 0 0 1 Pd 102 0 2-PhPh j
N/A N N Me Cl 0 0 0 1 Pd 103 0 2-PhPh Me N/A N N Me Cl 0 0 0 1 Pd
104 0 2-PhPh H N/A N N Me 0 0 0 1 Pd 105 0 2-PhPh An N/A N N Me Cl
0 0 0 1 Pd 106 0 2,6-EtPh j N/A N N Me Me 0 0 0 1 Pd 107 0 2,6-EtPh
Me N/A N N Me Me 0 0 0 1 Pd 108 0 2,6-EtPh H N/A N N Me Me 0 0 0 1
Pd 109 0 2,6-EtPh An N/A N N Me Me 0 0 0 1 Pd 110 0 2,6-EtPh j N/A
N N Me Cl 0 0 0 1 Pd 111 0 2,6-EtPh Me N/A N N Me Cl 0 0 0 1 Pd 112
0 2,6-EtPh H N/A N N Me Cl 0 0 0 1 Pd 113 0 2,6-EtPh An N/A N N Me
Cl 0 0 0 1 Pd 114 0 2-t-BuPh j N/A N N Me Me 0 0 0 1 Pd 115 0
2-t-BuPh Me N/A N N Me Me 0 0 0 1 Pd 116 0 2-t-BuPh H N/A N N Me Me
0 0 0 1 Pd 117 0 2-t-BuPh An N/A N N Me Me 0 0 0 1 Pd 118 0
2-t-BuPh j N/A N N Me Cl 0 0 0 1 Pd 119 0 2-t-BuPh Me N/A N N Me Cl
0 0 0 1 Pd 120 0 2-t-BuPh H N/A N N Me Cl 0 0 0 1 Pd 121 0 2-t-BuPh
An N/A N N Me Cl 0 0 0 1 Pd 122 0 1-Np j N/A N N Me Me 0 0 0 1 Pd
123 0 1-Np Me N/A N N Me Me 0 0 0 1 Pd 124 0 1-Np H N/A N N Me Me 0
0 0 1 Pd 125 0 1-Np An N/A N N Me Me 0 0 0 1 Pd 126 0 PhMe j N/A N
N Me Cl 0 0 0 1 Pd 127 0 PhMe Me N/A N N Me Cl 0 0 0 1 Pd 128 0
PhMe H N/A N N Me Cl 0 0 0 1 Pd 129 0 PhMe An N/A N N Me Cl 0 0 0 1
Pd 130 0 PhMe j N/A N N Me Me 0 0 0 1 Pd 131 0 PhMe Me N/A N N Me
Me 0 0 0 1 Pd 132 0 PhMe H N/A N N Me Me 0 0 0 1 Pd 133 0 PhMe An
N/A N N Me Me 0 0 0 1 Pd 134 0 PhMe j N/A N N Me Cl 0 0 0 1 Pd 135
0 PhMe Me N/A N N Me Cl 0 0 0 1 Pd 136 0 PhMe H N/A N N Me Cl 0 0 0
1 Pd 137 0 PhMe An N/A N N Me Cl 0 0 0 1 Pd 138 0 Ph.sub.2Me j N/A
N N Me Me 0 0 0 1 Pd 139 0 Ph.sub.2Me Me N/A N N Me Me 0 0 0 1 Pd
140 0 Ph.sub.2Me H N/A N N Me Me 0 0 0 1 Pd 141 0 Ph.sub.2Me An N/A
N N Me Me 0 0 0 1 Pd 142 0 Ph.sub.2Me j N/A N N Me Cl 0 0 0 1 Pd
143 0 Ph.sub.2Me Me N/A N N Me Cl 0 0 0 1 Pd 144 0 Ph.sub.2Me H N/A
N N Me Cl 0 0 0 1 Pd 145 0 Ph.sub.2Me An N/A N N Me Cl 0 0 0 1 Pd
146 0 2,6-t-BuPh j N/A N N Me Me 0 0 0 1 Pd 147 0 2,6-t-BuPh Me N/A
N N Me Me 0 0 0 1 Pd 148 0 2,6-t-BuPh H N/A N N Me Me 0 0 0 1 Pd
149 0 2,6-t-BuPh An N/A N N Me Me 0 0 0 1 Pd 150 0 2,6-t-BuPh j N/A
N N Me Cl 0 0 0 1 Pd 151 0 2,6-t-BuPh Me N/A N N Me Cl 0 0 0 1 Pd
152 0 2,6-t-BuPh H N/A N N Me Cl 0 0 0 1 Pd 153 0 2,6-t-BuPh An N/A
N N Me Cl 0 0 0 1 Pd 154 0 2,6-t-BuPh H N/A N N Br Br 0 0 0 1 Ni
155 0 2,6-t-Bu.sub.2Ph Me N/A N N Br Br 0 0 0 1 Ni 156 0
2,6-t-Bu.sub.2Ph An N/A N N Br Br 0 0 0 1 Ni 157 0 2,6-t-Bu.sub.2Ph
H N/A N N Br Br 0 0 0 1 Ni 158 0 2,6-t-Bu.sub.2Ph Me N/A N N Br Br
0 0 0 1 Ni 159 0 2-6-t-Bu.sub.2Ph An N/A N N Br Br 0 0 0 1 Ni 160 0
Ph H N/A N N Br Br 0 0 0 1 Ni 161 0 Ph Me N/A N N Br Br 0 0 0 1 Ni
162 0 Ph An N/A N N Br Br 0 0 0 1 Ni 163 0 2-PhPh H N/A N N Br Br 0
0 0 1 Ni 164 0 2-PhPh Me N/A N N Br Br 0 0 0 1 Ni 165 0 2-PhPh An
N/A N N Br Br 0 0 0 1 Ni 166 0 2-iPr-6-MePh H N/A N N Br Br 0 0 0 1
Ni 167 0 2-iPr-6-MePh Me N/A N N Br Br 0 0 0 1 Ni 168 0
2-iPr-6-MePh An N/A N N Br Br 0 0 0 1 Ni 169 0 2,5-t-BuPh H N/A N N
Br Br 0 0 0 1 Ni 170 0 2,5-t-BuPh Me N/A N N Br Br 0 0 0 1 Ni 171 0
2,5-t-BuPh An N/A N N Br Br 0 0 0 1 Ni 172 0 2,6-EtPh H N/A N N Br
Br 0 0 0 1 Ni 173 0 2,6-EtPh Me N/A N N Br Br 0 0 0 1 Ni 174 0
2,6-EtPh An N/A N N Br Br 0 0 0 1 Ni 175 0 1-Np H N/A N N Br Br 0 0
0 1 Ni 176 0 1-Np Me N/A N N Br Br 0 0 0 1 Ni 177 0 1-Np An N/A N N
Br Br 0 0 0 1 Ni 178 0 Ph Ph N/A N N Br Br 0 0 0 1 Ni 179 0
2,4,6-Me.sub.3Ph H N/A N N Br Br 0 0 0 1 Ni 180 0 2,4,6-Me.sub.3Ph
Me N/A N N Br Br 0 0 0 1 Ni 181 0 2,4,6-Me.sub.3Ph An N/A N N Br Br
0 0 0 1 Ni 182 0 2,4,6-Me.sub.3Ph Ph N/A N N Br Br 0 0 0 1 Ni 183 1
2,6-Pr.sub.2Pr H H N N Cl Cl 0 0 0 1 SY 184 2 2,6-Pr.sub.2Pr H H N
N Cl Cl 0 0 0 1 SY 185 3 2,6-Pr.sub.2Pr H H N N Cl Cl 0 0 0 1 SY
186 1 2,6-Pr.sub.2Pr Me Me N N Cl Cl 0 0 0 1 SY 187 2
2,6-Pr.sub.2Pr Me Me N N Cl Cl 0 0 0 1 SY 188 3 2,6-Pr.sub.2Pr Me
Me N N Cl Cl 0 0 0 1 SY 189 1 2,6-Me.sub.2Ph H H N N Cl Cl 0 0 0 1
SY 190 2 2,6-Me.sub.2Ph H H N N Cl Cl 0 0 0 1 SY 191 3
2,6-Me.sub.2Ph H H N N Cl Cl 0 0 0 1 SY 192 1 2,6-Me.sub.2Ph Me Me
N N Cl Cl 0 0 0 1 SY 193 2 2,6-Me.sub.2Ph Me Me N N Cl Cl 0 0 0 1
SY 194 3 2,6-Me.sub.2Ph Me Me N N Cl Cl 0 0 0 1 SY 195 1
2,4,6-Me.sub.3Ph H H N N Cl Cl 0 0 0 1 SY 196 2 2,4,6-Me.sub.3Ph H
H N N Cl Cl 0 0 0 1 SY 197 3 2,4,6-Me.sub.3Ph H H N N Cl Cl 0 0 0 1
SY 198 1 2,4,6-Me.sub.3Ph Me Me N N Cl Cl 0 0 0 1 SY 199 2
2,4,6-Me.sub.3Ph Me Me N N Cl Cl 0 0 0 1 SY 200 3 2,4,6-Me.sub.3Ph
Me Me N N Cl Cl 0 0 0 1 SY *201 1 2,6-iPr.sub.2Ph H H N N Cl Cl 1 0
0 1 CMW 202 2 2,6-iPr.sub.2Ph H H N N Cl Cl 1 0 0 1 CMW 203 3
2,6-iPr.sub.2Ph H H N N Cl Cl 1 0 0 1 CMW 204 1 2,6-iPrPh Me Me N N
Cl Cl 1 0 0 1 CMW 205 2 2,6-iPrPh Me Me N N Cl Cl 1 0 0 1 CMW 206 3
2,6-iPrPh Me Me N N Cl Cl 1 0 0 1 CMW 207 1 2,6,Me.sub.2Ph H H N N
Cl Cl 1 0 0 1 CMW 208 2 2,6,Me.sub.2Ph H H N N Cl Cl 1 0 0 1 CMW
209 3 2,6,Me.sub.2Ph H H N N Cl Cl 1 0 0 1 CMW 210 1 2,6,Me.sub.2Ph
Me Me N N Cl Cl 1 0 0 1 CMW 211 2 2,6,Me.sub.2Ph Me Me N N Cl Cl 1
0 0 1 CMW 212 3 2,6,Me.sub.2Ph Me Me N N Cl Cl 1 0 0 1 CMW 213 1
2,4,6-Me.sub.3Ph H H N N Cl Cl 1 0 0 1 CMW 214 2 2,4,6-Me.sub.3Ph H
H N N Cl Cl 1 0 0 1 CMW 215 3 2,4,6-Me.sub.3Ph H H N N Cl Cl 1 0 0
1 CMW 216 1 2,4,6-Me.sub.3Ph Me Me N N Cl Cl 1 0 0 1 CMW 217 2
2,4,6-Me.sub.3Ph Me Me N N Cl Cl 1 0 0 1 CMW 218 3 2,4,6-Me.sub.3Ph
Me Me N N Cl Cl 1 0 0 1 CMW 219 1 2,6-iPr.sub.2Ph H H N N Cl Cl 1 0
0 1 TZH 220 2 2,6-iPr.sub.2Ph H H N N Cl Cl 1 0 0 1 TZH 221 3
2,6-iPr.sub.2Ph H H N N Cl Cl 1 0 0 1 TZH 222 1 2,6-iPr.sub.2Ph Me
Me N N Cl Cl 1 0 0 1 TZH 223 2 2,6-iPr.sub.2Ph Me Me N N Cl Cl 1 0
0 1 TZH 224 3 2,6-iPr.sub.2Ph Me Me N N Cl Cl 1 0 0 1 TZH 225 1
2,6-Me.sub.2Ph H H N N Cl Cl 1 0 0 1 TZH 226 2 2,6-Me.sub.2Ph H H N
N Cl Cl 1 0 0 1 TZH 221 3 2,6-Me.sub.2Ph H H N N Cl Cl 1 0 0 1 TZH
228 1 2,6-Me.sub.2Ph Me Me N N Cl Cl 1 0 0 1 TZH 229 2
2,6-Me.sub.2Ph Me Me N N Cl Cl 1 0 0 1 TZH 230 3 2,6-Me.sub.2Ph Me
Me N N Cl Cl 1 0 0 1 TZH 231 1 2,4,6-Me.sub.3Ph H H N N Cl Cl 1 0 0
1 TZH 232 2 2,4,6-Me.sub.3Ph H H N N Cl Cl 1 0 0 1 TZH 233 3
2,4,6-Me.sub.3Ph H H N N Cl Cl 1 0 0 1 TZH 234 1 2,4,6-Me.sub.3Ph
Me Me N N Cl Cl 1 0 0 1 TZH 235 2 2,4,6-Me.sub.3Ph Me Me N N Cl Cl
1 0 0 1 TZH 236 3 2,4,6-Me.sub.3Ph Me Me N N Cl Cl 1 0 0 1 TZH e =
the group (CH.sub.2).sub.3CO.sub.2Me *L' is Cl for #'s 201 to 236
Note - In Table I, above, the following convention and
abbreviations are used. For R.sup.1 and R.sup.4, when a substituted
phenyl ring is present, the amount of substitution is indicated by
the number of numbers indicating positions on the phenyl ring, as,
for example, 2,6-iPr.sub.2Ph represents 2,6-diisopropyl phenyl; iPr
= isopropyl; Pr = propyl; Me = methyl; Et = ethyl; t-Bu =
tert-butyl; Ph = phenyl; Np = naphthyl; An = 1,8-naphthalene; # j
is the group --C(Me).sub.2--CH.sub.2--C(Me).sub.2--; and e is the
group (CH.sub.2).sub.3CO.sub.2Me--, SY = Sc or Y; CMW = Cr, Mo or
W; TZH = Ti, Zr, or Hf and N/A = not applicable.
[0100] The typical tridentate pre-catalyst compounds may, for
example, be represented by the formula: 5
[0101] wherein:
[0102] R.sup.5 and R.sup.6 are each independently selected from
hydrogen, or an unsubstituted or substituted aryl group wherein
said substitution is an alkyl or a functional hetero group which is
inert with respect to the contemplated polymerization;
[0103] R.sup.7 and R.sup.8 are each independently selected from
hydrogen, an unsubstituted or substituted C.sub.1-C.sub.20
(preferably C.sub.1-C.sub.6) hydrocarbyl as, for example, alkyl
(methyl, ethyl, propyl, pentyl and the like); aryl (phenyl, toluyl
and the like) or a functional group which is inert with respect to
the polymerization (e.g., nitro, halo and the like);
[0104] R.sup.9 to R.sup.19 are each independently selected from
hydrogen, an unsubstituted or substituted C.sub.1-C.sub.20
hydrocarbyl or an inert functional group, all as described above
for R.sup.7;
[0105] a, b and c are each independently 0 or 1 and represent
whether their associated R group is present or not;
[0106] Z is a transition metal as defined above, preferably Fe(II),
Co(II) or Fe(III);
[0107] each A.sup.1 to A.sup.3 is independently selected as defined
in connection with A of Formula I;
[0108] and each L and L' is independently selected from a halogen
such as chlorine, bromine, iodine or a C.sub.1-C.sub.8 (preferably
C.sub.1-C.sub.5) alkyl, or any two L groups, together in
combination, represent an unsubstituted or substituted, saturated
or unsaturated, hydrocarbylene group which together with Z forms a
cyclic group, preferably a 3 to 7, most preferably 3 to 5 member
ring cyclic group.
[0109] Preferred compounds of II(a) are those wherein each R.sup.9,
R10 and R.sup.11 are hydrogen; b is 0, c is 1, and R.sup.7 and
R.sup.8 are each independently selected from halogen, hydrogen or a
C.sub.1-C.sub.6 alkyl, preferably each is independently selected
from methyl or hydrogen; and wherein R.sup.5 and R.sup.6 of IIa are
each an aryl or substituted aryl group, preferably wherein the aryl
contains substitution in the 2 position, the 2,6 positions or the
2,4,6 positions which is selected from a C.sub.1-C.sub.6 (most
preferably C.sub.1-C.sub.3) alkyl and the remaining positions are
each independently selected from hydrogen (most preferred), halogen
or a C.sub.1-C.sub.6 (preferably C.sub.1-C.sub.3) alkyl.
[0110] Illustrative examples of tridentate pre-catalyst compounds
which are useful in providing the catalyst composition of the
present invention are compounds of Formula IIa having the following
combination of groups shown in Table II below:
2TABLE II IIa 6 # R.sup.5/R.sup.6 R.sup.7/R.sup.8 R.sup.9 R.sup.10
R.sup.11 A.sup.1 A.sup.2 A.sup.3 a b c L L' Z 1 2,6-di-iPrPh Me H H
H N N N 0 0 1 * NA Fe 2 2,6-di-iPrPh Me H H H N N N 0 0 1 * NA Fe 3
2-t-BuPh Me H H H N N N 0 0 1 * NA Fe 4 Ph Me H H H N N N 0 0 1 *
NA Fe 5 2,6-di-iPrPh Me H Me H N N N 0 0 1 * NA Fe 6 2,6-di-iPrPh
Me H Me H N N N 0 0 1 * NA Fe 7 2-t-BuPh Me H Me H N N N 0 0 1 * NA
Fe 8 Ph Me H Me H N N N 0 0 1 * NA Fe 9 2,6-di-iPrPh Me Me Me Me N
N N 0 0 1 * NA Fe 10 2,6-di-iPrPh Me Me Me Me N N N 0 0 1 * NA Fe
11 2-t-BuPh Me Me Me Me N N N 0 0 1 * NA Fe 12 Ph Me Me Me Me N N N
0 0 1 * NA Fe 13 2,4,6-Me.sub.3Ph Me H H H N N N 0 0 1 * NA Fe 14
2,3,4,5,6- Me H H H N N N 0 0 1 * NA Fe Me.sub.5Ph 15 (2-t- Me H H
H N N N 0 0 1 * NA Fe BuMe.sub.2Sil)Bz 16 (2-Me.sub.3Sil)Bz Me H H
H N N N 0 0 1 * NA Fe 17 (2- Me H H H N N N 0 0 1 * NA Fe
PhMe.sub.2Sil)Bz 18 (2- Me H H H N N N 0 0 1 * NA Fe PhMeSil)Bz 19
(2-Me.sub.2Sil)Bz Me H H H N N N 0 0 1 * NA Fe 20 2,6-di-iPrPh Me H
H H N N N 0 0 1 * NA Co 21 2,6-di-iPrPh Me H H H N N N 0 0 1 * NA
Co 22 2-t-BuPh Me H H H N N N 0 0 1 * NA Co 23 Ph Me H H H N N N 0
0 1 * NA Co 24 2,6-di-iPrPh Me H Me H N N N 0 0 1 * NA Co 25
2,6-di-iPrPh Me H Me H N N N 0 0 1 * NA Co 26 2-t-BuPh Me H Me H N
N N 0 0 1 * NA Co 27 Ph Me H Me H N N N 0 0 1 * NA Co 28
2,6-di-iPrPh Me Me Me Me N N N 0 0 1 * NA Co 29 2,6-di-iPrPh Me Me
Me Me N N N 0 0 1 * NA Co 30 2-t-BuPh Me Me Me Me N N N 0 0 1 * NA
Co 31 Ph Me Me Me Me N N N 0 0 1 * NA Co 32 2,4,6- Me H H H N N N 0
0 1 * NA Co (Me).sub.3Ph 33 2,3,4,5,6- Me H H H N N N 0 0 1 * NA Co
(Me).sub.5Ph 34 (2-t- Me H H H N N N 0 0 1 * NA Co BuMe.sub.2Sil)Bz
35 2-MePh Me H H H N N N 0 0 1 * NA Fe 36 (2-Me.sub.3Si1)Bz Me H H
H N N N 0 0 1 * NA Co 37 (2- Me H H H N N N 0 0 1 * NA Co
PhMe.sub.2Sil)Bz 38 (2- Me H H H N N N 0 0 1 * NA Co PhMeSil)Bz 39
(2-Me.sub.3Sil)Bz Me H H H O N 0 0 0 0 * NA Co 40 NA Me H H H O N 0
0 0 0 * NA Fe 41 NA Me H Me H O N 0 0 0 0 * NA Fe 42 NA i-Pr H H H
O N 0 0 0 0 * NA Fe 43 NA i-Pr H Me H O N 0 0 0 0 * NA Fe 44 NA
i-Pr Me Me Me O N 0 0 0 0 * NA Fe 45 NA Ph H H H O N 0 0 0 0 * NA
Fe 46 NA Ph H Me H O N 0 0 0 0 * NA Fe 47 NA Me H H H O N 0 0 0 0 *
NA Co 48 NA Me H Me H O N 0 0 0 0 * NA Co 49 NA i-Pr H H H O N 0 0
0 0 * NA Co 50 NA i-Pr H Me H O N 0 0 0 0 * NA Co 51 NA i-Pr Me Me
Me O N 0 0 0 0 * NA Co 52 NA Ph H H H O N 0 0 0 0 * NA Co 53 NA Ph
H Me H O N 0 0 0 0 * NA Co 54 2,6-iPr.sub.2Ph Me H F H N N N 1 0 1
Cl Cl VNT 55 2,6-iPr.sub.2Ph Me H Cl H N N N 1 0 1 Cl Cl VNT 56
2,6-iPr.sub.2Ph Me H Br H N N N 1 0 1 Cl Cl VNT 57 2,6-iPr.sub.2Ph
Me H I H N N N 1 0 1 Cl Cl VNT 58 2,6-iPr.sub.2Ph Me H H H N N N 1
0 1 Cl Cl VNT 59 2,6-iPr.sub.2Ph Me H H H N N N 1 0 1 Cl Cl VNT 60
2,6-iPr.sub.2Ph H H F H N N N 1 0 1 Cl Cl VNT 61 2,6-iPr.sub.2Ph H
H Cl H N N N 1 0 1 Cl Cl VNT 62 2,6-iPr.sub.2Ph H H Br H N N N 1 0
1 Cl Cl VNT 63 2,6-iPr.sub.2Ph H H I H N N N 1 0 1 Cl Cl VNT 64
2,6-Me.sub.2Ph Me H H H N N N 1 0 1 Cl Cl VNT 65 2,6-Me.sub.2Ph Me
H F H N N N 1 0 1 Cl Cl VNT 66 2,6-Me.sub.2Ph Me H Cl H N N N 1 0 1
Cl Cl VNT 67 2,6-Me.sub.2Ph Me H B H N N N 1 0 1 Cl Cl VNT 68
2,6-Me.sub.2Ph Me H I H N N N 1 0 1 Cl Cl VNT 69 2,6-Me.sub.2Ph H H
H H N N N 1 0 1 Cl Cl VNT 70 2,6-Me.sub.2Ph H H F H N N N 1 0 1 Cl
Cl VNT 71 2,6-Me.sub.2Ph H H Cl H N N N 1 0 1 Cl Cl VNT 72
2,6-Me.sub.2Ph H H Br H N N N 1 0 1 Cl Cl VNT 73 2,6-Me.sub.2Ph H H
I H N N N 1 0 1 Cl Cl VNT 74 2,4,6-Me.sub.3Ph Me H H H N N N 1 0 1
Cl Cl VNT 75 2,4,6-Me.sub.3Ph Me H F H N N N 1 0 1 Cl Cl VNT 76
2,4,6-Me.sub.3Ph Me H. Cl H N N N 1 0 1 Cl Cl VNT 77
2,4,6-Me.sub.3Ph Me H Br H N N N 1 0 1 Cl Cl VNT 78
2,4,6-Me.sub.3Ph H H I H N N N 1 0 1 Cl Cl VNT 79 2,4,6-Me.sub.3Ph
H H H H N N N 1 0 1 Cl Cl VNT 80 2,4,6-Me.sub.3Ph H H F H N N N 1 0
1 Cl Cl VNT 81 2,4,6-Me.sub.3Ph H H Cl H N N N 1 0 1 Cl Cl VNT 82
2,4,6-Me.sub.3Ph H H Br H N N N 1 0 1 Cl Cl VNT 83 2,4,6-Me.sub.3Ph
H H I H N N N 1 0 1 Cl Cl VNT 84 2,6-iPr.sub.2Ph H H H H N N N 1 0
1 Cl Cl MTR 85 2,6-iPr.sub.2Ph H H F H N N N 1 0 1 Cl Cl MTR 86
2,6-iPr.sub.2Ph H H Cl H N N N 1 0 1 Cl Cl MTR 87 2,6-iPr.sub.2Ph H
H B H N N N 1 0 1 Cl Cl MTR 88 2,6-iPr.sub.2Ph H H I H N N N 1 0 1
Cl Cl MTR 89 2,6-iPr.sub.2Ph Me H H H N N N 1 0 1 Cl Cl MTR 90
2,6-iPr.sub.2Ph Me H F H N N N 1 0 1 Cl Cl MTR 91 2,6-iPr.sub.2Ph
Me H Cl H N N N 1 0 1 Cl Cl MTR 92 2,6-iPr.sub.2Ph Me H Br H N N N
1 0 1 Cl Cl MTR 93 2,6-iPr.sub.2Ph Me H I H N N N 1 0 1 Cl Cl MTR
94 2,6-Me.sub.2Ph H H H H N N N 1 0 1 Cl Cl MTR 95 2,6-Me.sub.2Ph H
H F H N N N 1 0 1 Cl Cl MTR 96 2,6-Me.sub.2Ph H H Cl H N N N 1 0 1
Cl Cl MTR 97 2,6-Me.sub.2Ph H H B H N N N 1 0 1 Cl Cl MTR 98
2,6-Me.sub.2Ph H H I H N N N 1 0 1 Cl Cl MTR 99 2,6-Me.sub.2Ph Me H
H H N N N 1 0 1 Cl Cl MTR 100 2,6-Me.sub.2Ph Me H F H N N N 1 0 1
Cl Cl MTR 101 2,6-Me.sub.2Ph Me H Cl H N N N 1 0 1 Cl Cl MTR 102
2,6-Me.sub.2Ph Me H Br H N N N 1 0 1 Cl CT MTR 103 2,6-Me.sub.2Ph
Me H I H N N N 1 0 1 Cl Cl MTR 104 2,4,6-Me.sub.3Ph H H H H N N N 1
0 1 Cl Cl MTR 105 2,4,6-Me.sub.3Ph H H F H N N N 1 0 1 Cl Cl MTR
106 2,4,6-Me.sub.3Ph H H Cl H N N N 1 0 1 Cl Cl MTR 107
2,4,6-Me.sub.3Ph H H B H N N N 1 0 1 Cl Cl MTR 108 2,4,6-Me.sub.3Ph
H H I H N N N 1 0 1 Cl Cl MTR 109 2,4,6-Me.sub.3Ph Me H H H N N N 1
0 1 Cl Cl MTR 110 2,4,6-Me.sub.3Ph Me H F H N N N 1 0 1 Cl Cl MTR
111 2,4,6-Me.sub.3Ph Me H Cl H N N N 1 0 1 Cl Cl MTR 112
2,4,6-Me.sub.3Ph Me H Br H N N N 1 0 1 Cl Cl MTR 113
2,4,6-Me.sub.3Ph Me H I H N N N 1 0 1 Cl Cl MTR NA = Not Applicable
VNT = V, Nb, or Ta MTR = Mn, Tc, or Re
[0111] The asterisk (*) in Table II above represents both anionic
ligand groups (L) of the above preferred tridentate compounds II(a)
and for each of the above compounds both L groups are,
respectively, chlorine; bromine; methyl (--CH.sub.3); ethyl
(--C.sub.2H.sub.5); propyl (--C.sub.3H.sub.5, each of the isomers);
butyl (--C.sub.4H.sub.9, each of the isomers); dimethylamine;
1,3-butadiene-1,4 diyl; 1,4-pentadiene-1,5 diyl; C.sub.4 alkylene;
and C.sub.5 alkylene. Also in Table II B.sub.z=benzyl; Sil=siloxyl;
iPrPh=isopropylphenyl; t-Bu=tert-butyl; Me.sub.2=dimethyl,
Me.sub.3=trimethyl, etc.
[0112] It will be understood that the identity of L will determine
the nature of the process steps needed to form the ultimate
catalyst composition which is believed to exist, during
polymerization, as an activated pair of a cation, or cation like
(referred to herein collectively as Cationic) component and an
anion or anion like (referred to herein collectively as Anionic)
component. The Cationic component is the pre-catalyst which has
undergone activation typically by imparting a full or partial
positive charge to the metal center Z and the Anionic component is
a full or partial negatively charged component derived from the
support-activator and is believed to be in close proximity to, and
provides charge balance for, the activated metal center Z under
conventional polymerization reaction conditions while remaining
labile. The term "labile" is used herein to mean that under
polymerization conditions, the anionic component is only loosely
associated at the site of the catalyst activity so as to permit
displacement by a polymerizable monomer at the point of monomer
addition.
[0113] Thus, the manner in which the pre-catalyst is activated
typically depends on the identity of L.
[0114] From a generic standpoint, activation of pre-catalyst is
believed to result from removal of at least one L group from the
metal center in a manner sufficient to generate an open
coordination site at said metal center.
[0115] A variety of mechanisms and materials are known or possible
for accomplishing activation. Depending on the identity of L and
the support-activator, such mechanisms may be induced in 1 or 2
stages (relative to a designated molecule). Activation in a single
stage typically involves separately synthesizing a pre-catalyst
that can be activated directly by the support-activator (e.g.,
wherein L is initially selected as hydrocarbyl in the synthesis of
the pre-catalyst). Activation in 2 stages typically involves a
pre-activation first stage wherein at least one electronic
withdrawing L group (e.g. Cl) is replaced with at least one less
electronic withdrawing L group (e.g., alkyl) which is more easily
displaced in the second stage by the support-activator to cause
activation at the metal center Z. Accordingly, pre-activation can
be induced via known alkylation reactions with organometallic
compounds, such as organolithium or preferably organoaluminum
hydrides or alkyls. Pre-activation permits one to use the
support-activator in all instances for activation and eliminate use
of expensive methylalumoxane or ionizing agents such as boron
containing activators (or co-catalysts).
[0116] Thus, while activation mechanisms by which conventional
coordination catalyst systems operate include, but are not limited
to (a) abstraction of at least one L group by a Lewis acid by an
abstracting moiety such as carbonium, tropylium, carbenium,
ferrocenium and mixtures, and (b) protonation (by a Bronstead acid)
of the L group, when L constitutes a hydride or hydrocarbyl (e.g.
alkyl) group, such mechanisms typically require materials
additional to the support for implementation. The same is not true
for the present invention.
[0117] It is a particular advantage of the present invention that
such conventional ionizing agents used to produce ionic catalysts
can be eliminated and replaced with the support-activator of the
present invention which performs the dual function of activation
and supporting agent.
[0118] From a practical standpoint, it is preferred that L be
halogen, e.g., Cl, in the pre-catalyst. This stems from the fact
that when L is halogen (highly electron withdrawing) the
pre-catalyst is very stable and can be easily transported. However,
because L in this instance is highly electron withdrawing, it may
be more difficult to induce activation thereof by the
support-activator. Thus, as indicated above, it is possible to
pre-activate the pre-catalyst, by replacement of the halogens
constituting L with less electron withdrawing groups such as
hydrocarbyl groups, e.g., alkyl groups, using organometallic
compounds. The particular point in time when the organometallic
compound contacts the pre-catalyst is at the option of the
manufacturer and can be (a) before, during or after contact of the
support-activator with pre-catalyst prior to entry into the
polymerization zone and/or (b) upon or during polymerization by
direct addition to the polymerization zone. However, because
pre-activated catalysts are less stable than the halogenated
precursors thereof, organometallic compound addition, when
employed, is preferably conducted in the presence of the
support-activator. It is a further particular advantage of the
present invention that activation of the pre-catalyst (having
L=halogen) can be delayed by avoiding the use of the organometallic
compound to induce pre-activation until polymerization occurs.
Thus, such pre-catalyst can be impregnated into the support
activator and the same recovered without activation until used for
polymerization. Since it is possible to employ lower total amounts
of organometallic compound by adding it only to the reactor during
polymerization, this is the preferred approach.
[0119] Thus, one preferred embodiment comprises using pre-catalyst
transition metal compound I or II wherein each L group is a halogen
atom. In this embodiment the pre-catalyst and support-activator are
separately mixed. In another embodiment said pre-catalyst,
support-activator and at least one organometallic compound
(represented by Formula III below) are admixed simultaneously prior
to polymerization. In this embodiment, at least one of the halogens
constituting L becomes a new hydrocarbyl L group derived from the
organometallic, i.e., compound during pre-activation. More
specifically, when used as a scavenging and alkylating agent, the
organometallic compound is typically added directly to the
polymerization zone, whereas when employed as an alkylating agent
alone it is desirably added to the mixture of support-activator and
pre-catalyst.
[0120] Organometallic compounds suitable for use in pre-activation
include those represented by Formula (III):
M(R.sup.12).sub.s III
[0121] wherein M represents an element of the Group 1,2 or 13 of
the Periodic Table, a tin atom or a zinc atom; each R.sup.12
independently represents a hydrogen atom, a halogen atom, a
hydrocarbon based radical such as hydrocarbyl, typically C.sub.1 to
C.sub.24 hydrocarbyl, including C.sub.1 to C.sub.24 alkyl or alkoxy
and aryl, aryloxy, arylalkyl, arylalkoxy, alkylaryl or alkylaryloxy
group having 6 to 24 carbon atoms (such as a hydrogen atom, halogen
atom (e.g., chlorine fluorine, bromine, iodine and mixtures
thereof), alkyl groups (e.g., methyl, ethyl, propyl, pentyl, hexyl,
heptyl, decyl, isopropyl, isobutyl, s-butyl, t-butyl), alkoxy
groups (e.g., methyoxy, ethoxy, propoxy, butoxy, isopropoxy), aryl
groups (e.g., phenyl, biphenyl, naphthyl), aryloxy groups (e.g.,
phenoxy), arylalkyl groups (e.g., benzyl, phenylethyl), arylalkoxy
groups (benzyloxy), alkylaryl groups (e.g., tolyl, xylyl, cumenyl,
mesityl), and alkylaryloxy groups (e.g., methylphenoxy) and s is
the oxidation number of M. Preferably at least one R.sup.12 is
hydrocarbyl, e.g., an alkyl group having 1 to 24 carbon atoms or an
aryl, arylalkyl or alkylaryl group having 6 to 24 carbon atoms,
e.g., to provide a source of hydrocarbyl groups for alkylation of
the pre-catalyst when L is non-hydrocarbyl.
[0122] The preferred organometallic compounds are those wherein M
is aluminum.
[0123] Representative examples of organometallic compounds include
alkyl aluminum compounds, preferably trialkyl aluminum compounds,
such as trimethyl aluminum, triethyl aluminum, triisopropyl
aluminum, triisobutyl aluminum, tri-n-propylaluminum,
triisobutylaluminum, tri-n-butylaluminum, triamylaluminum, and the
like; alkyl aluminum alkoxides such as ethyl aluminum diethoxide,
diisobutyl aluminum ethoxide, di(tert-butyl) aluminum butoxide,
diisopropyl aluminum ethoxide, dimethyl aluminum ethoxide, diethyl
aluminum ethoxide, di-n-propyl aluminum ethoxide, di-n-butyl
aluminum ethoxide, and the like; aluminum alkoxides such as
aluminum ethoxide, aluminum propoxide, aluminum butoxide and the
like; alkyl or aryl aluminum halides such as diethyl aluminum
chloride, ethyl aluminum dichloride, diisopropyl aluminum chloride
and the like; aluminum aryloxides such as aluminum phenoxide, and
the like; and mixed aryl, alkyl or aryloxy, alkyl aluminum
compounds and aluminum hydrides such as dimethylaluminum hydride,
diethylaluminum hydride, diisopropylaluminum hydride,
di-n-propylaluminum hydride, diisobutylaluminum hydride, and
di-n-butylaluminum hydride. The most preferred organometallic
compounds are the trialkyl aluminum compounds.
[0124] When at least one L of the transition metal compounds is
halogen, the pre-catalyst and/or the organometallic compound can be
mixed in an inert diluent prior to, simultaneously with, or after
contact (of either one) with the support-activator. The
pre-catalyst, when two L groups are halogen, is more stable to
materials which are poisons to the activated catalyst.
[0125] In a second preferred embodiment wherein each L of the
pre-catalyst is a hydrocarbyl, a hydrocarbylene or a hydrocarbyloxy
group, there is no need for the addition or handling of the
organometallic compound. Thus, the catalyst composition can be
readily formed and used without pre-activation. However, even in
this instance, it is still preferred to employ at least some
organometallic compound as a scavenger during polymerization to
deactivate potential poisons to the activated catalyst.
[0126] The support-activator is a composite in the form of
agglomerates of at least two components, namely, (A) at least one
inorganic oxide component and (B) at least one ion-containing
layered component.
[0127] In addition, the morphology of the support-activator is
believed to significantly influence the performance of the catalyst
composition.
[0128] The inorganic oxide Component-A of the support-activator
agglomerate particles of the present invention are derived from
porous inorganic oxides including SiO.sub.2, Al.sub.2O.sub.3,
AlPO.sub.4, MgO, TiO.sub.2, ZrO.sub.2; mixed inorganic oxides
including SiO.sub.2.Al.sub.2O.sub.3, MgO.SiO.sub.2.Al.sub.2O.sub.3,
SiO.sub.2.TiO.sub.2.Al.sub.2O.sub.3, SiO.sub.2.Cr.sub.2O.sub.3
TiO.sub.2 and SiO.sub.2.Cr.sub.2O.sub.3 TiO.sub.2 based on the
weight of the catalyst support. Where the inorganic oxide
(including mixed inorganic oxides) is capable of forming a gel by
known commercial procedures, it is preferred to utilize the same in
a gel configuration for the milling procedures described herein. If
the inorganic oxide is not susceptible to gel formation, the free
oxide or mixed oxides derived from other conventional techniques
such as precipitation, coprecipitation, or just admixing, can be
utilized directly for the milling procedures after washing.
[0129] Most preferably, Component-A of the support-activator
contains typically at least 80, preferably at least 90, and most
preferably at least 95%, by weight, silica gel (e.g., hydrogel,
aerogel, or xerogel) based on the weight of the catalyst
support.
[0130] Silica hydrogel, also known as silica aquagel, is a silica
gel formed in water which has its pores filled with water. A
xerogel is a hydrogel with the water removed. An aerogel is a type
of xerogel from which the liquid has been removed in such a way as
to minimize any collapse or change in the structure as the water is
removed.
[0131] Silica gel is prepared by conventional means such as by
mixing an aqueous solution of an alkali metal silicate (e.g.,
sodium silicate) with a strong acid such as nitric or sulfuric
acid, the mixing being done under suitable conditions of agitation
to form a clear silica sol which sets into a hydrogel in less than
about one-half hour. The resulting gel is then washed. The
concentration of the SiO.sub.2 in the hydrogel which is formed is
usually in the range of typically between about 15 and about 40,
preferably between about 20 and about 35, and most preferably
between about 30 and about 35 weight percent, with the pH of that
gel being from about 1 to about 9, preferably 1 to about 4. A wide
range of mixing temperatures can be employed, this range being
typically from about 20 to about 50.degree. C.
[0132] Washing is accomplished simply by immersing the newly formed
hydrogel in a continuously moving stream of water which leaches out
the undesirable salts, leaving about 99.5 wt. % pure silica
(SiO.sub.2) behind.
[0133] The pH, temperature, and duration of the wash water will
influence the physical properties of the silica, such as surface
area (SA) and pore volume (PV). Silica gel washed at 65-90.degree.
C. at pH's of 8-9 for 28-36 hours will usually have SA's of 290-350
m.sup.2/g and form aerogels with PV's of 1.4 to 1.7 cc/gm. Silica
gel washed at pH's of 3-5 at 50-65.degree. C. for 15-25 hours will
have SA's of 700-850 m.sup.2/g and form aerogels with PV's of
0.6-1.3 cc/g.
[0134] When employing a Component-A inorganic oxide containing at
least 80 wt. % silica gel, the remaining balance of the inorganic
oxide Component-A can comprise various additional components. These
additional components may be of two types, namely (1) those which
are intimately incorporated into the gel structure upon formation,
e.g., by cogelling silica gel with one or more other gel forming
inorganic oxide materials, and (2) those materials which are
admixed with silica gel particles prior to milling or after milling
in slurry form just prior to spray drying. Thus, materials
includable in the former category are silica-alumina,
silica-titania, silica-titania-alumina, and silica-alumina
phosphate cogels.
[0135] In the latter category, components which may be admixed, in
slight proportions, with the silica hydrogel particles prior to
milling and/or just prior to agglomeration include those prepared
separately from inorganic oxides such as magnesium oxide, titanium
oxide, thorium oxide, e.g., oxides of Groups 4 and 16, as well as
other particulate constituents.
[0136] Other particulate constituents which may be present include
those constituents having catalytic properties, not adversely
affected by water, spray drying or calcination, such as finely
divided oxides or chemical compounds, recognizing, however, that
these constituents play no part in the agglomeration procedure.
Similarly, it is possible to add powders or particles of other
constituents to the silica hydrogel particles to impart additional
properties to the support-activator obtained. Accordingly, in
addition to those powders or particulates having catalytic
properties, there may be added materials which possess absorbent
properties, such as synthetic zeolites.
[0137] Thus, it is possible to obtain complex catalyst supports
wherein amorphous silica gel contains crystallizable elements and
the like. The skilled artisan will appreciate that the amounts of
such additional components must be restricted in order to avoid
compromising the desired agglomerate properties described
herein.
[0138] Also, it is feasible to add constituents to the inorganic
oxide which may be eliminated after agglomeration in order to
control porosity within a desired range; such agents as sulfur,
graphite, wood charcoal, and the like being particularly useful for
this purpose.
[0139] When non-silica gel components are to be employed with
silica gel, they may be added to the slurry to be agglomerated.
However, it is preferable that they be present in the silica gel
during or prior to milling as described hereinafter, since they
will be less likely to disturb the desired agglomerate morphology
after spray drying when they are also subjected to milling.
[0140] In view of the above, the term "silica gel", when used to
describe the process steps up to and including agglomeration, is
intended to include the optional inclusion of the aforementioned
non-silica gel constituents permitted to be present in Component-A
of the support-activator.
[0141] Component-B of the support-activator is a layered material
having a three-dimensional structure which exhibits the strongest
chemical bonds in only two dimensions. More specifically, the
strongest chemical bonds are formed in and within two dimensional
planes which are stacked on top of each other to form a three
dimensional solid. The two dimensional planes are held together by
weaker chemical bonds than those holding an individual plane
together and generally arise from Van der Waals forces,
electrostatic interactions, and hydrogen bonding. The electrostatic
interactions are mediated by ions located between the layers and in
addition, hydrogen bonding can occur between complimentary layers
or can be mediated by interlamellar bridging molecules.
[0142] Representative examples of suitable layered materials
includable in layered Component-B can be amorphous or crystalline,
preferably amorphous. Suitable layered Component-B materials
include clay, and clay minerals.
[0143] Clay is typically composed of clay minerals (i.e.,
crystalline silicate salts) as the main constituent. The clay or
clay mineral is usually an inorganic polymeric compound of high
molecular complexity constituted by a tetrahedral unit in which a
central silicon atom coordinates oxygen atoms and an octahedral
unit in which a central aluminum, magnesium or iron atom
coordinates oxygen or hydroxide. The skeletal structures of many
clays or clay minerals are not electrically neutral and have
positive, most typically negative, charges on their surfaces. When
possessing a negatively charged surface, they have cations in their
interlaminar structures to complement such negative charges. Such
interlaminar cations can be ion-exchanged by other cations. A
quantification of a clay's ability to exchange interlaminar cations
is called its cation exchange capacity (CEC) and is represented by
milliequivalents (meq) per 100 g of clay. CEC differs depending
upon the type of clay, and Clay Handbook, second edition (compiled
by Japanese Clay Association, published by Gihodo Shuppan K. K.)
gives the following information. Kaolinite: 3 to 15 meq/100 g,
halloysite: 5 to 40 meq/100 g, montmorillonite: 80 to 150 meq/100
g, illite: 10 to 40 meq/100 g, vermiculite: 100 to 150 meq/100 g,
chlorite: 10 to 40 meq/100 g, zeolite.multidot.attapulgite: 20 to
30 meq/100 g. Thus, layered Component-B to be used in the present
invention, is a material, e.g., clay or clay mineral, typically
having its surface negatively charged and preferably also having
the ability to exchange cations.
[0144] Thus, clay minerals generally have the characteristic layer
structure described above, containing between the layers, various
levels of negative charges. In this respect, the clay mineral is
substantially different from metal oxides having a
three-dimensional structure such as silica, alumina, and zeolite.
The clay minerals are classified according to the levels of the
aforementioned negative charge for the chemical formula: (1)
biophilite, kaolinite, dickalite, and talc having the negative
charge of 0 (zero), (2) smectite having the negative charge of from
-0.25 to -0.6, (3) vermiculite having the negative charge of from
-0.6 to -0.9, (4) mica having the negative charge of from about -1,
and (5) brittle mica having a negative charge of about -2. Each of
the above groups includes various minerals. For example, the
smectite group includes montmorillonite, beidellite, saponite,
nontronite hectorite, teniolite, suconite and related analogues;
the mica group includes white mica, palagonite and illite. These
clay minerals exist in nature, and also can be synthesized
artificially with a higher purity.
[0145] Any of the natural and artificial clay minerals having a
negative charge below 0 are useful in the present invention. The
presently preferred clay is montmorillonite, e.g., sodium
montmorillonite.
[0146] Further, clays and clay minerals may be used as they are
without subjecting them to any treatment prior to formation of the
support-activator therefrom, or they may be treated by ball
milling, sieving, acid treatment or the like prior to such
formation. Further, they may be treated to have water added and
adsorbed or may be treated for dehydration under heating before
support-activator formation. They may be used alone or in
combination as a mixture of two or more of them for
support-activation synthesis.
[0147] Component-B preferably has a pore volume of pores having a
diameter of at least 40.ANG. (e.g., 40-1000 .ANG.) as measured by a
mercury intrusion method employing a mercury porosimeter of at
least 0.1 cc/g, more preferably from 0.1 to 1 cc/g. The average
particle size of Component-B can vary typically from about 0.01 to
about 50, preferably from about 0.1 to about 25, and most
preferably from about 0.5 to about 10 microns.
[0148] The clays suitable for use as Component-B of the
support-activator may be subjected to pretreatment with chemicals
prior or subsequent to support-activator formation. Examples of the
chemical pretreatment include treatment with an acid or alkali,
treatment with a salt, and treatment with an organic or inorganic
compound. The last treatment can result in formation of a composite
material.
[0149] The treatment of the clay mineral with the acid or alkali
may not only remove impurities from the mineral, but also may elute
part of metallic cations from the crystalline structure of the
clay, or may destructively alter the crystalline structure into an
amorphous structure.
[0150] Examples of the acids used for this purpose are Br.o
slashed.nstead acids, such as hydrochloric, sulfuric, nitric,
acetic acid and the like.
[0151] Sodium hydroxide, potassium hydroxide and calcium hydroxide
are preferably used as alkali chemical in the alkali pretreatment
of the clay mineral.
[0152] In the case where the clay mineral is pretreated with a salt
or an inorganic, or organic compound to give a composite material,
the crystalline structure may be retained substantially without
being broken and, rather a product that has been modified by
ion-exchange may be obtained.
[0153] Examples of the inorganic salt compounds that may be used in
the pretreatment with salts include ionic halide salts, such as
sodium chloride, potassium chloride, lithium chloride, magnesium
chloride, aluminum chloride, iron chloride and anunonium chloride;
sulfate salts, such as sodium sulfate, potassium sulfate, aluminum
sulfate and ammonium sulfate; carbonate salts, such as potassium
carbonate, sodium carbonate and calcium carbonate; and phosphate
salts, such as sodium phosphate, potassium phosphate, aluminum
phosphate and ammonium phosphate. Examples of the organic salt
compounds include sodium acetate, potassium acetate, potassium
oxalate, sodium citrate, sodium tartarate and the like.
[0154] In the case where the clay mineral is treated with an
organic compound, such compounds will typically comprise a Lewis
basic functional group containing an element of the Group 15 or 16
of the Periodic Table, such as organoammonium cation, oxonium
cation, sulfonium cation, and phosphonium cation. The organic
compound may also preferably comprise a functional group other than
the Lewis basic functional group, such as carbonium cation,
tropylium cation, and a metal cation. After undergoing such
treatment, the exchangeable metallic cations originally present in
the clay mineral are exchanged with the enumerated organic cations.
Thus, compounds that yield a carbon cation, for example, trityl
chloride, tropylium bromide and the like; or a complex compound
that yields metallic complex cation, for example a ferrocenium salt
and the like; may be used as the organic compound in the
pretreatment. In addition to these compounds, onium salts may be
used for the same purpose.
[0155] As examples of the inorganic compound used for the synthesis
of inorganic composite material, metal hydroxides that yield
hydroxide anions, for example, aluminum hydroxide, zirconium
hydroxide, chromium hydroxide and the like may be mentioned.
[0156] Particular examples of guest organic cations that may be
introduced for modification of the clay minerals, include:
triphenylsulfonium, trimethylsulfonium, tetraphenylphosphonium,
alkyl tri(o-tolyl) phosphonium, triphenylcarbonium,
cycloheptatrienium, and ferrocenium; ammonium ions, for example
aliphatic ammonium cations, such as butyl ammonium, hexyl ammonium,
decyl ammonium, dodecyl ammonium, diamyl ammonium, tributyl
ammonium, and N,N-dimethyl decyl ammonium; and aromatic ammonium
cations such as anilinium, N-methyl anilinium, N,N-dimethyl
anilinium, N-ethyl anilinium, N,N-diethyl anilinium, benzyl
ammonium, toluidinium, dibenzyl ammonium, tribenzyl ammonium,
N,N-2,4,6-pentamethyl anilinium and the like; and also oxonium
ions, such as dimethyl oxonium, diethyl oxonium and the like. These
examples are not limiting.
[0157] Ion exchange of the exchangeable cations in the clay mineral
with selected organic cations is typically brought about by
contacting the clay with an onium compound (salt) comprising the
organic cations.
[0158] Particular examples of the onium salts which may be used,
include: ammonium compounds; for example aliphatic amine
hydrochloride salts, such as propylamine HCl salt, isopropylamine
HCl salt, butylamine HCl salt, hexylamine HCl salt, decylamine HCl
salt, dodecylamine HCl salt, diamylamine HCl salt, tributylamine
HCl salt, triamylamine HCl salt, N,N-dimethyl decylamine HCl salt,
N,N-dimethyl undecylamine HCl salt and the like; aromatic amine
hydrochloride salts, such as aniline HCl salt, N-methylaniline HCl
salt, N,N-dimethylaniline HCl salt, N-ethylaniline HCl salt,
N,N-diethylaniline HCl salt, o-toluidine HCl salt, p-toluidine HCl
salt, N-methyl-o-toluidine HCl salt, N-methyl-p-toluidine HCl salt,
N,N-dimethyl-o-toluidine HCl salt, N,N-dimethyl-p-toluidine HCl
salt, benzylamine HCl salt, dibenzylamine HCl salt,
N,N-2,4,6-pentamethyl aniline HCl salt and the like; hydrofluoric,
hydrobromic and hydroiodic acid salts and sulfate salts of the
above-listed aliphatic and aromatic amines; and oxonium compounds,
such as hydrochloric acid salts of methyl ether, ethyl ether,
phenyl ether and the like. Of the onionium compounds the
exemplified ammonium or oxonium compounds, preferably the ammonium
compounds and more preferably the aromatic amine salts are employed
in the modification of the clay mineral.
[0159] The onium compound to be reacted with the clay mineral may
be in the isolated form. Alternatively, the onium compound may be
formed in situ, for example by contacting the corresponding amine
compound, a heteroatom-containing compound, such as an ether or
sulfide compound, and a proton acid, such as hydrofluoric,
hydrochloric, hydroiodic or sulfuric acid, in the reaction solvent
in which the clay mineral is to be pretreated subsequently. The
reaction conditions under which the clay mineral can be modified by
the onium compound are not critical. Also the relative proportions
of the reactants used therein are not critical. Preferably,
however, when used the onium compound is employed in a proportion
of not less than 0.5 equivalents per equivalent of the cation
present in the clay mineral, and more preferably in a proportion of
at least equivalent amount. The clay mineral may be used singly or
in admixture with other clay mineral or minerals. Also the onium
compound may be used singly or in admixture with other onium
compounds. The reaction solvent used in the modification
pretreatment process may be water or a polar organic solvent.
Examples of the organic solvents which may be used suitably,
include alcohols, such as methyl alcohol, ethyl alcohol and the
like; acetone, tetrahydrofuran, N,N-dimethyl formamide,
dimethylsulfoxide, methylene chloride and the like. The solvent may
be used singly or as a mixture of two or more solvents. Preferably,
water or an alcohol is employed.
[0160] What can be viewed as separate and distinct classes of
chemical modification treatments to which the clays can be
subjected is referred to as pillaring and delamination. Pillaring
is a phenomena whereby the platelets of certain clays, such as
smectite clays, which are swellable, are separated by intercalation
of large guest cations between the negatively charged platelet
sheets, which cations function as molecular props or pillars
separating the platelets and preventing the layers from collapsing
under van der Waals forces.
[0161] Pillared clays are typically prepared by reacting a smectite
clay, such as montmorillonite, with polyoxymetal cations such as
polyoxycations of aluminum and zirconium. The reaction product is
normally dried in air and calcined to convert the intercalated
cations into metal oxide clusters interposed between the platelets
of the clay such that the spacing between the platelets ranges from
about 6 to about 10 Angstroms and is maintained at such values when
the clay is heated to a temperature between about 500.degree. C.
and 700.degree. C. When the reaction product is dried, the clay
platelets, which are propped apart by the metal oxide clusters,
orient themselves face-to-face, thereby forming a lamellar
structure which yields an X-ray diffraction pattern containing
distinct first order or (001) reflection. The extent of lamellar
ordering is indicated by the X-ray powder diffraction pattern of
the pillared clay. A well-ordered, air-dried, pillared
montmorillonite may exhibit six or more orders of reflection.
Pillared clays and their preparation are described more fully in
the article entitled "Intercalated Clay Catalysts," Science, Vol.
220, No. 4595 pp. 365-371 (Apr. 22, 1983) and in U.S. Pat. Nos.
4,176,090; 4,216,188; 4,238,364; 4,248,739; 4,271,043; 4,367,163;
4,629,712; 4,637,992; 4,761,391; 4,859,648; and U.S. Pat. No.
4,995,964. The disclosures of the aforementioned articles and
patents are incorporated herein by reference in their
entireties.
[0162] In contrast to pillared clays, having platelets which are
ordered in a face-to-face arrangement, delaminated clays also
contain large cations but the platelets are oriented edge-to-edge
and edge-to-face in what can be described as a "house-of-cards"
structure containing macropores of a size typically found in
amorphous aluminosilicates in addition to the micropores found in
pillared clays. (See U.S. Pat. No. 4,761,391 for a further
discussion.)
[0163] Accordingly, it is contemplated that such pillared and
delaminated clays are includable as further embodiments of modified
clays which may be employed as Component-B in the support
activator.
[0164] While it is possible and permissible to modify Component-B
with guest cations as described above, such procedures add process
steps to the overall preparation, and from a process point of view,
are preferably not employed.
[0165] However, when Component-B is modified by exchanging
originally present cations for guest cations, the goal sought to be
achieved by such exchange is to render the support-activator
capable of activating either the pre-catalyst or the pre-activated
catalyst as described above. It is believed that the indigenous
cations typically present in the aforementioned clays are already
capable of accomplishing this goal.
[0166] The support-activator is made from an intimate admixture of
Components-A and -B, which admixture is shaped in the form of an
agglomerate.
[0167] The weight ratio of Components-A:-B in the agglomerate can
vary typically from about 0.25:1 to about 99:1, preferably from
about 0.5:1 to about 20:1, most preferably from about 1:1 to about
10:1 (e.g., 4:1).
[0168] The term "agglomerate" refers to a product that combines
particles which are held together by a variety of physical-chemical
forces.
[0169] More specifically, each agglomerate is preferably composed
of a plurality of contiguous, constituent primary particles derived
primarily from Component-A and much smaller secondary constituent
particles derived from both Component-A and Component-B preferably
joined and connected at their points of contact.
[0170] The agglomerates of the present invention preferably will
exhibit a higher macropore content than the constituent primary or
secondary particles as a result of the interparticle voids between
the constituent particles. However, such interparticle voids may be
almost completely filled with the smaller secondary particles in
other embodiments of the spray dried agglomerates.
[0171] The agglomeration of Components-A and -B may be carried out
in accordance with the methods well known to the art, in
particular, by such methods as pelletizing, extrusion, shaping into
beads in a rotating coating drum, and the like. The nodulizing
technique whereby composite particles having a diameter of not
greater than about 0.1 mm are agglomerated to particles with a
diameter of at least about 1 mm by means of a granulation liquid
may also be employed.
[0172] However, the preferred agglomerates are made by drying,
preferably spray drying a slurry of Components-A and -B.
[0173] More specifically, in this embodiment, the support-activator
is made by admixing Components-A and -B to form a slurry,
preferably an aqueous slurry, comprising typically at least 50,
preferably at least 75 (e.g., at least 80), and most preferably at
least 85 (e.g., at least 90), wt. % water based on the slurry
weight. However, organic solvents, such as C.sub.5 to C.sub.12
alkanes, alcohols (e.g. isopropyl alcohol), may also be employed
although they represent a fire hazard relative to water and often
make agglomerates too fragile for use as polymerization
catalysts.
[0174] To render Component-A suitable for agglomerate formation,
e.g. drying or spray drying, various milling procedures are
typically employed. The goal of the milling procedure is to
ultimately provide Component-A, when intended to be spray dried,
with an average particle size of typically from about 2 to about 10
(e.g. 3 to about 7) preferably from about 4 to about 9, and most
preferably from 4 to 7 microns. Desirably the milling procedures
will also impart a particle size Distribution Span to the particles
in the slurry of typically from 0.5 to about 3.0, and preferably
from about 0.5 to about 2.0. The particle size Distribution Span is
determined in accordance with the following equation. 1
Distribution Span = D 90 - D 10 D 50 Equation1a
[0175] wherein D.sub.10, D.sub.50, and D.sub.90 represent the
10.sup.th, 50.sup.th, and 90.sup.th percentile, respectively, of
the particle size (diameter) distribution, i.e. a D.sub.90 of 100
microns means that 90 volume % of the particles have diameters less
than or equal to 100 microns. Still more preferably, the milling is
conducted to impart a particle size distribution to the Component-A
inorganic oxides in the slurry to be spray dried such that the
Component-A colloidal content is typically from about 2 to about 60
(e.g. 2 to about 40), preferably from about 3 to about 25, and most
preferably from about 4 to about 20 wt. %.
[0176] The colloidal content of Component-A to be spray dried is
determined by centrifuging a sample for 30 minutes at 3600 RPM. The
liquid (supernatant) which remains on top of the test tube is
decanted, and analyzed for % solids. The % of colloidal material is
then determined by the following equation: 2 % c o l l o i d = [ (
1 - B B ) - 2.2 ( 1 - A A ) - 2.2 ] * 100 Equation1b
[0177] wherein
[0178] A=wt. % solids in supernatant/100, and
[0179] B=wt. % solids of original slurry/100
[0180] The colloidal content will possess a particle diameter in
the colloidal range of typically less than about 1, preferably less
than about 0.5, and typically from about 0.4 to about 1 micron.
[0181] All particle size and particle size distribution
measurements described herein are determined by a Mastersizer unit
from Malvern, which operates on the principle of laser light
diffraction and is known to all familiar in the art of small
particle analysis.
[0182] As the colloidal content of the dry solids content of the
Component-A slurry exceeds about 60 wt. %, the constituent
particles of the agglomerate can become bound too tightly
together.
[0183] Conversely, while the presence of at least some colloidal
content of the slurry is desired, a slurry containing no colloidal
content (e.g. dry milled powder alone) will typically produce
agglomerates of the support-activator which have extremely low
physical integrity to an undesirable degree and typically will be
undesirable as a support for a polymerization catalyst without some
alternative source of binder.
[0184] One milling procedure which has been found to impart the
aforedescribed properties, as well as the desired morphology,
involves a wet milling procedure and optionally a dry milling
procedure.
[0185] A wet milling procedure is characterized by the presence of
liquid, e.g. water, during the milling procedure. Thus, wet milling
is typically performed on a slurry of the inorganic oxide particles
having a solids content of typically from about 15 to about 25
weight % based on the slurry weight.
[0186] More specifically, with wet milling, Component-A is slurried
in a media (usually water) and the mixture then subjected to
intense mechanical action, such as the high speed blades of a
hammer mill or rapidly churning media of a sand mill. Wet milling
reduces particle size and produces colloidal silica as well.
[0187] A dry milling procedure is characterized by the substantial
absence of the presence of free flowing liquid, e.g. water or
solvent. Thus, while the final dry milled material may contain some
absorbed moisture, it is essentially in powder form, not a
suspension or solution of particles in liquid.
[0188] The dry milling referred to typically takes particulate
inorganic oxide and reduces it in size either by mechanical action,
impingement onto a metal surface, or collision with other particles
after entrainment into a high-velocity air stream.
[0189] Accordingly, the inorganic oxide (typically while still wet)
is then subjected to a milling operation as described below to
prepare it for spray drying.
[0190] In the wet milling procedure, the washed inorganic oxide is
typically subjected to a milling procedure well known in the art
that is necessary to produce slurries with the particle sizes
specified above. Suitable mills include hammer mills, impact mills
(where particle size reduction/control) is achieved by impact of
the oxide with metal blades and retained by an appropriately sized
screen), and sand mills (where particle size control/reduction is
achieved by contact of the oxide with hard media such as sand or
zirconia beads).
[0191] The colloidal particles within the wet milled material are
the primary source of the colloid content in the slurry to be spray
dried as described above, and are believed to act as a binder upon
spray drying.
[0192] In the dry milling procedure, Component-A is typically
milled in a manner sufficient to reduce its average particle size
to typically from about 2 to about 10, preferably from about 3 to
about 7, and most preferably from about 3 to 6 microns, and its
moisture content to typically less that about 50, preferably less
than about 25, and most preferably less that about 15 weight %. In
order to attain the dry milling particle size targets at the higher
moisture contents, it may be necessary to conduct dry milling while
the particles are frozen.
[0193] The dry milling is also conducted to preferably impart a
particle size distribution such that the Distribution Span is
typically from about 0.5 to about 3.0, preferably from about 0.5 to
about 2.0, and most preferably from about 0.7 to about 1.3.
[0194] Thus, the resulting dry milled material exists in the form
of a powder prior to being slurried for spray drying.
[0195] The dry milling is preferably conducted in a mill capable of
flash drying the inorganic oxide while milling. Flash drying is a
standard industrial process where the material to be dried is
quickly dispersed into a hot air chamber and exposed to an air
stream of 370-537.degree. C. The rate of air and material input is
balanced such that the temperature of the outgoing air and the
material entrained in it is generally 121-176.degree. C. The whole
process of drying usually takes place in less than 10 seconds,
reducing the moisture content to less than about 10%.
Alternatively, the inorganic oxide can be separately flash dried to
the aforedescribed moisture content in a flash dryer and then
placed in a dry mill and milled. Suitable dry mills include an ABB
Raymond.TM. impact mill or an ALJET.TM. FLUID ENERGY MILL. Ball
mills can also be used. Suitable flash drying equipment includes
Bowen.TM. flash dryer. Other similar equipment is well known in the
chemical processing industry.
[0196] Flash drying is typically accomplished by exposing the
inorganic oxide to conditions of temperature and pressure
sufficient to reduce the moisture content thereof to levels as
described above over a period of time of typically less than about
60, preferably less than about 30, and most preferably less than
about 5 seconds.
[0197] Dry milling typically does not produce colloidal silica.
[0198] In accordance with one embodiment of the agglomerate
formation by spray drying, at least a portion of the material
constituting Component-A is derived from wet milling, and
optionally but preferably at least a portion is derived from dry
milling. Thus, prior to agglomeration, Component-A will typically
comprise a mixture of previously wet milled inorganic oxide, e.g.
silica gel, and dry milled inorganic oxide, e.g. silica gel powder.
More specifically, the weight ratio (on a dry solids content basis
as defined hereinafter) of the wet milled:dry milled inorganic
oxide solids in the slurry can vary typically from about 9:0 to
about 0.1:1 (e.g., 9:1), preferably from about 1.5:1 to about
0.1:1, and most preferably from about 0.6:1 to about 0.25:1.
[0199] The particular wet milled:dry milled solids ratio of
Component-A employed will be selected to achieve the target
properties in the final slurry to be used in agglomerate
formation.
[0200] In an alternative embodiment, a sequential milling procedure
can be employed to impart the target properties of average particle
size and particle size distribution. The sequential milling
procedure involves dry milling a sample of the Component-A
inorganic oxide and then wet milling the previously dry milled
sample.
[0201] It has been observed that drying of inorganic oxide starting
material during dry milling and then using the dry milled product
for wet milling tends to produce a lower colloidal content relative
to mixing a separately prepared dry milled product and a separately
prepared wet milled product. The reason for this phenomenon is not
entirely understood. However, sufficient colloidal content is
produced to bind the agglomerate together in a desirable
manner.
[0202] Once the target average particle size and preferably the
particle size Distribution Span is imparted to Component-A, a
slurry, preferably aqueous slurry, is prepared for agglomeration,
preferably by spray drying.
[0203] The Component-B layered material, e.g. clay, is typically
comprised of fine particles having an average particle size of
typically less than 10, preferably less than 5, and most preferably
less than 1 micron, such particle sizes ranging typically from
about 0.1 to about 10, preferably from about 0.1 to about 5, and
most preferably from about 0.1 to about 1 microns.
[0204] Other preferable physical properties of the clay include a
total nitrogen pore volume of typically greater than 0.005 (e.g.,
0.005 to 1.50), preferably greater than about 0.1 (e.g., 0.1 to 2)
cc/g; a nitrogen surface area of typically greater than 10,
preferably greater than 30 (e.g., 10 to 100) m.sup.2/g; and an
Apparent Bulk Density (ABD) of typically greater than 0.10,
preferably greater than 0.25 (e.g., 0.10 to 0.75) g/cc.
[0205] Milling procedures can be employed to achieve these target
properties, if necessary.
[0206] To agglomerate by spray drying, Components-A and -B are
admixed, typically in a suitable diluent, to form a slurry of the
same. The diluent can be aqueous or organic. The preferred liquid
slurry medium for spray drying is aqueous, typically greater than
75, preferably greater than 80, and most preferably greater than 95
wt. % water (e.g. entirely water).
[0207] The weight ratio of Component-A:Component-B in the slurry,
can vary typically from about 0.25:1 to about 99:1, preferably from
about 0.5:1 to about 20:1, and most preferably from about 1:1 to
about 10:1 (e.g., 4:1). The solids content of the slurry containing
the mixture of Components-A and -B can vary typically from about 5
to about 25, preferably from about 10 to about 20, and most
preferably from about 15 to about 20 wt. % based on the slurry
weight.
[0208] Accordingly, agglomerate formation is controlled to impart
preferably the following properties to the support-activator:
[0209] (1) A surface area of typically at least about 20,
preferably at least about 30, and most preferably from at least
about 50 m.sup.2/g, which surface area can range typically from
about 20 to about 800, preferably from about 30 to about 700, and
most preferably from about 50 to about 600 m.sup.2/g;
[0210] (2) A bulk density of the support-activator particles of
typically at least about 0.15, preferably at least about 0.20, and
most preferably at least about 0.25 g/ml, which bulk density can
range typically from about 0.15 to about 1, preferably from about
0.20 to about 0.75, and most preferably from about 0.25 to about
0.45 g/ml;
[0211] (3) An average pore diameter of typically from about 30 to
about 300, and most preferably from about 60 to about 150
Angstroms; and
[0212] (4) A total pore volume of typically from about 0.10 to
about 2.0, preferably from about 0.5 to about 1.8, and most
preferably from about 0.8 to about 1.6 cc/g.
[0213] The particle size and particle size distribution sought to
be imparted to the agglomerate support-activator particles is
dictated and controlled by the type of polymerization reaction in
which the ultimate supported catalyst will be employed. For
example, a solution polymerization process typically can employ an
average particle size of from about 1 to about 10 microns; a
continuous stirred tank reactor (CSTR) slurry polymerization
process of from about 8 to 50 microns; a loop slurry polymerization
process of from about 10 to about 150 microns; and a gas phase
polymerization process of from about 20 to about 120 microns.
Moreover, each polymer manufacturer has its own preferences based
on the particular reactor configuration.
[0214] Once the desired average particle size is determined for the
agglomerates based on the targeted polymerization process, the
particle size distribution will desirably be such that the
Distribution Span is typically from about 0.5 to about 4,
preferably from about 0.5 to about 3, and most preferably from
about 0.5 to 2.
[0215] Accordingly, as a generalization, the average particle size
of the agglomerates will range typically from about 4 to about 250
(e.g. about 8 to about 200), and preferably from about 8 to about
100 (e.g. about 30 to about 60) microns.
[0216] When the agglomerates are formed by spray drying, they can
be further characterized in that typically at least 80, preferably
at least 90, and most preferably at least 95 volume % of that
fraction of the support agglomerate particles smaller that the
D.sub.90 of the entire agglomerate particle size distribution
possesses microspheroidal shape (i.e., morphology). Evaluation of
the microspheroidal morphology is performed on that fraction of the
particle size distribution of the support agglomerates which is
smaller than the D.sub.90 to avoid distortion of the results by a
few large particle chunks which because of their large volume,
would constitute a non-representative sample of the agglomerate
volume. The term "spheroidal" as used herein means small particles
of a generally rounded, but not necessarily spherical shape. This
term is intended to distinguish from irregular jagged chunks and
leaf or rod like configurations. "Spheroidal" is also intended to
include polylobed configurations wherein the lobes are also
generally rounded, although polylobed structures are uncommon when
the agglomerate is made as described herein.
[0217] Each microspheroid is preferably composed of a loosely to
densely packed composite of Components-A and -B typically with
some, to substantially no, interstitial void spaces, and typically
substantially no visible boundaries, in an electron micrograph,
between particles originally derived from Components-A and -B.
[0218] However, microprobe image and elemental analysis of a
cross-sectioned view of preferred agglomerate particles reveals
that the Fe and Al ions associated with Component-B are distributed
in clusters of varying density around discrete sub-particles of
material-bearing no iron or aluminum. This leads to the conclusion
that, in the most preferred agglomerate particles, Component-B is
intimately admixed with Component-A such that islands of inorganic
oxide (e.g., silica) are surrounded by a matrix of inorganic oxide
(most likely derived from the colloidal constituents of the
inorganic oxide) and layered material (e.g., clay). It is believed
that the varying intensity (concentration) of Al and Fe, in the
matrix is indicative of varying ratios of Component-A to
Component-B in the matrix.
[0219] The microspherodial shape of the support-activator
significantly enhances the desired morphology of the polymers
derived therefrom. Thus, one is able to simultaneously
significantly enhance catalyst activity and desired polymer
morphology by utilizing the 2 components of support-activator.
[0220] The terms "surface area" and "pore volume" refer herein to
the specific surface area and pore volume determined by nitrogen
adsorption using the B.E.T. technique as described by S. Brunauer,
P. Emmett, and E. Teller in Journal of American Chemical society,
60, pp. 209-319 (1939).
[0221] Bulk density is measured by quickly transferring (in 10
seconds) the sample powder into a graduated cylinder which
overflows when exactly 100 cc is reached. No further powder is
added at this point. The rate of powder addition prevents settling
within the cylinder. The weight of the powder is divided by 100 cc
to give the density.
[0222] Spray drying conditions are typically controlled in order to
impart the desired target properties described above to the
agglomerate. The most influential spray drying conditions are the
pH of the aqueous slurry to be spray dried, as well as its dry
solids content. By "dry solids content" as used herein is meant the
weight of solids in the slurry after such solids have been dried at
175.degree. C. for 3 hours, and then at 955.degree. C. for 1 hour.
Thus, dry solids content is used to quantify the weight of solid
ingredients which exist in the slurry and to avoid inclusion of
adsorbed water in such weight.
[0223] Typically, the pH of the slurry will be controlled or
adjusted to be from about 5 to about 10 (e.g., 8 to 9), preferably
from about 7 to about 9, and the dry solids content will be
controlled or adjusted to be typically from about 12 to 30,
preferably from about 15 to about 25, and most preferably from
about 18 to about 22 (e.g. 20) weight % based on the weight of the
slurry and the dry weight of the gel.
[0224] Control of the remaining variables in the spray drying
process, such as the viscosity and temperature of the feed, surface
tension of the feed, feed rate, the selection and operation of the
atomizer (preferably an air atomizer is employed and preferably
without the use of a pressure nozzle), the atomization energy
applied, the manner in which air and spray are contacted, and the
rate of drying, are well within the skill of the spray dry artisan
once directed by the target properties sought to be imparted to the
product produced by the spray drying. (See for example U.S. Pat.
No. 4,131,452.)
[0225] Product separation from the drying air follows completion of
the spray drying stage when the dried product remains suspended in
the air. Any convenient collection method can be employed, such as
removal from the base of the spray dryer by the use of separation
equipment.
[0226] To provide uniformity to the catalyst as well as the
resulting polymer, it is desirable to calcine the support-activator
to control any residual moisture present in the support.
[0227] When calcination is employed, it will typically be conducted
at sufficient temperature and time to reduce the total volatiles to
between about 0.1 and 8 wt. % where the total volatiles are
determined by measuring the weight loss upon destructive
calcination of the sample at 1000.degree. C. However, the
calcination temperature will also affect the interrelationship
between the desired silica:clay ratio and the orgnao aluminum
compound amount, and the activity of the catalyst as described
hereinafter in more detail. Accordingly, calcination, when
employed, will typically be conducted by heating the
support-activator to temperatures of typically from about 100 to
about 800, preferably from about 150 to about 600, and most
preferably from about 200 to about 300.degree. C. for periods of
typically from about 1 to about 600 (e.g., 50 to 600), and
preferably from about 50 to about 300 minutes. The atmosphere of
calcination can be air or an inert gas. Calcination should be
conducted to avoid sintering.
[0228] After formation, the support-activator is preferably sized
prior to calcination since the agglomerates will pick up moisture
if sized after calcination. This can be conveniently accomplished
by screening or air classifying as is well known in the art.
[0229] The particle size and particle size distribution selected
will depend on the catalyst type and polymerization process to be
applied, as would be well known in the art.
[0230] The preferred manner in which the support-activator is
combined with the pre-catalyst will depend in part on the
polymerization technique to be employed.
[0231] More specifically, the catalyst system components described
herein are useful to produce polymers using high pressure
polymerization, solution polymerization, slurry polymerization, or
gas phase polymerization techniques. As used herein, the term
polymerization includes copolymerization and terpolymerization, and
the terms olefins and olefinic monomers include olefins,
alpha-olefins, diolefins, styrenic monomers, acetylenically
unsaturated monomers, cyclic olefins, and mixtures thereof.
[0232] For example, polymerization of olefin monomers can be
carried out in the gas phase by fluidizing, under polymerization
conditions, a bed comprising the target polyolefin powder and
particulates of the catalyst composition using a fluidizing gas
stream comprising gaseous monomer. In a solution process the
(co)polymerization is typically conducted by introducing the
monomer into a solution or suspension of the catalyst composition
in a liquid hydrocarbon under conditions of temperature and
pressure such that the produced polyolefin forms as a solution in
the hydrocarbon diluent. In the slurry process, the temperature,
pressure and choice of diluent are such that the produced polymer
forms as a suspension in a liquid hydrocarbon diluent.
[0233] It will be apparent from the above discussion, that
deployment of the catalyst system can vary depending on the
polymerization process employed with a preference for permitting
the formation in-situ of the activated system in the presence of
the polymerizable monomer.
[0234] Thus, for gas phase polymerizations, the pre-catalyst and
optionally an organometallic compound can be impregnated into the
support-activator with a solvent and the solvent optionally
evaporated, whereas for polymerizations which occur in the liquid
state the catalyst system components can be simply mixed in a
hydrocarbon media for addition to the polymerization zone, or to a
media used as the liquid in which the polymerizations are
conducted.
[0235] As indicated above, an organometallic compound can be
employed for pre-activation of the pre-catalyst, e.g., where L of
the pre-catalyst is chlorine. It can also be employed as a
scavenger for poisons in the polymerization zone.
[0236] The mixing of pre-catalyst (referred to in the following
discussion as Component I), support-activator (referred to in the
following discussion as Component II), and optionally
organometallic compound (referred to in the following discussion as
Component III) can be readily accomplished by introducing the
components into a substantially inert (to chemical reaction with
Components I, II and III) liquid, which can serve as a diluent or
solvent for one or more of the catalyst components.
[0237] More specifically, the inert liquid preferably is a
non-solvent for the Component II support-activator at contact
temperatures to assure that the same will be suspended or dispersed
in the liquid during contact with Component I. The inert liquid can
be a solvent for the Component I transition metal compound.
[0238] Suitable inert liquids include hydrocarbon liquids,
preferably C.sub.5-C.sub.10 aliphatic or cycloaliphatic
hydrocarbons, or C.sub.6-C.sub.12 aromatic or alkyl substituted
aromatic hydrocarbons and mixtures thereof.
[0239] The components are introduced into the liquid and maintained
therein under agitation and at low temperature and pressure
conditions. Particularly suitable hydrocarbons include, for
example, 1,2-dichloroethane, dichloromethane, pentane, isopentane,
hexane, heptane, octane, isooctane, nonane, isononane, decane,
cyclohexane, methylcyclohexane, toluene, and combinations of two or
more of such diluents. Ethers such as diethylether and
tetrahydrofuran can also be used.
[0240] The Components I, II and III can be introduced into the
inert liquid in any order or substantially simultaneously. It is
preferred that, when the components are introduced sequentially,
they are introduced in rapid order; that is, without a substantial
period of delay between each components introduction. When
sequential introduction is conducted, it is preferred that the
components be added in the sequence of Component III if employed,
then Component II followed by Component I.
[0241] The temperature may range typically from about 0 to about
80, preferably from about 5 to about 60, and most preferably from
about 10 to about 40.degree. C. (e.g., 15 to about 25.degree. C.).
The Components can be contacted at reduced, atmospheric or elevated
pressure. Ambient conditions are preferred. The atmospheric
condition of the mixing zone should preferably be substantially
anaerobic and anhydrous.
[0242] The components are mixed for a period, preferably from 0.5
minute to 1440 minutes (more preferably from 1 to 600 minutes), to
provide a substantially uniform mixed catalyst composition.
[0243] The formed mixture can be separated from the inert liquid,
by filtration, vacuum distillation or the like to provide a solid
preformed catalyst composition.
[0244] The solid preformed catalyst is preferably stored under
anaerobic conditions until being introduced into a polymerization
reaction zone for use in forming polyolefin products. The resultant
catalyst composition is storage stable for about 3 to 6 months or
longer.
[0245] Alternatively, the mixture of Components I, II and III in
the inert liquid hydrocarbon, can remain without separation or
purification as a slurry and be used directly as a polymerization
catalyst composition. Thus, the present catalyst composition can be
formed by the single-step of mixing the readily available
components in an inert liquid and then either directly transferring
the formed liquid dispersion to the polymerization reaction zone or
placing it in storage under anerobic conditions. In this
embodiment, the inert liquid used to form the dispersion preferably
is chosen from those liquids which (a) are miscible with the
liquids used in the polymerization reaction zone, (b) are inert
with respect to the solvents, monomer(s) and polymer products
contemplated and (c) are capable of suspending or dispersing
Component II (e.g., is a non-solvent for the
support-activator).
[0246] The present polymerization catalyst composition can be
formed in-situ in a liquid phase polymerization reaction zone. The
organometallic compound (if employed) can be introduced neat or as
a solution in an inert liquid, which may be the same liquid as that
of the polymerization media. The other components may be introduced
into the polymerization zone either as solids or as slurries in
inert liquids. In all cases, the liquid(s) used to introduce the
components forming the present catalyst composition preferably is
miscible with the liquid used as the polymerization media.
[0247] A slurry of Components I, II and II can even be injected
into a gas phase polymerization zone under conditions where the
liquid slurry medium desirably would be sprayed into the reaction
zone whereby it would desirably evaporate leaving the catalyst in a
fluidized solid form.
[0248] In batch polymerization processes, the components forming
the present catalyst composition may be introduced prior to,
concurrently with or subsequent to the introduction of the olefinic
monomer feed. It has been found that the present catalyst
composition forms rapidly under normal polymerization conditions to
exhibit high catalytic activity and provide a high molecular weight
polymer product.
[0249] The amount of Components I and II in the inert liquid
hydrocarbon is controlled to be such as to provide a ratio of
micromoles of Component I (pre-catalyst) to grams of Component II
(support-activator) of typically from about 5:1 to about 500:1,
preferably from about 10:1 to about 250:1, and most preferably from
about 30:1 to about 100:1 (e.g., 60:1).
[0250] The amount of optional organometallic compound in the inert
liquid hydrocarbon depends on whether it is intended to be employed
for pre-activation of the pre-catalyst or as a scavenger in the
polymerization zone. When employed for pre-activation it is
controlled to be such as to provide a molar ratio of Component III
(organometallic compound to Component I (pre-catalyst) of typically
from about 0.001:1 to about 250:1, preferably from about 0.01:1 to
about 125:1, and most preferably from about 0.1:1 to about 10:1.
When employed as a scavenger by addition directly to the
polymerization zone the molar ratio can vary typically from about
1:1 to about 1000:1, preferably from about 2:1 to about 500:1, most
preferably from about 10:1 to about 250:1.
[0251] Alternatively, one can express the amount of the
organometallic compound, when employed, as a function of the weight
of the support-activator. More specifically, the ratio of
millimoles (mmol) of organometallic compound: grams of
support-activator employed can vary typically from about 0.001:1 to
about 2:1 (e.g., 0.05:1 to about 1:1), preferably from about 0.01:1
to about 1:1 (e.g., 0.01:1 to about 0.6:1), and most preferably
from about 0.1:1 to about 0.8:1 (e.g., 0.1;1 to about 0.5:1).
[0252] The amount of liquid hydrocarbon can vary typically from
about 50 to about 98, preferably from about 60 to about 98, and
most preferably from about 75 to about 90 wt. % based on the
combined weight of liquid hydrocarbon and Components I and II.
[0253] Without wishing to be bound to any particular theory, it is
believed that even without separation of the catalyst system from
the inert liquid, the pre-catalyst and optional organometallic
compound are very quickly adsorbed (adhere to the surface of the
support-activator agglomerate) and/or absorbed (penetrate into the
inner structure of the support-activator agglomerate particles) by
the support-activator. It is believed that the pre-catalyst slowly
reacts with the support-activator thereby promoting the solubility
of the pre-catalyst into the solution phase and resulting in
effective immobilization of the pre-catalyst onto the
support-activator matrix via mesoporous channels. This is believed
to result in improved dispersion of pre-catalyst throughout the
particles.
[0254] More specifically, x-ray powder diffraction analysis of the
support-activator impregnated with pre-catalyst displays an
amorphous x-ray diffraction pattern wherein a sharp distinct peak
originally present and attributable to pre-catalyst, has
disappeared. Moreover, resolubilization of pre-catalyst was not
observed when the catalyst system was washed with CH.sub.2 Cl.sub.2
(a known solvent which can dissolve pre-catalyst). When a blue
solution of pre-catalyst in CH.sub.2 Cl.sub.2 was mixed with a tan
slurry of support-activator in toluene, the color of the
support-activator solid turned light blue while the supernatant
CH.sub.2 Cl.sub.2 solution turned clear, further supporting the
conclusion that some type of reaction has taken place between the
support-activator and pre-catalyst.
[0255] The organometallic compound, when employed during in-situ
catalyst formation, pre-activates the pre-catalyst which is then
believed to be fully activated by the Lewis acidity of the
support-activator.
[0256] While the above discussion provides direction for
controlling the support-activator calcination temperature, the
Component-A (inorganic oxide):Component-B (layered material) wt.
ratio, and the Component III (organometallic compound) content
relative to either the support-activator weight or Component I
pre-catalyst molar ratio, it will be understood that it is desired
to control such variables to improve the catalyst activity relative
to the activity of a corresponding catalyst system employing either
Component-A alone or Component-B alone.
[0257] The catalyst composition of the present invention can be
used for polymerization, typically additional polymerization,
processes wherein one or more monomers are contacted with the
coordination catalyst system (either in its original inert liquid
or as separated solid product, as described above) by introduction
into the polymerization zone under polymerization conditions.
[0258] Suitable polymerizable monomers include ethylenically
unsaturated monomers, acetylenic compounds, conjugated or
non-conjugated dienes, and polyenes. Preferred monomers include
olefins, for example alpha-olefins having from 2 to 20,000,
preferably from 2 to 20, and more preferably from 2 to 8 carbon
atoms and combinations of two or more of such alpha-olefins.
Particularly suitable alpha-olefins include, for example, ethylene,
propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene or combinations thereof,
as well as long chain vinyl terminated oligomeric or polymeric
reaction products formed during the polymerization and C.sub.10-30
.alpha.-olefins specifically added to the reaction mixture in order
to produce relatively long chain branches in the resulting
polymers. Preferably, the alpha-olefins are ethylene, propene,
1-butene, 4-methyl-pentene -1,1-hexene, 1-octene, and combinations
of ethylene and/or propene with one or more of such other
alpha-olefins. The most preferred is ethylene alone or with other
alpha-olefins. Other preferred monomers include styrene, halo- or
alkyl substituted styrenes, tetrafluoroethylene, vinylcyclobutene,
1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and
1,7-octadiene. Mixtures of the above-mentioned monomers may also be
employed.
[0259] In addition, the polymerization monomers may include
functionalized ethylenically unsaturated monomers wherein the
functional group is selected from hydroxyl, carboxylic acid,
carboxylic acid esters, acetates, ethers, amides, amines and the
like.
[0260] The present coordination catalyst system (composition) can
be advantageously employed in a high pressure, solution, slurry or
gas phase polymerization process.
[0261] Methods and apparatus for effecting such polymerization
reactions are well known. The catalyst system according to the
present invention can be used in similar amounts and under similar
conditions known for olefin polymerization catalysts. Typically for
the slurry process, the temperature is from approximately 0.degree.
C. to just below the temperature at which the polymer becomes
soluble in the polymerization medium. For the gas phase process,
the temperature is from approximately 0.degree. C. to just below
the melting point of the polymer. For the solution process, the
temperature is typically the temperature from which the polymer is
soluble in the reaction medium, up to approximately 275.degree.
C.
[0262] The pressure used can be selected from a relatively wide
range of suitable pressures, e.g., from subatmospheric to about
20,000 psi. Preferred pressures can range from atmospheric to about
1000 psi, and most preferred from 50 to 550 psi. In the slurry or
particle form process, the process is suitably performed with a
liquid inert diluent such as a saturated aliphatic hydrocarbon. The
hydrocarbon is typically a C.sub.3 to C.sub.10 hydrocarbon, e.g.,
propane, isobutane or an aromatic hydrocarbon liquid such as
benzene, toluene or xylene. The polymer can be recovered directly
from the gas phase process, by filtration or evaporation of the
slurry from the slurry process, or evaporation of solvent in the
solution process.
[0263] All references herein to elements or metals belonging to a
certain Group refer to the Periodic Table of the Elements in
Hawley's Condensed Chemical Dictionary, 12.sup.th Edition. Also,
any references to the Group or Groups shall be to the Group or
Groups as reflected in this Periodic Table of Elements using the
new notation system for numbering groups.
[0264] The following examples are given as specific illustrations
of the claimed invention. It should be understood, however, that
the invention is not limited to the specific details set forth in
the examples. All parts and percentages in the examples, as well as
in the remainder of the specification, are by weight unless
otherwise specified.
[0265] Further, any range of numbers recited in the specification
or claims, such as that representing a particular set of
properties, units of measure, conditions, physical states or
percentages, is intended to literally incorporate expressly herein
by reference or otherwise, any number falling within such range,
including any subset of numbers within any range so recited.
EXAMPLE 1
Preparation of Support-Activator
[0266] Part A--Preparation of Base Silica Hydrogel
[0267] Silica gel is prepared by mixing an aqueous solution of
sodium silicate and sulfuric acid under suitable agitation and
temperature to form a silica sol that sets to a gel in about 8
minutes. The resulting gel is base washed with dilute (about 2 wt.
%) ammonia (NH.sub.3) solution at 65.5.degree. C. (150.degree. F.)
for 18 to 36 hours. During this time, the silica gel is cleansed of
salt by-products and the surface area is modified. The base wash is
followed by a fresh water wash wherein the gel is placed in a
recirculating bath at 82.degree. C.
[0268] The base washed gel was aged at 65-82.degree. C. for about
36 hours and a pH of 6 to 7 for one sample designated 1A, and a pH
of 7.5 to 9 for another sample designated 1B. The surface area of
the gel is thereby reduced to about 600 m.sup.2/g for Sample 1A and
to 300 m.sup.2/g for Sample 1B. The resulting water washed gel of
Samples 1A and 1B have a SiO.sub.2 content of about 35 wt. % with
the balance being water, and an Average Particle Size (APS) of
Samples 1A and 1B from 0.5 to 2.0 cm.
[0269] Part B(i)--Preparation of Wet Milled Hydrogel Sample 2A (SA
600 m.sup.2/g)
[0270] A Sample 1A silica gel prepared in accordance with Part A
was subjected to wet milling in a sand mill. Sufficient water was
then added thereto to make a slurry of 20 wt. % solids. The bulk
sample particle size was reduced with a blade mill and further
processed through a wet sand mill to reduce the average particle
size (APS) to <100 microns. The sample was then sand milled. The
slurry was pumped through the sand mill at 1 liter per minute with
a media load of 80% (4 liters) zirconia silicate 1.2 mm beads. The
average particle size was reduced to 8 and 10 microns and the
particle size distribution was 4/8/15 microns for D10, D50 and D90.
The surface area was 600 m.sup.2/g. The resulting wet milled sample
was designated Sample 2A. Sample 2A had a colloidal content between
20 and 25 wt. % as determined by centrifugation.
[0271] Part B(ii)--Preparation of Wet Milled Hydrogel Sample 2B (SA
300 m.sup.2/g)
[0272] Example 1, Part B(i) was repeated using base silica gel
Sample 1B. The resulting wet milled sample was designated Sample 2B
and had a colloidal content between 15 and 30 wt. % as determined
by centrifugation and a SA of 300 m.sup.2/g. The resulting material
was designated Sample 2B.
[0273] Part C--Preparation of Dry Milled Sample 3B (SA 300
m.sup.2/g)
[0274] A base silica gel Sample 1B prepared in accordance with Part
A was subjected to dry milling procedure as follows:
[0275] The sample was flash or spray dried to a moisture content
below 10 wt. %. The dried powder sample was then milled to an
average particle size (APS) of about 5 microns, a surface area (SA)
of still about 300 m.sup.2/g, and a N.sub.2 pore volume of 1.5
cc/g. The resulting sample was designated Sample 3B.
[0276] Part D--Preparations of Dry Milled Sample 3A (600
m.sup.2/g)
[0277] Part C was repeated except that the base silica gel was
Sample 1A prepared in accordance with Example 1, Part A. The
resulting dry milled sample had a moisture content of less than 10
wt. %, an APS of 5 microns and a SA of 600 m.sup.2/g. The resulting
sample was designated Sample 3A.
[0278] Part E--Preparation of Silica Slurry
[0279] Seven different blends (designated Runs 1 to 6 and Run 9) of
Sample 2B and Sample 3B were prepared at weight ratios of Sample 3B
(dry milled):Sample 2B (wet milled) as reported in Table IV. Before
blending, Sample 3B was slurried in water to a 20 wt. % solids
content using a mixer. The Sample 3B slurry was then added to the
20 wt. % solids content aqueous slurry of Sample 2B at amounts
sufficient to achieve the ratios reported in Table IV.
3TABLE IV Silica Support Slurries Run Ex or Comp Sample 3B (Dry
Milled):Sample 2B (Wet Milled) Number Ex No Weight % Ratio Weight
Ratio 1 Ex 1 Part E 79/21 3.75:1 2 Ex 1 Part E 78/22 3.50:1 3 Ex 1
Part E 75/25 3.00:1 4 Ex 1 Part E 70/30 2.25:1 5 Ex 1 Part E 60/40
1.50:1 6 Ex 1 Part E 0/100 0:1 7* Ex 2 70/30 0.43:1 8* Ex 3 100/0
0:1 9 Ex. 1, Part E 80/20 0.25:1 * = tray dried
[0280] Part F--Preparation of Alternate Silica Support Slurries
[0281] Part E was repeated except that Sample 3B (300 m.sup.2/g)
was replaced with Sample 3A (600 m.sup.2/g) and Sample 2B (300
m.sup.2/g) was replaced with Sample 2A (600 m.sup.2/g). The dry
milled/wet milled ratios employed are summarized at Table V and the
slurries designated Runs 10 to 12.
4TABLE V Run Sample 3A (Dry Milled):Sample 2A (Wet Milled) Number
Weight % Ratio Weight Ratio 10 75/25 3.00:1 11 60/40 1.50:1 12
0/100 0:1
[0282] Part G--Preparation of Clay Slurry
[0283] A montmorillonite clay available from Southern Clay, under
the trade names, Montmorillonite BP Colloidal Clay, was obtained.
This clay has the following properties as summarized at Table
VI.
5TABLE VI Chemical Composition of Montmorillonite BP Colloidal Clay
Component Weight % S.sub.iO.sub.2 69.5 Fe.sub.2O.sub.3 4.4
Al.sub.2O.sub.3 19.0 M.sub.gO 2.3 C.sub.aO 1.0 Na.sub.2O 2.7
SO.sub.4 0.6 Physical Properties Appearance Tan Powder Apparent
Bulk Density 0.45 g/cc Surface Area 70 m.sup.2/g APS 1.5 microns
Average Pore Diameter 114 .ANG. Total Pore Volume 0.20 cc/g
[0284] Part H--Preparation of Silica/Clay Slurry for Spray
Drying
[0285] Each of the silica slurries of Runs 1 to 6 and 10 to 12 was
combined with the clay slurry of Part G in a manner sufficient to
control the weight ratio of silica: clay dry solids to be as
reported at Table VII. Each slurry was adjusted with acid (sulfuric
acid) or base (ammonium hydroxide) to achieve a slurry pH of 7-8.5.
The APS of the slurry solids was about 4 to 5 microns, the total
dry solids content of the slurry was about 15 to 18 wt. %. The
resulting slurries are designated Runs 13 to 21.
[0286] Part I--Spray Drying of Silica/Clay Slurry
[0287] Each pH adjusted slurry of Runs 13 to 21 was then pumped to
a spray dryer to dry the mixture and to form microspheroidal
agglomerates. All spray drying is conducted by using a Bowen 3-ft.
diameter spray dryer with inlet-outlet temperatures of
350/150.degree. C. and a two-fluid spray nozzle using air at 10-30
psi to atomize the slurry. The air through-put of the Niro is
dampened to keep the spray chamber under 7" water vacuum and the
slurry is fed at 250-300 cc/min. The product is then collected in
the chamber collection pot, located directly under the drying
chamber, where the coarsest fraction drops out from air
entrainment. Other, smaller fractions go to a cyclone collection
pot and the smallest to a baghouse. The chamber material is then
screened through 200 to 250 mesh to give the desired APS of 40-55
microns. The Total Volatiles (TV %) at 954.4.degree. C.
(1750.degree. F.) of the spray dried product is in the range of
2-20 wt. %, so further drying in a static bed oven at
150-800.degree. C. is then used to lower the total volatiles down
to 0.5-5%.
[0288] The total yield of material from the spray dryer chamber
collection pot and from screening the same is about 15-20 wt.
%.
[0289] Table VIII below reports silica/clay morphological
properties of the resulting agglomerates. The resulting Agglomerate
Samples are designated Runs 27 to 35.
EXAMPLE 2
Tray Dried--Silica/Clay Support-Activator
[0290] 65 parts by weight of a silica sample (designated Run 7) I
prepared in accordance with Example 1, Part E, but containing 30
wt. % wet milled silica hydrogel Sample 2B (prepared in accordance
with Example 1, Part B(ii) 300 m.sup.2/g) and 70 wt. % dry milled
silica powder Sample 3B (prepared in accordance with Example 1,
Part C (SA=300 m.sup.2/g)), were mixed with 35 parts by weight
montmorillonite clay available under the tradename Mineral
Colloidal BP from Southern Clay Company.
[0291] The mixture (designated Run 22) was made by adding the clay
powder to a 10% dry solids content slurry of the silica to bring
the total solids content of clay plus silica to 15 wt. %. The
slurry was then mixed.
[0292] At the solids content employed, the slurry existed as a
paste which was spread out on a tray to dry. The paste was then
tray dried in a vacuum oven at 204.4.degree. C. (400.degree. F.)
for 16 hours. The tray dried sample was crushed and sieved through
200 U.S. mesh screen to yield an average particle size of about 50
microns. A portion of the sieved sample was tested for BET Surface
Area and Nitrogen Pore Volume and found to be 215 m.sup.2/g and
0.85 cc/g respectively. The resulting tray dried agglomerate sample
was designated Run 36.
EXAMPLE 3
Tray Dried Silica/Clay Support-Activator
[0293] Example 2 was repeated except that the silica sample
(designated Run 8) employed was entirely dry milled silica powder
(no wet milled silica gel) prepared in accordance with Example 1,
Part C.
[0294] The surface area and pore volume was analyzed and found to
be 224 m.sup.2/g. and 0.82 cc/g respectively. The resulting tray
dried sample was designated Run 23.
Comparative Example 1
Spray Dried 100% Clay
[0295] 5 parts-by-weight montmorillonite clay available from
Southern Clay Company under the tradename Mineral Colloidal BP was
mixed with 28 parts-by-weight water. The slurry (designated Run
24C) was the then fed to a Niro Spray Dryer in accordance with
Example 1, Part I to make clay microspheres. The resulting product
never agglomerated into microspheroids. A very small quantity of
material accumulated in the spray dryer chamber collection pot
(<5% yield) and the remainder was observed as dust and build-up
on the spray dryer wall. After screening, <1 wt. % of the
collected sample was in the form of microspheroids with most of the
clay being carried over to the cyclone or baghouse as dust. The
resulting spray dried clay, designated Run 38C, was unusable and
discarded.
Comparative Example 2
Spray Dried 100% Clay
[0296] Comparative Example 1 was repeated except that the clay
employed was montmorillonite available under the tradename Gel
White from Southern Clay Products. The slurry to be spray dried is
designated Run 25C. Only 1.3 wt. % of the starting clay was
recovered as agglomerates that accumulated in the spray dryer
chamber collection pot.
[0297] The crude agglomerated product was screen through 200 mesh
screen to remove large agglomerates and give an APS of 40-55
microns (based on Malvern particle size analysis). This product has
a pore volume of 0.21.cc/g and the surface area is 72
m.sup.2/g.
[0298] The resulting spray dried clay powder was designated Run
39C.
Comparative Example 3
100% Spray Dried Silica
[0299] Example 1, Part I was repeated except that the slurry
(designated Run 26C) that was spray dried contained only silica,
and the silica was derived from Run 9, i.e., a mixture containing:
80 wt. % dry milled silica powder Sample 3B and 20 wt. % wet milled
silica hydrogel Sample 2B. No clay was employed. The resulting
spray dried product was a microspheroidal agglomerate with a pore
volume of 1.69 cc/g, a surface area of 277 m.sup.2/g and an average
particle size (APS) of 47 microns. The resulting spray dried
product was designated Run 40C.
EXAMPLE 4
Preparation of Tridentate Catalyst System
[0300] The support-activators of Runs 27 to 34 were subjected to
various calcination temperatures and times as indicated at Table IX
to control the total volatiles thereof. Each designated calcined
support-activator was then added to 25 ml of toluene along with
sufficient tridentate transition metal pre-catalyst, i.e., 2,6 bis
(2,4,6-trimethylarylimino) pyridyl iron dichloride, to provide the
ratio of micromoles of pre-catalyst per gram of support-activator
reported at Table IX Runs 41 to 93 and 101 to 104. Triisobutyl
aluminum (1M in toluene solution) was also added to the toluene in
amounts sufficient to give the reported micromoles of
triisobutylaluminum per gram of support-activator when
employed.
Comparative Example 4
[0301] Example 4 was repeated two additional times and designated
Runs 94C and 95C except that the silica/clay support activator was
replaced with colloidal (<1 micron particle size) undehydrated
and non-spray dried montmorillonite available from Aldrich under
the tradename K10 Montmorillonite (Run 95C) and undehydrated
non-spray dried Mineral Colloidal BP (Run 94C) (as described in
Example 1, Part G). The ratios of triisobutylaluminum and
Fe-pre-catalyst are summarized at Table IX at Runs 95C and 94C
respectively.
Comparative Example 5
[0302] Example 4 was repeated except that the silica-clay
agglomerate was replaced with an unagglomerated physical blend of
Mineral Colloidal (<1 micron particle size) BP montmorillonite
clay and silica hydrogel powder (Sample 4) prepared by the
following procedure: A base silica hydrogel Sample 1B (SA 300
m.sup.2/g) was wet milled to an APS of 15-25 microns to form a 20
wt. % solids slurry in water. The silica hydrogel was then spray
dried and the fraction of fines contained therein was collected by
air classification and designated Sample 4. Sample 4 had an APS of
10 microns, a Nitrogen pore volume of 1.6 cc/g and a surface area
of 300 m.sup.2/g. Pre-catalyst was then added in accordance with
Example 4 and the resulting mixtures tested in accordance with
Example 6 as Runs 96C and 97C. The amounts of triisobutylaluminum
and Fe-pre-catalyst ratios are reported at Table IX.
Comparative Example 6
[0303] Example 4 was repeated except that the Silica/Clay support
activator was replaced with the silica agglomerate prepared in
accordance with Run 40C. The amounts of triisobutylaluminum and
Fe-pre-catalyst are reported at Runs 98C, 99C and 100C.
EXAMPLE 5
[0304] Example 4 was repeated except that the Silica/Clay
support-activator was replaced with the tray dried samples of Runs
36 and 37 respectively. The amounts and ratios of
triisobutylaluminum and Fe-pre-catalyst employed are summarized at
Table IX Runs 105 and 106.
EXAMPLE 6
Polymerization Method
[0305] In the slurry polymerization experiments of this Example,
unless otherwise indicated, a 2-liter Zipperclave (Autoclave
Engineers, Inc.) reactor was rendered inert by heating under vacuum
at 70.degree. C. for 90 minutes. A reactor charge consisting of a
mixture of 350 ml of dry, degassed heptane and 200 micromoles of
triisobutyl aluminum scavenger dissolved in toluene and,
separately, 0.3 to 0.5 ml liters (depending on catalyst activity)
of a slurry of triisobutylaluminum, pre-catalyst and
support-activator derived from one of Runs 41 to 106 of Table IX
were injected into the reactor. While the reactor contents were
stirred at 500 rpm, ethylene and hydrogen were quickly admitted to
the reactor until a final reactor pressure of 200 psig was
attained. This pressure comprised a hydrogen/ethylene partial
pressure ratio of 0.05. The polymerization temperature was
70.degree. C. which was maintained by a circulating water bath.
Ethylene was supplied on demand via a mass flow controller to
maintain the reactor pressure of 200 psig. After 60 minutes, the
ethylene feed was stopped and the reactor cooled to room
temperature and vented. The polymer was filtered and washed with
methanol and acetone to deactivate any residual catalyst, filtered
and dried in a vacuum oven for at least three hours to constant
weight. After drying, the polymer was weighed to calculate catalyst
activity and a sample of dried polymer was used to determine
apparent bulk density according to the procedure of ASTM 1895.
[0306] The results of each polymerization are summarized at Table
IX Runs 41 to 106. Column 7 depicts the amount (mmole) of
triisobutylaluminum (AlBu.sub.3) used with respect to the amount
(grams) of support-activator material during the active catalyst
preparation. Column 8 depicts the amount of Fe pre-catalyst and the
amount (grams) of support-activator used during the active catalyst
preparation. Column 11 depicts the bulk density of the resulting
polyethylene (PE) product (determined by ASTM 1895 method). The
catalyst performance data include: (i) catalyst activity data
(Column 9) (KgPE/gCat-h) which is based on the total amount (grams)
of polyethylene product produced per gram of total catalyst used
per hour; and (ii) activity as a function of Fe concentration.
Thus, Column 10 represents gPEx10.sup.-6/gFe-h which is related to
the total amount (gram) of polyethylene product produced per gram
of Fe metal present in the pre-catalyst per hour. More
specifically, a reported value of 1 in Column 9 indicates 1,000,000
g of PE is produced per gram of Fe per hour. The particle size
distributions of the resulting polymer particles produced by Runs
45, 56, 67 (spray dried support-activator), 105 and 106 (tray dried
support-activator), 94C (100% clay) and 96C (non-agglomerated
physical mixture of silica and clay) are provided at Table X.
Discussion of Results
[0307] Comparing Runs 105 and 106 (tray dried) to Runs 62 to 65
(spray dried), it can be seen that spray dried agglomerates exhibit
an activity between 6.5 and 8 at AlBu.sub.3 contents below 1 and
between 5.5 and 8 for tray dried. However, it is believed that
because the tray dried support-agglomerates of Runs 105 and 106 are
non-uniform in shape and size, they produce a wide distribution in
the polymer particle sizes (see Table X). In contrast, spray dried
Runs 45, 56 and 67 produce no polymer particles between 0 and 250
micron diameters. This reduces polymer fines and increases the ease
with which the polymer can be handled. Similar considerations apply
to the polymer of Run 94C which employs no silica and consequently
was not spray dried because the product disintegrates into fines
(see Run 38C). The resulting morphology of this comparative
clay-only support is believed to be responsible for the poor
polymer morphology.
[0308] Comparing Run 96C (80:20 silica:clay physical admixture)
with Run 102 (80:20 spray dried agglomerate), it can be seen that
the activity of Run 102 is almost 4 times greater than that of Run
96C. Thus, the configuration as an agglomerate is considered
critical to the present invention relative to merely mixing silica
particles with clay particles in the polymerization zone or during
activation. The physical blend of support-activator components of
Run 96C also yields a poor polymer morphology (see Table X Run
96C).
[0309] Comparing Runs 94C and 95C (100% clay) with Runs 41 to 45
(80:20 silica:clay), it can be seen that very low activities (2.92
and 0 respectively) are associated with a clay-only support versus
activities of 5 to 10.3 for silica-clay support-activators.
[0310] Similar results are obtained by silica only
support-activators. For example compare Runs 98C, 99C and 100C to
Runs 101 to 104 wherein the activities of the later are more than
double those of the comparative runs.
EXAMPLE 7
Cross Section Scanning Electron Micrograph (SEM)
[0311] A small portion of the sample from Run 30 was dispersed into
an apoxy resin and allowed to cure overnight in a glove box
containing Argon. Once the epoxy cured, the mounted sample was
polished until the internal matrix of several particles was exposed
and a 0.05 um smooth surface was achieved.
[0312] A small portion of the polished sample block was placed on a
SEM stub in a glove box under Argon. Once the sample is mounted, it
is placed into a jar in the glove box. The sealed jar containing
the sample was then placed in a glove bag that has been placed over
the opening of the SEM and is purged with Argon. Once the bag has
been flushed with Argon three times, the sample jar is opened and
the sample is placed into the SEM for analysis. Images are obtained
on the dry uncoated sample using a Hitachi S4500 scanning electron
microscope using a beam accelerating voltage of 1.0 kV. The results
are shown at FIGS. 1 and 2.
EXAMPLE 8
Activity Response Contour Map
[0313] The data based on the 300 m.sup.2/g SA support-activator
Samples 2B and 3B from Table IX conducted in accordance with
Example 6, were categorized by their 4 hour calcination
temperatures and subjected to a Hyper-Greco-Latin Square (HGLS)
experimental design algorithm. Four variables were examined,
namely, (1) triisobutylaluminum loading, (2) wt. % clay in
support-activator, (3) pre-catalyst loading, and (4) calcination
temperature of support-activator. For each of these variables, a
four-factor, four-level HGLS Design as shown by Table XI was
created. From the 34 available data points (16 from the design and
18 extra data points, all reported at Table IX) and a 92% model
coefficient, the average catalyst activities were then calculated
in accordance with the following equations: 3 L n . ( C A ) =
1.97260 - 1.03944 * ( A l B u 3 - 0.6 ) - 0.00472 * ( C l a y - 45
) - .0014556 * ( D r y - 370 ) - .00023776 * ( C l a y - 45 ) * ( C
l a y - 45 ) - .000003075 * ( D r y - 370 ) * ( D r y - 370 ) -
.0019575 * ( A l B u 3 - 0.6 ) * ( D r y - 370 ) = .00004975 * ( C
l a y - 45 ) * ( D r y - 370 ) a n d Eq . 2 L n . C a t A c t i v i
t y = ( L n . ( C A ) ) - 1 E q . 3
[0314] wherein:
[0315] Ln.=natural log
[0316] Dry=4 hour support-activator Calcination Temperature
.degree. C.
[0317] Clay=wt. % clay in support-activator
[0318] AlBu.sub.3=m moles/g support-activator employed
[0319] These calculated activities were then employed to make the
activity contour maps of FIGS. 3 to 13.
[0320] The number on each line of each plot represents the catalyst
activity, in units as described above, that would be expected at
the illustrated combination of wt. % clay and triisobutyl aluminum
content.
[0321] Comparing FIGS. 3 to 14, it can be seen that catalyst
activities as high as 13 can be achieved at very low AlBu.sub.3
contents between 0.1 and 0.2 and clay contents in the
support-activator between 20 and 30 wt. % when the
support-activator is uncalcined or calcined up to 200.degree. C. As
the calcination temperature increases from 250 to 800.degree. C.,
the highest activities drop below 13 and the clay content of the
support-activator can be progressively increased in association
with decreases in the AlBu.sub.3 content and vice-versa to maintain
a given activity It will be further observed that the activity
consistently decreases as the AlBu.sub.3 content increases up to
1.
[0322] As a general proposition therefore, clay content in the
support-activator and calcination temperature thereof are believed
to be directly proportional to catalyst activity at increasingly
higher calcination temperatures. However, the relationship between
clay content and activity becomes inversely proportional at a given
calcination temperature. Also the AlBu.sub.3 content is inversely
proportional to catalyst activity at all tested calcination
temperatures at least up to a AlBu.sub.3 content of 1. Moreover,
clay content and AlBu.sub.3 are generally inversely proportional
over a segment of a plot; e.g., at high clay contents and directly
proportional over another segment of the same activity plot. This
transition from direct to inverse proportionality to maintain a
given activity occurs at higher clay contents for higher
calcination temperatures.
EXAMPLE 9
[0323] Example 4 was repeated using the support-activator of Run 33
except that the reaction mixture of support-activator pre-catalyst
and toluene was agitated with an orbital shaker for 24 hours. The
slurry was then filtered, washed two times with 20 ml toluene, two
times with 20 ml of heptane and dried in vacuo. The resulting
powdered catalyst system was then employed for polymerization of
ethylene in accordance with Example 6 by reslurry of the powder
into toluene prior to injection into the polymerization reactor.
The results are summarized at Run 107. The polymer product had a Mw
of 358,100 an Mn of 37,600 and an Mw/Mn of 9.5.
6TABLE VII Spray Drying or Tray Drying Slurry and Conditions Ex.
No. or Source of Silica:Clay Comp. Ex Silica Dry Solids Run No. No.
(Run Nos.) Ratio (w/w) 13 Ex 1 Pt H 1 95:5 14 Ex 1 Pt H 2 90:10 15
Ex 1 Pt H 3 80:20 16 Ex 1 Pt H 4 65:35 17 Ex 1 Pt H 5 50:50 18 Ex 1
Pt H 6 25:75 19 Ex 1 Pt H 10 80:20 20 Ex 1 Pt H 11 50:50 21 Ex 1 Pt
H 12 25:75 22 Ex 2 7 65:35 23 Ex 3 8 65:35 24C Comp Ex 1 none 0:1
25C Comp Ex 2 none 0:1 26C Comp Ex 3 9 1:0
[0324]
7TABLE VIII Spray Dried Silica/Clay Support-Activator Product
Properties Column No. 1 2 3 4 5 6 7 Ex. No. Slurry Source
Agglomerate Properties Run or from Table VII Silica/Clay APS SA
Pore Vol. Drying No. Comp Ex. (Run No.) (Weight Ratio) (microns)
(m.sup.2/g) (cc/g) Procedure 27 Ex 1 13 95:5 45 275 1.65 Spray 28
Ex 1 14 90:10 45 268 1.61 Spray 29 Ex 1 15 80:20 45 251 1.48 Spray
30 Ex 1 16 65:35 45 213 1.28 Spray 31 Ex 1 17 50:50 45 185 1.04
Spray 32 Ex 1 18 25:75 45 160 0.64 Spray *33 Ex 1 19 80:20 45 494
1.16 Spray *34 Ex 1 20 50:50 45 322 0.83 Spray *35 Ex 1 21 25:75 45
192 0.54 Spray 36 Ex 2 22 65:35 45 215 0.85 Tray 37 Ex 3 23 65:35
45 224 0.82 Tray **38C Comp Ex .sup. 24C 0:1 N/A N/A N/A Spray 1
39C Comp Ex .sup. 25C 0:1 40-55 72 0.21 Spray 2 40C Comp Ex .sup.
26C 1:0 47 277 1.68 Spray 3 *= Made from 600 m.sup.2/g silica **=
Discarded APS = Average Particle Size PSD = Particle Size
Distribution based on D10, D50, D90 percentile
[0325]
8 TABLE IX 2 8 Support- 7 Fe Pre- 9 Activator 3 4 5 6 AlBu.sub.3
Cat Cat 10 1 Source Corresponding Silica:Clay Calcination mmol/g-
.mu.mol/g Activity Fe Activity 11 Run (Run Ex or Comp (Weight Temp
Time Support- Support- KgPE/ gPE .times. 10.sup.-6/ B.D. No. No.)
Ex No. Ratio) .degree. C. (hr) Activator Activator gCat-h gFe-h
g/cc 41 27 Ex 4 95:5 UC N/A 1 57.3 5.13 1.60 0.37 42 28 Ex 4 90:10
UC N/A 1 57.3 7.75 2.42 0.34 43 29 Ex 4 80:20 UC N/A 1 73.8 10.11
2.37 0.41 44 29 Ex 4 80:20 UC N/A 1 57.3 10.26 3.20 0.41 45 29 Ex 4
80:20 UC N/A 1.2 38.2 8.87 4.29 0.46 46 29 Ex 4 80:20 150 4 0.4
76.3 7.86 1.84 0.42 47 29 Ex 4 80:20 250 4 1 57.3 0 0.00 NA 48 29
Ex 4 80:20 250 4 0.7 57.3 9.93 3.11 0.40 49 29 Ex 4 80:20 250 4 0.6
57.3 9.85 3.09 0.39 50 29 Ex 4 80:20 250 4 0.4 57.3 8.78 2.74 0.42
51 29 Ex 4 80:20 250 4 0.3 57.3 9.6 3.00 0.43 52 29 Ex 4 80:20 250
4 0.3 38.1 7.14 3.35 0.42 53 29 Ex 4 80:20 250 4 0.2 57.3 9.28 3.00
0.44 54 29 Ex 4 80:20 250 4 0.1 57.3 7 2.19 0.44 55 29 Ex 4 80:20
500 4 0.1 95.4 7.52 1.41 0.46 56 29 Ex 4 80:20 500 4 0.3 57.3 8.68
2.71 0.44 57 29 Ex 4 80:20 800 4 0.1 57.3 1.72 0.54 NA 58 29 Ex 4
80:20 800 4 0.12 57.3 2.35 0.73 0.29 59 29 Ex 4 80:20 800 4 0.8
57.3 0.04 0.01 NA 60 30 Ex 4 65:35 UC N/A 0.5 57.3 9.7 3.03 0.34 61
30 Ex 4 65:35 UC N/A 0.4 95.4 8.54 1.60 0.38 62 30 Ex 4 65:35 150 4
1.2 57.3 1.66 0.78 NA 63 30 Ex 4 65:35 150 4 0.6 57.3 6.7 2.10 0.38
64 30 Ex 4 65:35 150 4 0.3 57.3 7.1 2.22 0.41 65 30 Ex 4 65:35 150
4 0.12 57.3 7.73 2.42 0.43 66 30 Ex 4 65:35 500 4 0.30 57.3 9.38
2.93 0.41 67 30 Ex 4 65:35 500 4 0.12 57.3 11.4 3.57 0.42 68 30 Ex
4 65:35 500 4 0.10 57.3 8.87 2.78 0.43 69 30 Ex 4 65:35 500 4 0.08
57.3 5.27 1.65 0.41 70 30 Ex 4 65:35 500 4 0.80 38.2 2.18 0.68 0.38
71 30 Ex 4 65:35 800 4 0.10 76.3 3.02 0.71 0.35 72 31 Ex 4 50:50 UC
N/A 0.1 57.3 8.51 2.66 0.37 73 31 Ex 4 50:50 150 4 0.2 57.3 6.48
2.00 0.40 74 31 Ex 4 50:50 150 4 0.3 57.3 7.52 2.35 0.38 75 31 Ex 4
50:50 150 4 0.4 57.3 11.04 3.45 0.41 76 31 Ex 4 50:50 150 4 0.8
95.4 6.54 1.23 0.44 77 31 Ex 4 50:50 500 4 0.12 57.3 10.58 3.31 0.4
78 31 Ex 4 50:50 500 4 0.1 57.3 6.53 2.04 0.38 79 31 Ex 4 50:50 500
4 1.2 76.3 1.14 0.27 NA 80 31 Ex 4 50:50 800 4 0.1 57.3 2.35 0.73
0.29 81 31 Ex 4 50:50 800 4 0.4 38.2 2.06 0.97 0.31 82 32 Ex 4
25:75 UC N/A 0.8 57.3 1.45 0.45 NA 83 32 Ex 4 25:75 UC N/A 0.8 76.3
1.77 0.42 0.27 84 32 Ex 4 25:75 UC N/A 1.2 57.3 2.77 0.87 0.34 85
32 Ex 4 25:75 UC N/A 1.4 57.3 2.77 0.87 0.32 86 32 Ex 4 25:75 UC
N/A 0.5 57.3 1.22 0.38 NA 87 32 Ex 4 25:75 150 4 0.1 38.2 6.11 2.87
0.38 88 32 Ex 4 25:75 250 4 0.4 57.3 2.67 0.83 0.32 89 32 Ex 4
25:75 250 4 0.3 57.3 2.1 0.65 NA 90 32 Ex 4 25:75 250 4 0.2 57.3
5.5 1.70 0.38 91 32 Ex 4 25:75 250 4 0.1 57.3 6.84 2.10 0.40 92 32
Ex 4 25:75 500 4 0.4 57.3 5.97 1.87 0.35 93 32 Ex 3 25:75 800 4 1.2
95.4 0 0.00 NA 94C Ex 1, PtG Comp Ex 4 0:1 UC N/A 0.5 57.3 2.92
0.91 0.31 95C Comp Comp Ex 4 0:1 UC N/A 1.2 57.3 0 0 NA Ex 4 **96C
Comp Comp Ex 5 80:20 UC N/A 0.8 57.3 3.94 1.20 0.36 Ex 5 **97C 39C
Comp Ex 2 0:1 250 4 0 57.3 0.26 0.08 NA 98C 40C Comp Ex 6 1:0 UC
N/A 1 57.3 3.62 1.13 0.30 99C 40C Comp Ex 6 1:0 250 4 0.5 57.3 4.21
1.32 0.37 100C 40C Comp Ex 6 1:0 250 4 0.3 57.3 3.55 1.11 0.38 101
33 Ex 3 80:20 250 4 0 57.3 9.98 3.12 0.43 102 33 Ex 3 80:20 250 4
0.3 57.3 11.05 3.45 0.41 103 34 Ex 3 50:50 250 4 0 57.3 14.69 4.59
0.41 104 34 Ex 3 50:50 250 4 0 38.2 8.11 3.81 0.37 105* 36 Ex 5
65:35 250 4 0 57.3 5.89 1.84 .37 106* 37 Ex 5 65:35 250 4 0 57.3
7.74 2.44 .37 107 33 Ex 9 80:20 250 4 0 57.3 9.47 2.98 .43 UC =
uncalcined N/A--not applicable *= Tray Dried **= Non-Agglomerated
physical blend
[0326]
9 TABLE X Clay (Wt. % in Polymer Particle Size Distribution
(Microns) Support- 0-75 75-150 150-250 250-500 500-850 850-2000
>2000 Run No. Activator) (Wt. %) (Wt. %) (Wt. %) (Wt. %) (Wt. %)
(Wt. %) (Wt. %) +45* 20 0 0 0 12.3 70 17.2 0.1 56* 20 0 0 0 14.4 80
4.2 0 67* 35 0 0 0 2.6 29 68.9 0 94C 100 7.0 19.6 23.4 31.2 11.4
3.8 7.2 96C*** 20 7.7 32.3 34 15 7.3 4.5 2 105** 35 3.2 4.8 8 24.2
41.5 18.2 0 106** 35 4.5 5.8 8.7 23.5 37.2 20.4 0 *= Spray Dried
**= Tray Dried ***= Physical Mixture += Polymer has Mw = 348,200,
Mn = 34,700 and Mw/Mn = 10.0
[0327]
10TABLE XI AlBu.sub.3 (mmol/g) 1.2 Fe = 38.2 Fe = 52.3 Fe = 76.3 Fe
= 95.4 .mu.mol .mu.mol .mu.mol .mu.mol RT 150.degree. C.
500.degree. C. 800.degree. C. 0.8 Fe = 52.3 Fe = 38.2 Fe = 95.4 Fe
= 76.3 .mu.mol .mu.mol .mu.mol .mu.mol 800.degree. C. 500.degree.
C. 150.degree. C. RT 0.4 Fe = 76.3 Fe = 95.4 Fe = 38.2 Fe = 52.3
.mu.mol .mu.mol .mu.mol .mu.mol 150.degree. C. RT 800.degree. C.
500.degree. C. 0.1 Fe = 95.4 Fe = 76.3 Fe = 52.3 Fe = 38.2 .mu.mol
.mu.mol .mu.mol .mu.mol 500.degree. C. 800.degree. C. RT
150.degree. C. 20% Clay 35% Clay 50% Clay 75% Clay
[0328] The principles, preferred embodiments, and modes of
operation of the present invention have been described in the
foregoing specification. The invention which is intended to be
protected herein, however, is not to be construed as limited to the
particular forms disclosed, since these are to be regarded as
illustrative rather than restrictive. Variations and changes may be
made by those skilled in the art, without departing from the spirit
of the invention.
* * * * *