U.S. patent application number 10/382742 was filed with the patent office on 2003-09-11 for metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation.
Invention is credited to Carney, Michael John, Denton, Dean Alexander, Shih, Keng-Yu.
Application Number | 20030171207 10/382742 |
Document ID | / |
Family ID | 23714362 |
Filed Date | 2003-09-11 |
United States Patent
Application |
20030171207 |
Kind Code |
A1 |
Shih, Keng-Yu ; et
al. |
September 11, 2003 |
Metallocene and constrained geometry 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 metallocene or constrained geometry
pre-catalyst transition metal compound, (e.g.,
di-(n-butylcyclopentadienyl) zirconium 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) ; Denton, Dean Alexander; (Baltimore, MD)
; Carney, Michael John; (Eldersburg, MD) |
Correspondence
Address: |
Robert A. Maggio
W. R. Grace & Co.-Conn.
Patent Dept.
7500 Grace Drive
Columbia
MD
21044-4098
US
|
Family ID: |
23714362 |
Appl. No.: |
10/382742 |
Filed: |
March 6, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10382742 |
Mar 6, 2003 |
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09432008 |
Nov 1, 1999 |
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6559090 |
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Current U.S.
Class: |
502/102 ;
502/103; 502/114; 502/117; 502/118 |
Current CPC
Class: |
C08F 4/65922 20130101;
C08F 4/6592 20130101; C08F 4/65912 20130101; C08F 10/02 20130101;
C08F 10/02 20130101; C08F 4/65916 20130101; C08F 4/025 20130101;
C08F 2500/24 20130101; C08F 2500/18 20130101; C08F 110/02 20130101;
C08F 10/02 20130101; C08F 110/02 20130101 |
Class at
Publication: |
502/102 ;
502/103; 502/117; 502/118; 502/114 |
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 metallocene or
constrained geometry, 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, 4
or the Lanthanide metals, of the Periodic Table of Elements; 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, 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 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 1:1 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.2).sub.s (VIII) 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 hydrocarbyl 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
2000:1.
3. The catalyst system of claim 1 wherein the pre-catalyst is at
least one transition metal compound represented by the formula:
Cp*.sub.qZL.sup.1.sub.mL.sup.2.sub.nL.sup.3.sub.p (1) wherein: each
Cp* independently represents anionic, delocalized, .pi.-bonded,
cyclopentadienyl group, substituted cyclopentadienyl group,
cyclopentadienyl derivative group, or substituted cyclopentadienyl
derivative group, with two Cp* groups being optionally joined
together by a moiety having up to 30 non-hydrogen atoms thereby
forming a bridged structure; Z represents at least one transition
metal selected from Ti, Zr, and Hf in the +2 oxidation state;
L.sup.1 is an optional divalent substituent of up to 50
non-hydrogen atoms that, when present, together with Cp* forms a
metallocycle with Z; L.sup.2 each occurrence independently
represents an optional neutral Lewis base having up to 20
non-hydrogen atoms, or L.sup.2 can represent a second transition
metal compound of the same type as formula I such that two metal Z
centers are bridged by one or two L.sup.3 groups; L.sup.3 each
occurrence independently represents a monovalent, anionic moiety
having up to 50 non-hydrogen atoms, or a neutral, conjugated or
non-conjugated diene .pi.-bonded to Z, with two L.sup.3 groups
together optionally constituting a divalent anionic moiety having
both valences bound to Z, and with L.sup.3 and L.sup.2 together
optionally constituting a moiety both covalently bound to Z and
coordinated thereto by a Lewis base functionality; "q" is an
integer of 1 or 2 and represents the number of Cp* groups bound to
Z; m is an integer of 0 or 1 and represents the number of L.sup.1
groups bound to Z; n and p are independently integers of from 0 to
3; the sum of q+m+p being equal to the formal oxidation state of Z;
and provided that where any one of L.sup.1 to L.sup.3 is
hydrocarbyl containing, such L group is not Cp*.
4. The catalyst system of claim 2 wherein the pre-catalyst is a
metallocene transition metal compound represented by at least one
of the formulae: 4wherein: Cp*, Z and each L.sup.3 are as defined
in claim 2; R.sup.1 each occurrence independently represents
hydrogen, silyl, hydrocarbyl, hydrocarbyloxy and mixtures thereof
having up to 30 carbon or silicon atoms; and x is an integer of 1
to 8.
5. The catalyst system of claim 2 wherein the pre-catalyst is a
constrained geometry transition metal compound represented by the
formula: 5wherein: Z, CP*, and L are as defined in claim 2; G is a
divalent moiety comprising oxygen, boron, or a member of Group 14
of the Periodic Table of Elements; and Y is a linking group
comprising nitrogen, phosphorous, oxygen or sulfur, with G and Y
together optionally constituting a fused ring structure.
6. The catalyst system of any one of claims 3, 4 and 5, wherein Cp*
is selected from cyclopentadienyl, indenyl, fluorenyl,
tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl,
pentadienyl, cyclohexadienyl, dihydroanthracenyl,
hexahydroanthracenyl, and decahydroanthracenyl.
7. The catalyst system of claim 6 wherein Cp* is substituted with
at least one C.sub.1 to C.sub.10 hydrocarbyl group.
8. The catalyst system of any one of claims 4 and 5 wherein at
least one L.sup.3 group is selected from halogen, hydrocarbyl and
mixtures.
9. The catalyst system of any one of claims 4 and 5 wherein 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 4 and 5 wherein
L.sup.3 is selected from halogen or hydrogen, and the catalyst
system further comprises at least one organometallic compound
represented by the formula: M(R.sup.2).sub.s wherein M is aluminum,
R.sup.2 is hydrocarbyl, and "s" is 3, intimately associated wraith
the 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 1000:1.
11. The catalyst system of claim 11 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 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 5:1 to about 200:1.
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 10:1 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 20:1 to about 60:1.
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
metallocene, or constrained geometry, 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, 4
or the Lanthanlide metals, of the Periodic Table of Elements; (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 1:1 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.2).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.2 independently
represents at least one of hydrogen, halogen, or hydrocarbyl 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 2000:1.
19. The catalyst system of claim 17 wherein the pre-catalyst is at
least one transition metal compound represented by the formula:
Cp*.sub.qZL.sup.1.sub.mL.sup.2.sub.nL.sup.3.sub.p wherein: each Cp*
independently represents anionic, delocalized, .pi.-bonded,
cyclopentadienyl group, substituted cyclopentadienyl group,
cyclopentadienyl derivative group, or substituted cyclopentadienyl
derivative group, with two Cp* groups being optionally joined
together by a moiety having up to 30 non-hydrogen atoms thereby
forming a bridged structure; Z represents at least one transition
metal selected from Ti, Zr, and Hf in the +2 oxidation state;
L.sup.1 is an optional, divalent substituent of up to 50
non-hydrogen atoms that, when present, together with Cp* forms a
metallocycle with Z; L.sup.2 each occurrence independently
represents an optional neutral Lewis base having up to 20
non-hydrogen atoms, or L.sup.2 can represent a second transition
metal compound of the same type as formula I such that two metal Z
centers are bridged by one or two L.sup.3 groups; L.sup.3 each
occurrence independently represents a monovalent, anionic moiety
having up to 50 non-hydrogen atoms, a neutral, conjugated or
non-conjugated diene .pi.-bonded to Z, with two L.sup.3 groups
together optionally constituting a divalent anionic moiety having
both valences bound to Z, and with L.sup.3 and L.sup.2 together
optionally constituting a moiety both covalently bound to Z and
coordinated thereto by a Lewis base functionality; "q" is an
integer of 1 or 2 and represents the number of Cp* groups bound to
Z; m is an integer of 0 or 1 and represents the number of L.sup.3
groups bound to Z; n and p are independently integers of from 0 to
3; the sum of q+m+p being equal to the formal oxidation state of Z;
and provided that where any one of L.sup.1 to L.sup.3 is
hydrocarbyl containing, such L group is not Cp*.
20. The catalyst system of claim 17 wherein the pre-catalyst is at
least one transition metal compound represented by the formulae:
6wherein: Cp*, Z and each L.sup.3 are as defined in claim 2;
R.sup.1 each occurrence independently represents hydrogen, silyl,
hydrocarbyl, hydrocarbyloxy and mixtures thereof having up to 30
carbon or silicon atoms; and x is an integer of 1 to 8.
21. The catalyst system of claim 20 wherein the pre-catalyst is at
least one transition metal compound represented by the formula:
7wherein: Z, Cp* and L.sup.3 are as defined in claim 2; G is a
divalent moiety comprising oxygen, boron, or a member of Group 14
of the Periodic Table of Elements; and Y is a linking group
comprising nitrogen, phosphorous, oxygen or sulfur, with G and Y
together optionally constituting a fused ring structure.
22. The catalyst system of any one of claims 19, 20 and 21 wherein
Cp* is selected from cyclopentadienyl, indenyl, fluorenyl,
tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl,
pentadienyl, cyclohexadienyl, dihydroanthracenyl,
hexahydroanthracenyl, and decahydroanthracenyl.
23. The catalyst system of claim 18 wherein M is aluminum, "s" is
3, and R.sup.2 is C.sub.1 to C.sub.24 alkyl.
24. The catalyst system of any one of claims 20 and 21 wherein at
least one L.sup.3 of the pre-catalyst is hydrocarbyl.
25. The catalyst system of claim 24 wherein Cp* is substituted with
at least one C.sub.1 to C.sub.10 hydrocarbyl group.
26. The catalyst system of any one of claims 20 and 21 wherein at
least one L.sup.3 group is selected from halogen, hydrocarbyl and
mixtures.
27. The catalyst system of any one of claims 20 and 21 wherein each
L.sup.3 is independently selected from chlorine, bromine, iodine,
or C.sub.1-C.sub.8 alkyl.
28. 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.2).sub.s (VIII) wherein M represents at least one element
of Group 1, 2, or 13 of the Periodic Table, tin or zinc, and each
R.sup.2 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 1000:1.
29. 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.2).sub.s (VIII) 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 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 1000:1.
30. The catalyst system of claim 21 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.2).sub.s (VIII) 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 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 1000:1.
31. The catalyst system of claim 28 wherein M is aluminum, R.sup.2
is alkyl or alkoxy, "s" is 3, Z is selected from at least one of
Zr, Ti, and Hf, and L.sup.3 is halogen.
32. The catalyst system of claim 29 wherein M is aluminum, R.sup.2
is alkyl or alkoxy, "s" is 3, Z is selected from at least one of
Zr, Ti, and Hf, and L.sup.3 is halogen.
33. The catalyst system of claim 30 wherein M is aluminum, R.sup.2
is alkyl or alkoxy, "s" is 3, Z is selected from at least one of
Zr, Ti, and Hf, and L.sup.3 is halogen.
34. 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.
35. The catalyst system of claim 34 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 5:1 to about 200:1.
36. The catalyst system of claim 35 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 10:1 to
about 100:1.
37. The catalyst system of claim 17 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 20:1 to about 60:1.
38. 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.
39. The catalyst system of claim 38 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.
40. A process for preparing a catalyst system capable of
polymerizing at least one olefin 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 metallocene, or constrained geometry
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,
4 or Lanthamide metals, of the Periodic Table of Elements; (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 1:1 or to
about 500:1, and to cause at least one of absorption and adsorption
of the pre-catalyst by the support-activator.
41. The process of claim 40 further comprising including at least
one organometallic compound in the inert liquid hydrocarbon of step
III represented by the structure formula: M(R.sup.2).sub.s (VIII)
wherein M represents at least one element of Groups 1, 2, or 13 of
the Periodic Table, tin or zinc, and each R.sup.2 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 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 2000:1.
42. The process of claim 40 wherein the pre-catalyst is a
transition metal compound represented by the formula:
Cp*.sub.qZL.sup.1.sub.mZ.sup.2.sub.n- L.sup.3.sub.p wherein: each
Cp* independently represents anionic, delocalized, .pi.-bonded,
cyclopentadienyl group, substituted cyclopentadienyl group,
cyclopentadienyl derivative group, or substituted cyclopentadienyl
derivative group, with two Cp* groups being optionally joined
together by a moiety having up to 30 non-hydrogen atoms thereby
forming a bridged structure; Z represents at least one transition
metal selected from Ti, Zr, and Hf in the +2 oxidation state;
L.sup.1 is an optional, divalent substituent of up to 50
non-hydrogen atoms that, when present, together with Cp* forms a
metallocycle with Z; L.sup.2 each occurrence independently
represents an optional neutral Lewis base having up to 20
non-hydrogen atoms or L.sup.2 can represent a second transition
metal compound of the same type as formula I such that two metal Z
centers are bridged by one or two L.sup.3 groups; L.sup.3 each
occurrence independently represents a monovalent, anionic moiety
having up to 50 non-hydrogen atoms, a neutral, conjugated or
non-conjugated diene .pi.-bonded to Z, with two L.sup.3 groups
together optionally constituting a divalent anionic moiety having
both valences bound to Z, and with L.sup.3 and L.sup.2 together
optionally constituting a moiety both covalently bound to Z and
coordinated thereto by a Lewis base functionality; "q" is an
integer of 1 or 2 and represents the number of Cp* groups bound to
Z; m is an integer of 0 or 1 and represents the number of L.sup.1
groups bound to Z; n and p are independently integers of from 0 to
3; the sum of q+m+p being equal to the formal oxidation state of Z;
and provided that where any one of L.sup.1 to L.sup.3 is
hydrocarbyl containing, such L group is not Cp*.
43. The process of claim 42 wherein the pre-catalyst is a
transition metal compound represented by the formulae: 8wherein:
Cp*, Z and each L.sup.3 are as defined in claim 42; R.sup.1 each
occurrence independently represents hydrogen, silyl, hydrocarbyl,
hydrocarbyloxy and mixtures thereof having up to 30 carbon or
silicon atoms; and x is an integer of 1 to 8.
44. The process of claim 42 wherein the pre-catalyst is a
transition metal compound represented by the formula: 9wherein: Z,
Cp* and L.sup.3 are as defined in claim 42; G is a divalent moiety
comprising oxygen, boron, or a member of Group 14 of the Periodic
Table of Elements; and Y is a linking group comprising nitrogen,
phosphorous, oxygen or sulfur, with G and Y together optionally
constituting a fused ring structure.
45. The process of any one of claims 42, 43 and 44 wherein Cp* is
selected from cyclopentadienyl, indenyl, fluorenyl,
tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl,
pentadienyl, cyclohexadienyl, dihydroanthracenyl,
hexahydroanthracenyl, and decahydroanthracenyl.
46. The process of claim 41 wherein M is aluminum, "s" is 3, and
R.sup.2 is C.sub.1 to C.sub.24 alkyl.
47. The process of any one of claims 42, 43 and 44 wherein Cp* is
selected from cyclopentadienyl, indenyl, fluorenyl,
tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl,
pentadienyl, cyclohexadienyl, dihydroanthracenyl,
hexahydroanthracenyl, and decahydroanthracenyl.
48. The process of any one of claims 42, 43 and 44 wherein Cp* is
substituted with at least one C.sub.1 to C.sub.10 hydrocarbyl
group.
49. The process of any one of claims 43 and 44 wherein at least one
L.sup.3 group is selected from halogen, hydrocarbyl and
mixtures.
50. The process of any one of claims 43 and 44 wherein each L.sup.3
is independently selected from chlorine, bromine, iodine, or
C.sub.1-C.sub.8 alkyl.
51. The process of claim 42 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.2).sub.s (VIII) 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 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 0.1:1 to about
1000:1.
52. The process of claim 43 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.2).sub.s (VIII) 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 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 1000:1.
53. The process of claim 44 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.2).sub.s (VIII) 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 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 1000:1.
54. The process of claim 51 wherein M is aluminum, R.sup.2 is alkyl
or alkoxy, "s" is 3, Z is selected from at least one of Zr and Ti,
and L.sup.3 is halogen.
55. The process of claim 52 wherein M is aluminum, R.sup.2 is alkyl
or alkoxy, "s" is 3, Z is selected from at least one of Zr or Ti,
and L.sup.3 is halogen.
56. The process of claim 53 wherein M is aluminum, R.sup.2 is alkyl
or alkoxy, "s" is 3, Z is selected from at least one of Zr or Ti,
and L.sup.3 is halogen.
57. The process of claim 40 wherein the support-activator is at
least one of clay or clay mineral having a negative charge below
0.
58. The process of claim 57 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 5:1 to about 200:1.
59. The process of claim 58 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 20:1 to about 60:1.
60. The process of claim 40 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 20:1 to about 60:1.
61. The process of any one of claims 42, 43 and 44 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.
62. The process of claim 61 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.
63. The process of claim 40 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.
64. The process of claim 40 wherein the liquid hydrocarbon is
separated from the mixture of support-activator and
pre-catalyst.
65. The process of claim 41 wherein the liquid hydrocarbon is
separated from the mixture of support-activator, pre-catalyst and
organometallic compound.
66. The process of claim 41 wherein the organometallic compound is
contacted with pre-catalyst prior to contract with the
support-activator.
67. The process of claim 40 further comprising including in the
inert liquid hydrocarbon of step III, at least one organometallic
compound represented by the structural formula: M(R.sup.2).sub.s
(VIII) wherein M represents at least one element of Groups 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
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 100:1.
68. The process of claim 67 wherein said ratio is from about 0.1:1
to about 20:1.
69. The process of claim 40 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.
70. The process of claim 40 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
metallocene and/or constrained geometry 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 diethylaluminium 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 are neutral metallocenes
which have been activated, e.g., ionized, by an activator such that
the active catalyst species incorporates 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 5,643,847; and EP 426 637 and EP 426 638, the disclosures of
which are incorporated herein by reference.
[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.
Constrained geometry catalysts are disclosed in U.S. Pat. Nos.
5,064,802 and 5,321,106. Constrained geometry catalysts can also be
employed in neutral or cationic form and use methylalumoxane or
ionization activators respectively in the same fashion as
metallocenes.
[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
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., methylalumoxane (MAO)) (characterized
as operating through a hydrocarbyl abstraction mechanism). Such
activators or cocatalysts are pyrophoric, 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 and require
pyrophoric reagents to make the same. 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.
[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.
[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 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 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.
[0022] 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
[0023] 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.
[0024] 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.
[0025] There has also been a particular need to discover catalyst
systems which are adapted to more readily cope with the propensity
to deactivate and/or are less hazardous in use.
[0026] The present invention was developed in response to these
searches.
[0027] 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.
[0028] U.S. Pat. No. 5,633,419 discloses the use of spray dried
silica gel agglomerates as supports for Ziegler-Natta catalyst
systems.
[0029] 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 5,403,809; and EP
490 226 for similar disclosures.
[0030] 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.
[0031] 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.
[0032] EP 426,638 discloses a process for polymerizing olefins
which comprises mixing an aluminum alkyl with the olefin to be
polymerized, preparing the metallocene catalyst, and mixing the
catalyst with the aluminum alkyl-olefin mixture without a
methylaluminoxane co-catalyst. The metallocene catalyst is an ion
pair formed from a neutral metallocene compound and an ionizing
compound such as triphenylcarbenium tetrakis (pentafluorophenyl)
borate.
[0033] U.S. Pat. No. 5,238,892 discloses the use of undehydrated
silica as a support for metallocene and trialkylaluminum
compounds.
[0034] 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).
[0035] 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.
[0036] 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.
[0037] 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. Tile 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.
[0038] 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, tropynium, 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.
[0039] 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 mineral 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.
[0040] 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.
[0041] 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.
[0042] 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 from 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.
[0043] 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.
[0044] 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.)
[0045] 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, enidellite, 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.
[0046] Additional patents which disclose intercalated clays are
U.S. Pat. Nos. 4,629,712 and 4,637,992. Additional patents which
disclose pillared clays include U.S. Pat. Nos. 4,995,964 and
5,250,277.
[0047] A paper presented at the MetCon '99 Polymers in Transition
Conference in Houston, Texas, 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 Yuinito 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 to 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.
[0048] PCT International Application No. PCT/US96/17140,
corresponding to U.S. Serial 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.
[0049] 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 montimorillonite clay as
a support but polymer morphology is not disclosed for these
examples.
[0050] 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.
[0051] PCT International Application No. PCT/US98/00316 discloses a
process for polymerizing propylene using catalysts similar to the
above discussed PCT-23556 application.
[0052] 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.
[0053] U.S. Ser. No. ______ (Docket W-9459-01) filed on an even
date herewith by Keng-Yti Shill 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
[0054] 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 metallocene and constrained geometry
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 such as
borane/borate, and MAO activators which are expensive, and
introduce added complexity to the system. In contrast, the
support-activator is inexpensive, environmentally friendly, and
easy to manufacture.
[0055] 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 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.
[0056] 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 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.
[0057] 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.
[0058] 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:
[0059] (I) as a pre-catalyst, at least one metallocene or
constrained geometry, 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 (II)(B), wherein the transition
metal is at least one member selected from Groups 3, 4 or the
Lanthanide metals, of the Periodic Table of Elements; in intimate
contact with
[0060] (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,
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 polymerizing ethylene monomer,
expressed as Kg of 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 (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 1:1 to about 500:1.
[0061] In another aspect of the present invention, there is
provided a process for making the above catalyst system which
comprises:
[0062] (I) agglomerating to form a support-activator:
[0063] (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
[0064] (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;
[0065] (II) providing as a pre-catalyst, at least one metallocene,
or constrained geometry 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, 4 or Lanthanide metals, of the
Periodic Table of Elements;
[0066] (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 1:1 to about 500:1, and to cause at least one of absorption
and adsorption of the pre-catalyst by the support-activator.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0067] As indicated above, the present invention employs a
metallocene and/or 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.
[0068] More specifically, the transition metal pre-catalyst can be
at least one metallocene compound, at least one constrained
geometry 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.
[0069] The pre-catalyst compounds can be generically represented by
the formula:
Cp*qZL.sup.1.sub.mL.sup.2.sub.nL.sup.3.sub.p or a dimer thereof
(I)
[0070] wherein:
[0071] Cp* represents an anionic, delocalized, .pi.-bonded
cyclopentadienyl group, or substituted cyclopentadienyl group, as
well as a substituted or unsubstituted derivative of a
cyclopentadienyl group, that is bound to Z, containing up to 50
non-hydrogen atoms, optionally two Cp* groups may be joined
together by a moiety having up to 30 non-hydrogen atoms in its
structure thereby forming a bridged structures and further
optionally one Cp* may be bound to L.sup.1;
[0072] Z is a metal of Group 3 (Sc, Y, La, Ac), 4 (Ti, Zr, Hf), or
the Lanthanide metals (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er
Tm Yb, Lu), preferably Group 4 (Ti, Zr, Hf), of the Periodic Table
of the Elements in the +2, +3 or +4 formal oxidation state, counter
balancing the anionic Cp* and L group(s);
[0073] L.sup.1 is an optional, divalent substituent of up to 50
non-hydrogen atoms that, when present, together with Cp* forms a
metallocycle with Z;
[0074] L.sup.2 each occurrence independently represents an optional
neutral Lewis base having up to 20 non-hydrogen atoms;
[0075] L.sup.3 each occurrence independently represents a
monovalent, anionic moiety having up to 50 non-hydrogen atoms,
typically a hydrocarbon-based radical or group, optionally, two
L.sup.3 groups together may constitute a divalent anionic moiety
having both valences bound, preferably covalently bound, to Z, or a
neutral, conjugated or non-conjugated diene that is .pi.-bonded to
Z (whereupon Z is in the +2 oxidation state), or further optionally
one or more L.sup.3 and one or more L.sup.2 groups may be bonded
together thereby constituting a moiety that is both covalently
bound to Z and coordinated thereto by means of Lewis base
functionality;
[0076] q is 1 or 2;
[0077] m is an integer of 0 or 1;
[0078] n is an integer of 0 to 3;
[0079] p is an integer from 0 to 3; and
[0080] the sum of q+m+p is equal to the formal oxidation state of
Z; and
[0081] provided that Nowhere any one of L.sup.1 to L.sup.3 groups
is hydrocarbyl containing, such L group is not Cp*.
[0082] Examples of suitable anionic, delocalized .pi.-bonded
cyclopentadienyl derivative groups constituting Cp* include
indenyl, fluorenyl, tetrahydroidenyl, tetrahydrofluorenyl,
octahydrofluorenyl, cyclopentadienyl, cyclohexadienyl,
dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenyl
groups, as well as C.sub.1-10 hydrocarbyl-substituted derivatives
thereof.
[0083] Preferred Cp* groups are cyclopentadienyl,
pentamethylcyclopentadie- nyl, tetramethylcyclopentadienyl,
1,3-dimethylcyclopentadienyl, n-butylcyclopentadienyl, indenyl,
2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and
2-methyl-4-phenylindenyl.
[0084] Each carbon in the Cp* ring may independently be substituted
with, a radical, selected from halogen, hydrocarbyl,
halohydrocarbyl and hydrocarbyl substituted metalloid radicals
wherein the metalloid is selected from Group 14 (C, Si, Ge, Sn, Pb)
of the Periodic Table of the Elements. Included within the term
`hydrocarbyl` are C.sub.1-20 straight, branched and cyclic alkyl
radicals, C.sub.6-20 aromatic radicals, C.sub.7-20
alkyl-substituted aromatic radicals, and C.sub.7-20
aryl-substituted alkyl radicals. In addition two or more such
radicals may together form a fused ring system or a hydrogenated
fused ring system. Suitable hydrocarbyl-substituted organometalloid
radicals include mono-, di- and trisubstituted organometalloid
radicals of Group 14 elements wherein each of the hydrocarbyl
groups contains from 1 to 20 carbon atoms. Examples of suitable
hydrocarbyl-substituted organometalloid radicals include
trimethylsilyl, triethylsilyl, ethyldimethylsilyl,
methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.
The recitation `metalloid`, as used herein, includes nonmetals such
as boron, phosphorus and the like which exhibit semi-metallic
characteristics.
[0085] Representative examples of suitable L.sup.2 groups include
diethylether, tetrahydrofuran, dimethylaniline, aniline,
trimethylphosphine, and n-butylamine. L.sup.2 can also represent a
second transition metal compound of the same type as Formulas I,
III or IV such that two metal centers, e.g., Z and Z', are bridged
by one or two L.sup.3 groups. Such dual metal center bridged
structures are described in PCT/US91/4390.
[0086] Preferred pre-catalysts represented by Formula I include
those containing either one or two Cp* groups. The latter
pre-catalysts include those containing a bridging group linking the
two Cp* groups. Preferred bridging groups are those corresponding
to the Formula:
(E(R.sup.1).sub.2).sub.x (II)
[0087] wherein E is silicon or carbon.
[0088] R.sup.1 independently each occurrence is hydrogen or a group
selected from silyl, hydrocarbyl, hydrocarbyloxy and combination
thereof, said R.sup.1 having up to 30 carbon or silicon atoms, and
x is 1 to 8. Preferably, R.sup.1 independently each occurrence is
methyl, benzyl, tert-butyl or phenyl.
[0089] Examples of the foregoing bis(Cp*) containing pre-catalysts
are compounds corresponding to the formula: 1
[0090] wherein:
[0091] Cp* is as described previously;
[0092] Z is titanium zirconium or hafnium, preferably zirconium or
hafnium,
[0093] in the +2 or +4 formal oxidation state;
[0094] The optional substituents on the cyclopentadienenyl ring in
each occurrence independently can preferably selected from the
group of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and
combinations thereof, said substituents having up to 20
non-hydrogen atoms, or adjacent substituent groups together can
form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl or
germadiyl group) thereby forming a fused ring system; and
[0095] L.sup.3 independently each occurrence is an anionic ligand
group of up to 50 non-hydrogen atoms, or two L.sup.3 groups
together can constitute a divalent anionic ligand group Of Up to 50
non-hydrogen atoms or a conjugated diene having from 4 to 30
non-hydrogen atoms forming a .pi. complex with Z, whereupon Z is in
the +2 formal oxidation state, and R.sup.1, E and x are as
previously defined.
[0096] Thus, each L.sup.3 may be independently, each occurrence
hydride, C.sub.1C.sub.50 hydrocarbon-based radicals including
hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one
or more hydrogen atoms is replaced by an electron-withdrawing
group, such as a halogen atom or alkoxide radical, or
C.sub.1-C.sub.50 hydrocarbyl substituted metalloid radicals,
wherein the metalloid is selected from the Group 4 of the Periodic
Table of Elements, provided that where any L.sup.3 is hydrocarbon
based, such L.sup.3 is different from Cp*. In addition any two
L.sup.3 groups together, may constitute an alkylidene olefin,
acetylene or a cyclometallated hydrocarbyl group.
[0097] 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:
[0098] (1) Hydrocarbon radicals; that is, aliphatic radicals,
aromatic- and alicyclic-substituted radicals, and the like, of the
type known to those skilled in art.
[0099] (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.
[0100] (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,
phosphorus and sulfur. Such hydrocarbon-based radicals may be
bonded to Z through the heteroatom.
[0101] In general, no more than three substituents or heteroatoms,
and preferably no more than one, will be present for each 10 carbon
atoms in the hydrocarbon based radical.
[0102] More specifically, the hydrocarbon based radical or group of
L.sup.3 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.sup.3 groups
are independently selected from halo, hydrocarbyl, and substituted
hydrocarbyl radicals. The hydrocarbon based radical may typically
contain from 1 to about 50 carbon atoms, preferably from 1 to about
12 carbon atoms and the substituent group is preferably a halogen
atom.
[0103] Exemplary hydrocarbyl radicals for L.sup.3 are methyl,
ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl,
octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with
methyl being preferred. Exemplary substituted hydrocarbyl radicals
for L.sup.3 include trifluoromethyl, pentafluorphenyl,
trimethylsilylmethyl, and trimethoxysilylmethyl and the like.
Exemplary hydrocarbyl substituted metalloid radicals for L.sup.3
include trimethylsilyl, trimetliylgermyl, triphenylsilyl, and the
like. Exemplary alkyldiene radicals for two L.sup.3 groups together
include methylidene, ethylidene and propylidelle.
[0104] The foregoing metal complexes are especially suited for the
preparation of polymers having stereoregular molecular structure.
In such capacity it is preferred that the complex possess Cs
symmetry or possess a chiral, stereorigid structure. Examples of
the first type are compounds possessing different delocalized
.pi.-bonded systems, such as one cyclopentadienyl group and one
fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were
disclosed for preparation of, syndiotactic olefin polymers in Ewen,
et al. J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral
structures include bis-indenyl complexes. Similar systems based on
Ti(IV) or Zr(IV) were disclosed for preparation of isotactic olefin
polymers in Wild et al., J. Organomet. Chem, 232, 233-47
(1982).
[0105] Exemplary bridged ligands containing two .pi.-bonded groups
are: (dimethylsilyl-bis-cyclopentadienyl),
(dimethylsilyl-bismethylcyclopentad- ienyl),
(dimethylsilyl-bis-ethylcyclopentadienyl, (dimethylsilyl-bis-t-bul-
tylcyclopentadienyl),
(dimethylsilyl-bistetramethylcyclopentadienyl),
(dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroidenyl),
(dimethylsilyl-bis-fluorenyl),
(dimethylsilyl-bis-tetrahydrofluorenyl),
(dimethylsilyl-bis-2-methyl-4-phenylindenyl),
(dimethylsilyl-bis-2-methyl- indenyl),
(dimethylsilylcyclopentadienyl-fluorenyl),
(1,1,2,2-tetramethyl-1,2-disilyl-biscyclopentadienyl),
(1,2-bis(cyclopentadienyl))ethane, and
(isopropylidene-cyclopentadienyl-f- luorenyl).
[0106] Preferred L.sup.3 groups are selected from hydride,
hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl,
silylhydrocarbyl and aminohydrocarbyl groups, or two L.sup.3 groups
together can constitute a divalent derivative of a conjugated diene
or a neutral, .pi.-bonded, conjugated diene. Most preferred L.sup.3
groups are C.sub.1-20 hydrocarbyl groups.
[0107] Examples of preferred pre-catalyst compounds of Formula III
and IV include compounds wherein the Cp* group is selected from
cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and
octahydrofluorenyl; the substituents on the foregoing Cp* groups
each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl,
hexyl (including isomers), norbornyl, benzyl, phenyl, etc.; and
L.sup.3 is selected from methyl, neopentyl, trimethylsilyl,
nor-bornyl, benzyl, methylbenzyl, and phenyl; q is 2, and m and n
are zero.
[0108] A further class of metal complexes utilized in the present
invention correspond to the formula:
Cp*.sub.qZL.sup.1.sub.mL.sup.2.sub.nL.sup.3.sub.p or a dimer
thereof (V)
[0109] wherein:
[0110] Cp* is as defined previously;
[0111] Z is a metal of Group 4 of the Periodic Table of the
Elements in the +2.
[0112] +3 or +4 formal oxidation state;
[0113] L.sup.1 is a divalent substituent of up to 50 non-hydrogen
atoms that together with Cp* forms a metallocycle with Z;
[0114] L.sup.2 is an optional neutral Lewis base ligand having up
to 20 non-hydrogen atoms;
[0115] L.sup.3 each occurrence is a monovalent, anionic moiety
having up to 20 non-hydrogen atoms, optionally two L.sup.3 groups
together may form a divalent anionic moiety having both valences
bound to Z or a neutral C.sub.5-30 conjugated diene, and further
optionally L.sup.2 and L.sup.3 may be bonded together thereby
forming a moiety that is both covalently bound to Z and coordinated
thereto by means of Lewis base functionality;
[0116] q is 1 or 2;
[0117] m is 1;
[0118] n is a number from 0 to 3;
[0119] p is a number from 1 to 2; and
[0120] the sum of q+m+p is equal to the formal oxidation state of
Z.
[0121] Preferred divalent L.sup.1 substituents include groups
containing up to 30 non-hydrogen atoms comprising at least one atom
that is oxygen, sulfur, boron or a member of Group 14 of the
Periodic Table of the Elements directly attached to the Cp* group,
and a different atom, selected from the group consisting of
nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to
Z.
[0122] As indicated above, an alternative class of pre-catalysts is
constrained geometry catalyst. By use of the term "constrained
geometry" herein is meant that the metal atom is forced to greater
exposure of the active metal site because of one or more
substituents on the Cp* group forming a portion of a ring structure
wherein the metal is both bonded to an adjacent covalent moiety and
is held in association with the Cp* group through .eta..sup.5
bonding interaction. It is understood that each respective bond
between the metal atom and the constituent atoms of the Cp* group
need not be equivalent. That is, the metal may be symetrically or
unsymetrically .pi.-bound to the Cp* group.
[0123] The geometry of the active metal site is typically such that
the centroid of the Cp* group may be defined as the average of the
respective X, Y, and Z coordinates of the atomic centers forming
the Cp* group. The angle, .theta., formed at the metal center
between the centroid of the Cp* group and each other ligand of the
metal complex may be easily calculated by standard techniques of
single crystal X-ray diffraction. Each of these angles may increase
or decrease depending on the molecular structure of the constrained
geometry metal complex. Those complexes, wherein one or more of the
angles, .theta., is less than in a similar, comparative complex
differing only in the fact that the constrain-inducing substituent
is replaced by hydrogen, have a constrained geometry. Preferably
one or more of the above angles, .theta., decrease by at least 5%,
more preferably 7.5% compared to the comparative complex.
Preferably, the average value of all bond angles, .theta., is also
less than in the comparative complex. Monocyclopentadienyl metal
coordination complexes of Group 4 or lanthanide metals according to
the present invention have constrained geometry such that typically
the smallest angle, .theta., is less than 115 degree(s), more
preferably less than 110 degree(s), most preferably less than 105
degree(s).
[0124] Typical, constrained geometry pr-e-catalysts can be
represented by the Formula: 2
[0125] wherein:
[0126] Z, Cp*, and L.sup.3 are as defined previously;
[0127] G is a divalent moiety comprising oxygen, boron, or a member
of Group 14 of the Periodic Table of Elements, such as,
Si(R.sup.1).sub.2, C(R.sup.1).sub.2,
Si(R.sup.1).sub.2--Si(R.sup.1).sub.2,
C(R.sup.1).sub.2--C(R.sup.1).sub.2,
Si(R.sup.1).sub.2--C(R.sup.1).sub.2, C R.sup.1.dbd.CR.sup.1, and
Ge(R.sup.1).sub.2;
[0128] Y is a linking group comprising nitrogen, phosphorus, oxygen
or sulfur, such as --O--, --S--, --N R.sup.1--, PR.sup.1-- or
optionally G and Y together can constitute a user ring structure,
the combination of G and Y constituting an L.sup.1 group of Formula
I; and
[0129] R.sup.1 is as described previously.
[0130] A further subset of constrained geometry pre-catalysts are
amidosilane or amidoalkanediyl-compounds corresponding to the
formula: 3
[0131] wherein:
[0132] Z is as previously described;
[0133] R.sup.2 each occurrence is independently selected from the
group of hydrogen, silyl, alkyl, aryl and combinations thereof
having up to 10 carbon or silicon atoms;
[0134] E is silicon or carbon; and
[0135] L.sup.3 independently each occurrence is hydride, alkyl, or
aryl of up to 10 carbons;
[0136] m is an integer of 1 or 2; and
[0137] n is an integer of 1 or 2 depending on the valence of Z.
[0138] Examples of preferred metal coordination compounds of
Formula VII include compounds wherein the R.sup.2 on the amido
group is methyl, ethyl, propyl, butyl, pentyl, hexyl, (including
isomers), norbornyl, benzyl, phenyl, etc.; the Cp* group is
cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and
octahydrofluorenyl; the substituents on the foregoing
cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl,
propyl, butyl, pentyl, hexyl, (including isomers), norbornyl,
benzyl, phenyl, etc.; and L.sup.3 is methyl, neopentyl,
trimethylsilyl, norbornyl, benzyl, methylbenzyl, phenyl, etc.
[0139] Illustrative pre-catalysts that may be employed in the
practice of the present invention include:
[0140] cyclopentadienyltitaniumtrimethyl,
cyclopentadienyltitaniumtrietliy- l,
cyclopentadienyltitaniumtriisopropyl,
cyclopentadienyltitaniumtriplieny- l,
cyclopentadienyltitaniumiitribenzyl,
cyclopentadienyltitanium-2,4-penta- dieiiyl,
cyclopentadienyltitaniumdimetliylmetlioxide, cycl
opentadienyltitaniumdimethiylclhloride,
pentamethylcyclopentadienyltitanl- iumtrimethyl,
indenyltitaiiiujiitrimethyl, indenyltitani umtriethyl,
ijndenyltitaiiiuiiitripropyl, iindenyltitaniumtriphenyl,
tetrahydroiindenyltitaniumtribeiizyl,
pentametihylcyclopentadienyltitalli- umtri isopropyl,
pentaiiiethylcyclopentadienyltitanliumtribenzyl,
peiitaiiietiiylcyclopeiitadienyltitaiiiuiidiiiiethyliiethloxide,
pentamethlylcyclopentad ienyltitaniiumdimethylchloride,
(q.sup.5-2,4-dimethyl-1,3-pentadien)yl)titaiLiumtrimethyl,
octahydrofl uLorenyltitaiiiu Litrimethyl, tetrahydroinideinyltitai
Ullltlimethyl, tetrallydi-ofluoienyltitanLiuiiitrimethyl,
[0141] (1-diimetliyl-2,3,4.9, 1 0-q-1, 4,5,6,7,
8-hexaliydroniapihtihaleny )titaniumlitrimethyl,
[0142] (1, 1, 2,3-tr(1methyl-2,3,4,9, 10-,-],4,
5,6,7,8-hexallydi-oiiaplit- lialeiyli)titaniuilLtriinethyl,
(tert-butylaiido) (tetraiiietliyl-,5-cyclo-
pentadien)yl)dlimetiylsislaiietitaiium dichloride,
(tert-butylamido) (tetraiiiethyl-,q5-cyclopentadieiyl)d imetliylsi
lanetitanium dimethyl, (tert-butylamiido) (tetrametihyl
5-cyclopentadienyl) - , 2-ethanedjyltitaniumn dimethyl,
(tert-butylaiido) (tetramethyl- 5-indenyl)diiiiethylsi
laLnetitallium dimethyl, (tert-butylamido)
(tetramethyl-5-cyclopentadienyl)dimethylsi lane titanium (111)
2-(diniethylaiiiino)benzyl;
[0143] (tert-butylamiido)
(tetramethyl.sup.5-cyclopentadieiiyl)dlimetihyls- ilanetitanium
(III) allyl, (tert-butylanmido) (tetraniethyl-1.sup.5-cyclop-
entadien)yl)di methyl si lanetitanium (11) 1
,4-diphenyl-1,3-butadiene, (tert-butylamiiido)
(2-methylindenyl)dimethylsilanetitanium (11) 114-diphenyl-
1,3-butadiene, (tert-butylamido)(2-iietiiyllidenyl)di(ethyl-
silanetitanium (IV) 13-butadiene,
(tert-butylamido)(2,3-dimethylidenyl)dim- ethylsilailetitanium (11)
1,4diphenyl- 1,3-butadiene,
(tert-butylaiiiido)(2,3-diiiietliyliideiiyl)diiietli),lsllaletitallium
(I V ) 1 ,3-butadiene,
(tert-butylamildo)(2,3-dimethylinideiiyl)dimetiyl silanetitallium
(11) 1,3-pentadiene., (tert-butylamiiido)(2-iiietihyl
indeiiyl)diiietliyl silanetitanium (11)1 ,3-pentadiene,
(tert-butylamildo)(2-methyli ndenyl)dlimetiiylsilaiietitanium (IV)
diniethyl, (tert-butylamido)(2-iiietliyl-4-plieinyl
indeiiyl)diimethylsilaiietitallium (11)1
,4-dipheiiyl-1,3-butadiene, (tert-butylamido)
(tetramethyl-5-cyclopentadienyl)dimethyl- silanetitanium (IV)
1,3-butadiene, (tert-butylamido) (letraiiiethyl-
5-cyclopentadienyl)dimethyl- silanetitanium (11)
1,4-dibenzyl-1,3-butadie- ne. (tert-butylamido) (tetramethyl-
5-cyclopentadienyl)dinletilyl- silanetitanium (11) 2,4-hexadiene,
(tert-butylamido) (tetramethyl-1 5-cyclopentadienyl)dimethyl-
silanetitanium (11) 3-methyl-1,3-pentadiene,
(tert-butylamido)(2,4-dimethyl-1,3-pentadien-2-yl)dimethyl-
silanetitaniumdimethyl, (tert-butylamido)(1, 1-dimetliyl-2,3,4,9,I,
O-Tl-1,4,5,6,7,8-hexalhydroniaphitlialen-4-yl)
dimethylsilanietitaniuLiid- imethlyl, and (tert-butylamido)(I 1
,,2,3-tetramethyl-2,3,4,9,1
0-n-1,4,5,6,7,8-hexaliydronlaphtlialen-4-yl)
dimetliylsilanetitaniumdimet- hyl.
[0144] Bis(Cp*) containing complexes including bridged complexes
suitable for use in thie present invention include:
[0145] biscyclopentadienylzrconiuLmidiiiiethyl,
biscyclopentadienyltitaiii- uiiidietlyl,
cyclopeiitadienyltitaniumdiJ isopropyl, biscyclopeiitadienyltitan
iuiiidiphenyl, biscycl opeitadienylzirconium dibenzyl,
biscyclopeniditclyltitaiium-2,4-pentadienyi, biscyclopcitad
lenyltitanii ummethlylmethoxide, biscyclopentadienyltitalLi
umiimetliyl chloride,
blslpeiitaiiietliyicyclopeiitadienyltitanliumdimethlyl,
bisiidenyltitanii uLndidlethyl, indeiiy fluorenyltitaiii
umdietiiyi, bisindei)yltitani umictliyl(2-(dimethylamino) benzyl),
bisindeiiyltitaiiujiiiiietliyltriiniethylsilyl,
bistetiahydroilndeiiyitit- aiiuimmethyltrimethylsilyl, bi
speiitamietlbylcycl opentadienyltitaniumdii- sopropyl,
bispentaiiiethylcyclopeiitadienyltitaiiumdibeiizyl,
bispentaiietiylcyclopeiitadienyltitaniummethylethoxide,
bispentaiiietliylcyclopentadienyltitani ummetlylclcloride,
(dimethylsi lyl-bis-cyclopeiitadienyl)zirconiumdimethyl,
(dimethylsilyl
-bis-pentaiiiethylcyclopentadienyl)titanium-2,4-pentadienyl,
(dimetiiylsi lyl-bis-t-butylcyclopentadienyl)zirconiumdichloride,
(metllyleiie-bis-petitaiietiylcyclopeiitadienyl)titanin(III)
2-(dimethylaiiiino)beiizyl, (dihetliylsilyl-bis-iideiiyl)
zirconiumdichloride, (dimetlbylsi Iyl-bis-2-inetliylindenyl)
zirconiumdimethyl, (dimethylsi lyl-bis-2-metliyl-4-phenylindenyl)
zirconiumdimethyl, (dimetlylsi
lyl-bis-2-methylinidenyl)zlrconiiun-1,4-di- phenyl-1,3-butadiene,
(di metiylsi lyl -bi s-2-nietlyl -4-phejiy]indenyl)zirconium (11)
1,4-diphenyl-1,3-butadiene, (di methylsilyl
-bis-tetrahydroindenyl)zirconium(lI) 1 ,4-diphenyl-1 ,3-butadiene,
(dimethylsilyl-bis-fluorenyl) zirconiumidichloride, (di
methylsilyl-bi s-tetralhydr-oiluoren,yl) zi-conliumlid (trimethyl
silyl) (isopropy] idenie) (cyclopentadieiyl) (fluorenyl)
zirconiumltdibenzyl, and
(dimethylsilylpentaiiiethylcyclopeiitadieiiylfluoreiiyl)
zirconiumdimethyl.
[0146] Specific compounds represented by Formiiula V11 include:
[0147]
(tet-butylamido)(leti-ametli)]-715-cyclopentadienlyl)-1,2-ethanediy-
lz irconium dimethyl, (tert-butylamido)
(tetramethyl-115-cyclopeiitadienyl- )-1 ,2-ethaniediyltitanium
dimethylbenzyl, (methylamido)
(tetramethyly-5-cyclopeniadieilyl)-1,2-ethlaniediylzirconiuimi
dibenzhydryl, (methylamido)
(tetramethyl-[5-cyclopentadien)yl)-1,2-ethani- edlyltitani unm
dineopecntyl, (ethylamido)(tetramie thy
l-cyclopentadienyl)-methylenietitanium diphenyl,
(tert-btitylamildo)dibej- izyl(tetramethyl-115
_cyclopentadienyl)silaniezirconliumll dibenzyl,
(benzylamido)dimethyl(tetrametliyl-,5-cyclopentadienyl)silanetitanium
di(trimethylsilyl), (phenylpl1osphiido)dimet hyl
(tetramethyl-,q-cyclopen- tadienyl)silanezirconliuiii dibenzyl, and
the like.
[0148] Other compounds which are usefcul in the preparation of
catalyst compositions according to this invention, especially
compounds containing other Group 4 metals, will, of course, be
apparent to those skilled in the art.
[0149] Methods for preparing the above catalysts are conventional
and well known in the art.
[0150] The above described metallocene and constrained geometry
pre-catalyst compounds from which the subject catalyst is derived
are well known. The disclosure of such components and the methods
of forming the same have been described in various publications,
including U.S. Pat. Nos. 5,064,802: 5,321,106; 5,399,636;
5,541,272; 5,624,878; 5,807,938; EP 890 581; PCT/US91/01860; and
PCT/US91/04390. The teaching of each of the above cited references
are incorporated herein in its entirety by reference.
[0151] In formulas I and II to VII, each L.sup.3 group is
preferably a halogen atom, an unsubstituted hydrocarbyl or a
hydrocarbyloxy group. The most preferred compounds are those having
each L.sup.3 being halogen.
[0152] It will be understood that the identity of the L groups 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.
[0153] Thus, the manner in which the pre-catalyst is activated
typically depends on the identity of the L groups, particularly
L.sup.3.
[0154] From a generic standpoint, activation of pre-catalyst is
believed to result from removal of at least one L.sup.3 group from
the metal center in a manner sufficient to generate an open
coordination site at said metal center.
[0155] A variety of mechanisms and materials are known or possible
for accomplishing activation. Depending on the identity of L.sup.3
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.sup.3 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).
[0156] Thus, while activation mechanisms by which conventional
coordination catalyst systems operate include, but are not limited
to (a) abstraction of at least one L.sup.3 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.sup.3 group, when L.sup.3 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.
[0157] 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.
[0158] From a practical standpoint, it is preferred that L.sup.3 be
halogen, e.g. Cl, in the pre-catalyst. This stems from the fact
that when L.sup.3 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.sup.3 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 tile
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.
[0159] Accordingly, one preferred embodiment comprises using
pre-catalyst wherein each L.sup.3 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
VIII below) as a scavenger and/or alkylating agent are admixed
simultaneously prior to polymerization. In this embodiment, at
least one of the halogens constituting L.sup.3 becomes a new
hydrocarbyl L.sup.3 group derived from the organometallic 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.
[0160] Organometallic compounds suitable for use in pre-activation
include those represented by formula (VIII):
M(R.sup.2).sub.s VIII
[0161] 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.2
independently represents a hydrogen atom, a halogen atom,
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, naphthlyl), aryloxy groups (e.g., phenyloxy),
arylalkyl groups (e.g., benzyl, phenylethyl), arylalkoxy groups
(benzyloxy), alkylaryl groups (e.g., tolyl, xylyl, cumenyl,
mesityl), and alkylaryloxy groups (e.g., methylphenoxy) provided
that at least one R.sup.2 is a hydrogen atom, an alkyl group having
1 to 24 carbon atoms or an aryl, arylalkyl or alkylaryl group
having 6 to 24 carbon atoms; and s is the oxidation number of
M.
[0162] The preferred organometallic compounds are those wherein M
is aluminum.
[0163] Representative examples of organometallic compounds include
alkyl aluminum compounds, preferably trialkyl aluminum compounds,
such as trimethyl aluminum, triethyl aluminum, tri isopropyl
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.
[0164] When at least one L.sup.3 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 stable to materials
which are poisons to the activated catalyst.
[0165] In a second preferred embodiment wherein each L.sup.3 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.
[0166] 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.
[0167] In addition, the morphology of the support-activator is
believed to significantly influence the performance of the catalyst
composition.
[0168] 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.
[0169] 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.
[0170] 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.
[0171] 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.
[0172] 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.
[0173] 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
[0174] 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.
[0175] 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.
[0176] 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.
[0177] 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.
[0178] 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.
[0179] 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.
[0180] 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.
[0181] 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 arc 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.
[0182] 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.
[0183] 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, mouitmllorillonite: 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.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
[0184] 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.
[0185] 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.
[0186] 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.
[0187] Component-B preferably has a pore volume of pores having a
diameter of at least 40A (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.
[0188] 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 wraith an organic or inorganic
compound. The last treatment can result in formation of a composite
material.
[0189] 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.
[0190] Examples of the acids used for this purpose are Bronstead
acids, such as hydrochloric, sulfuric, nitric, acetic acid and the
like.
[0191] Sodium hydroxide, potassium hydroxide and calcium hydroxide
are preferably used as alkali chemical in the alkali pretreatment
of the clay mineral.
[0192] 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.
[0193] 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 ammonium 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.
[0194] 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.
[0195] 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.
[0196] Particular examples of guest organic cations that may be
introduced ion modification of the clay minerals, include:
triphenylsulfonium, trimethylsulfonium, tetraphenylphosphonium,
alkyl tri(o-tolyl) phosphonium triphelylcarbonium
cyclolheptatrienium, 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.
[0197] 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. 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.
[0198] 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.
[0199] 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 tile layers from collapsing
under van der Waals forces.
[0200] 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 4,995,964. The
disclosures of the aforementioned articles and patents are
incorporated herein by reference in their entireties.
[0201] 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.)
[0202] 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.
[0203] 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.
[0204] 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.
[0205] The support-activator is made from an intimate admixture of
Components-A and -B, which admixture is shaped in the form of an
agglomerate.
[0206] 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).
[0207] The term "agglomerate" refers to a product that combines
particles which are held together by a variety of physical-chemical
forces.
[0208] 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.
[0209] 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 inter-particle 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.
[0210] The agglomeration of Components-A and -B may be carried out
in accordance wraith 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.
[0211] However, the preferred agglomerates are made by drying,
preferably spray drying a slurry of Components-A and -B.
[0212] 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 tire hazard relative to water and often
make agglomerates too fragile for use as polymerization
catalysts.
[0213] 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
[0214] 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. %.
[0215] 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 Oil top of the test tube is
decanted, and analyzed for % solids. The % of colloidal material is
then determined by the following equation: 2 % colloid = [ ( 1 - B
B ) - 2.2 ( 1 - A A ) - 2.2 ] * 100 Equation1b
[0216] wherein
[0217] A=wt. % solids in supernatant/100, and
[0218] B=wt. % solids of original slurry/100
[0219] 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.
[0220] 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.
[0221] 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.
[0222] 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.
[0223] 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.
[0224] 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.
[0225] 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.
[0226] 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.
[0227] 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.
[0228] Accordingly, the inorganic oxide (typically while still wet)
is then subjected to a milling operation as described below to
prepare it for spray drying.
[0229] 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).
[0230] 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.
[0231] 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.
[0232] 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.
[0233] Thus, the resulting dry milled material exists in the form
of a powder prior to being slurried for spray drying.
[0234] 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.
[0235] 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.
[0236] Dry milling typically does not produce colloidal silica.
[0237] 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 10.5:1 to about
0.1:1, and most preferably from about 0.6:1 to about 0.25:1.
[0238] 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.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] 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.
[0243] 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 thin 10,
preferably greater than 30 (e.g., 10 to 100) m.sup.2/g; and all
Apparent Bulk Density (ABD) of typically greater than 0.10,
preferably greater than 0.25 (e.g., 0.10 to 0.75) g/cc.
[0244] Milling procedures can be employed to achieve these target
properties, if necessary.
[0245] 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).
[0246] 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.
[0247] Accordingly, agglomerate formation is controlled to impart
preferably the following properties to the support-activator:
[0248] (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;
[0249] (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;
[0250] (3) An average pore diameter of typically from about 30 to
about 300, and most preferably from about 60 to about 150
Angstroms; and
[0251] (4) A total pore volume of typically from about 0.0 to about
2.0, preferably from about 0.5 to about 1.8, and most preferably
firm about 0.8 to about 1.6 cc/g.
[0252] 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.
[0253] 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.
[0254] Accordingly, as a generalizations 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.
[0255] 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 nonrepresentative 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.
[0256] 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.
[0257] 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.
[0258] 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).
[0259] 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.
[0260] 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.
[0261] 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.
[0262] 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.)
[0263] 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.
[0264] 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.
[0265] 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 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.
[0266] 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.
[0267] 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.
[0268] 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.
[0269] 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.
[0270] 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.
[0271] 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.
[0272] 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.
[0273] As indicated above, an organometallic compound can be
employed for pre-activation of the pre-catalyst, e.g., where
L.sup.3 of the pre-catalyst is chlorine. It can also be employed as
a scavenger for poisons in the polymerization zone.
[0274] 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 II) 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.
[0275] 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.
[0276] 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.
[0277] The components arc 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,
cyclolhexane, methylcyclohexane, toluene, and combinations of two
or more of such diluents. Ethers such as diethylether and
tetrahydrofuran can also be used.
[0278] 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.
[0279] 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 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.
[0280] 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 and to
permit the pre-catalyst to be adsorbed and/or absorbed by the
support-activator.
[0281] The formed mixture can be separated from the inert liquid,
by filtration, vacuum distillation or the like to provide a solid
preformed catalyst compositional.
[0282] 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.
[0283] 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 tile
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).
[0284] 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 liquids 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.
[0285] A slurry of Components I, II and III 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.
[0286] 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 round that the present catalyst
composition forms rapidly under normal polymerization conditions to
exhibit high catalytic activity and provide a high molecular weight
polymer product.
[0287] The amount of Components I and II in the inert liquid
hydrocarbon is controlled to be such as to provide a ratio of
micromoles (i.e., millimoles) of Component I (pre-catalyst) to
grams of Component II (support-activator) of typically from about
1:1 to about 500:1, preferably from about 5:1 to about 200:1, and
most preferably from about 10:1 to about 100:1 (e.g., 20:1 to about
60:1).
[0288] 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 2000:1 (e.g., 0.01 to about
1000:1), preferably from about 0.1:1 to about 1000:1 and most
preferably from about 1:1 to about 500:1 (e.g., 100:1 to
300:1).
[0289] 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 100:1 (e.g., 0.01:1 to about 90:1), preferably from about
0.1:1 to about 75:1 (e.g., 2:1 to about 50:1), and most preferably
from about 0.1:1 to about 20:1 (e.g., 3:1 to about 15:1).
[0290] The amount of liquid hydrocarbon can vary typically from
about 50 to about 98, preferably firm 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.
[0291] Without wishing to be bound to ally 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 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.
[0292] 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.
[0293] 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.
[0294] 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.
[0295] 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 oligoomeric 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.
[0296] 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.
[0297] The present coordination catalyst system (composition) can
be advantageously employed in a high pressure, solution, slurry or
gas phase polymerization process.
[0298] 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.
[0299] 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.
[0300] 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.
[0301] 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.
[0302] 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 of
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
[0303] Part A--Preparation of Base Silica Hydrogel
[0304] 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 C (150 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.
[0305] 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 30 m.sup.2/g for Sample 1B. The resulting water washed gel of
Samples 1A and 1B have a SiO, 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.
[0306] Part B(i)--Preparation of Wet Milled Hydrogel (SA 600
m.sup.2/g) (Sample 2A)
[0307] 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 sand mill with a 0.016 inch screen to reduce
the average particle size (APS) to <100 microns. The sample was
then sand milled with a Premier Sand Mill (model HLM-5 with a 5
liter capacity barrel). 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.
[0308] Part B(ii)--Preparation of Wet Milled Hydrogel (SA 300
m.sup.2/g) (Sample 2B) 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.
[0309] Part C--Preparation of Dry Milled Sample (SA 300 m.sup.2/g)
(Sample 3B)
[0310] A base silica gel Sample 1B prepared in accordance with Part
A was subjected to dry milling procedure as follows:
[0311] The sample was flash or spray dried to a moisture content
below 10 wt. %. The dried powder sample was then fluid energy
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, pore
volume of 1.5 cc/g. The resulting sample was designated Sample
3B.
[0312] Part D--Preparation of Dry Milled Sample (600 m.sup.2/g)
(Sample 3A)
[0313] 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.
[0314] Part E--Preparation of Silica Slurry
[0315] Four different blends (designated Runs 1 to 4) of Sample 2B
and Sample 3B were prepared at weight ratios of Sample 3B (dry
milled):Sample 2B (wet milled) as reported in Table I. 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 I.
1TABLE I 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 75:25 3.00:1 2 Ex 1 Part E 70:30 2.25:1 3 Ex 1
Part E 60:40 1.50:1 4 Ex 1 Part E 0:100 0:1
[0316] Part F--Preparation of Alternate Silica Support Slurries
[0317] (i) Part E was repeated except that Sample 3B (300
m.sup.2/g) was replaced with Sample 3A (600 nm/g) and Sample 2B
(300 m.sup.2/g) was replaced with Sample 2A (600 m.sup.2/g) The
drib milled/wet milled ratios employed are summarized at Table II
and the slurries designated Runs 5 and 6.
[0318] (ii) 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 Run 7. The sample of Run 7 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.
2TABLE II Run Ex or Comp Sample 3A (Dry Milled):Sample 2A (Wet
Milled) Number Ex No Weight % Ratio Weight Ratio 5 Ex 1 Pt F 75:25
3.00:1 6 Ex 1 Pt F(i) 60:40 1.50:1 7 Ex 1 Pt F(ii) 0:100 0:1
(Fines)
[0319] Part G--Preparation of Clay Slurry
[0320] 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 III.
The clay composition properties of an alternate clay product
available under the tradename Gel White is also provided at Table
III.
3TABLE III Chemical Composition of Montmorillonite BP Colloidal
Clay BP Gel White Component Weight % Weight % S.sub.1O.sub.2 69.5
73.0 Fe.sub.2O.sub.3 4.4 0.97 Al.sub.2O.sub.3 19.0 17.1 MgO 2.3 3.6
CaO 1.0 2.3 Na.sub.2O 2.7 -- SO.sub.4 0.6 0.2
Physical Properties of BP Colloidal Clay
[0321]
4 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 A Total
Pore Volume 0.20 cc/g
[0322] Part H--Preparation of Silica/Clay Slurry for Spray
Drying
[0323] Each of the silica slurries of Runs 1 to 6 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
V. Each slurry was adjusted with acid (sulfuric acid) or base
(ammonium hydroxide) to achieve a slurry pH of 8-13. 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 8 to 13.
[0324] Part I--Spray Drying of Silica/Clay Slurry
[0325] Each pH adjusted slurry of Runs 8 to 13 was then pumped to a
spray dryer to dry the mixture and to form microspheroidal
agglomerates. All spray drying is conducted by using a Niro 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/mill. 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. %. Further drying in a static bed oven at 150-800.degree.
C. can then be used to adjust the total volatiles to 0.5-5 wt.
%.
[0326] The yield of material from the spray dryer chamber
collection pot is around 40 wt. %. The yield from screening is also
around 40 wt. %, for an overall yield of 15-20 wt. %.
[0327] Table VI below reports silica/clay morphological properties
of the resulting agglomerates. The resulting Agglomerate Samples
are designated Runs 16 to 21.
COMPARATIVE EXAMPLE 1
100% Spray Dried Clay Support
[0328] 5 parts-by-weight montmorillonite clay available from
Southern Clay Products under the tradename Gel White was mixed with
28 parts-by-weight water using a mixer. The slurry (designated Run
14C) was the then fed to a Niro Spray Dryer in accordance with
Example 1, Part I to make clay microspheres. Only 1.3 wt. % of the
starting clay was recovered as agglomerates that accumulated in the
spray dryer chamber collection pot (<5% yield) and the remainder
was observed as dust and build-tip on the spray dryer wall. 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.
[0329] The resulting spray dried clay powder was designated Run 22C
and is summarized at Table VI.
COMPARATIVE EXAMPLE 2
100% Spray Dried Silica Support
[0330] Example 1, Part 1 was repeated except that the slurry
(designated Run 15C) that was spray dried contained only silica,
and the silica was derived from Run 1, 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 microsphieroidal 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 23C and is summarized at Table VI.
EXAMPLE 2
Preparation of Catalyst System
[0331] Part A--Method 1
[0332] 1 g of support-activator was added to a bottle that contains
toluene solvent (25 ml) and Al-i-Bu.sub.3 (triusobutylaluminium) or
AlMe.sub.3 (trimethylaluminum) (both of which were present as a
25-wt. % solution of toulenie and were purchased from Aldrich). The
resulting mixture was then treated with a known amount of
metallocene pre-catalyst (.mu.mole/g-support-activator). This
catalyst mixture was sealed and agitated in an orbital shaker for
at least 12 hours in an argon atmosphere. An aliquot of 1 to 3 ml
of reaction slurry was used for polymerization depending on the
catalyst activity as indicated at Table VII.
[0333] Part B--Method 2
[0334] Part A was repeated except that the metallocene pre-catalyst
was contacted with the organoaluminium compound before contacting
the support-activator.
[0335] Part C--Method 3
[0336] Part B was repeated and a sample of reaction slurry obtained
therefrom was agitated in an argon-filled drybox for 5-12 hours.
The resulting reaction mixture was then filtered, washed with
toluene (2.times.10 ml), heptane (2.times.10 ml) and dried in a
vacuum. The ICP analysis of this dry powder is shown in Table
IV.
5 TABLE IV Run No. Zr wt. % Al wt. % Si wt. % 48 0.098 5.700 36.800
60 0.117 5.100 38.100 62 0.064 5.500 40.00 63 0.085 6.700 36.900 64
0.080 6.800 36.300
[0337] For Parts A to C, the metallocene pre-catalyst identity is
shown at Table VII, Column 9 and the amount thereof shown at Table
VII, Column 10. The identity and amount of organometallic compound
(Al-i-Bu.sub.3 or AlMe.sub.3) is reported at Table VII, Columns 7
and 8. The support-activator source and catalyst system preparation
method are also provided at Table VII, Columns 2 and 11
respectively.
COMPARATIVE EXAMPLE 3
100% Spray Dried Silica Fines
[0338] Example 2 was repeated except that the silica-clay
agglomerate was replaced with an unagglomerated physical blend of
Mineral Colloidal (<1 micron particle size) BP monitmorillonite
clay and silica hydrogel powder of Run 7. Pre-catalyst was then
added in accordance with Example 2 and the resulting mixtures
tested in accordance with Example 3 as Run 83C. The amounts of
triusobutylaluminum and pre-catalyst ratios are reported at Table
VII.
EXAMPLE 3
Polymerization Method
[0339] 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 80.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, a slurry of triisobutylaluminum, pre-catalyst and
support-activator prepared in accordance with the method number of
Example 2 indicated at Table VI, 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. The polymerization temperature
was 80.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 at about 200 psig. After 60 minutes,
the ethylene feed was stopped and the reactor cooled to room
temperature and vented. The resulting polymer slurry was filtered
and washed with methanol and acetone to deactivate any residual
catalyst, filtered and dried in a vacuum oven at about 500.degree.
C. 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.
[0340] The results of each polylimerization are summarized at Table
VII runs 24 to 83C. Columns 7 and 8 depict the identity and amount
(mmole) of organoaluminum compound used with respect to the amount
(grams) of support-activator material during the active catalyst
preparation. Columns 9 and 10 depict the identity and amount of
pre-catalyst and tile amount (grams) of support-activator used
during the active catalyst preparation. Column 14 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 12) (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
pre-catalyst concentration (Column 13). Thus, Column 13 represents
gPE.times.10.sup.-5/g Transition Metal (M)-h which is related to
the total amount (gram) of polyethylene product produced per gram
of transition metal present in the pre-catalyst per hour. More
specifically, a reported value of 1 in Column 13 indicates 100,000
g of PE is produced per gram of Zr per hour.
Discussion of Results
[0341] Comparing Run 83C (80:20 silica:clay physical admixture)
with Run 61 (80:20 spray dried agglomerate), it can be seen that
the activity of Run 61 is almost 10 times greater than that of Run
83C. 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 83C also yields a poor polymer morphology with a bulk density
of only 0.14 g/cc.
[0342] Comparing Run 81C (100% clay) with Run 86 (50:50
silica:clay), it can be seen that very low activities (0.29 and
1.3.g PE.times.10.sup.5/gZr.hr) are associated with a clay only
support versus activities of 2.42 g PE.times.10.sup.5/gZr.hr for
silica-clay support activators.
[0343] Similar results are obtained by silica only supports. For
example Runs 82C, 45C and 46C all exhibited little or no
activity.
[0344] It will be further observed from a comparison of Runs 35 and
36 that contacting the pre-catalyst with organoaluminum compound
before contact with the support activator cuts the activity nearly
in half. This is believed to be attributable to a lower stability
of the pre-activated catalyst relative to a fully activated one
which forms sooner in Method 1. Comparing Runs 36 and 37 it will be
observed that changing the organoaluminum compound from triisobutyl
aluminum (Run 36) to aluminumtrimethyl (Run 37) further reduces the
activity from 0.64 to <0.5. Moreover, the drop in activity
attributable to the choice of organoaluminum compound is not
reversed by employing the preferred sequence of contact represented
by Method 1 (compare Run 38 with Run 37). This suggests that the
choice of organoaluminum compound is more influential on activity
than the contact sequence.
6TABLE V Spray Drying Slurry and Conditions Source of Silica:Clay
Dry Solids Ex. No. or Comp. Ex Silica Ratio Run No. No. (Run Nos.)
(w/w) 8 Ex 1 Pt H 1 80:20 9 Ex 1 Pt H 2 65:35 10 Ex 1 Pt H 3 50:50
11 Ex 1 Pt H 4 25:75 12 Ex 1 Pt H 5 80:20 13 Ex 1 Pt H 6 50:50 14C
Comp Ex 1 none 0:1 15C Comp Ex 2 none 1:0
[0345]
7TABLE VI Spray Dried Silica/Clay Support-Activator Product
Properties Column No. 2 3 4 5 6 Slurry Agglomerate Properties
Source Silica/ 1 from Clay Pore Run Ex. No. or Table VII (Weight
APS SA Vol. No. Comp Ex. (Run No.) Ratio) (microns) (m.sup.2/g)
(cc/g) 16 Ex 1 8 80:20 45 251 1.48 17 Ex 1 9 65:35 45 213 1.28 18
Ex 1 10 50:50 45 185 1.04 19 Ex 1 11 25:75 45 160 0.64 20 Ex 1 12
80:20 45 494 1.16 21 Ex 1 13 50:50 45 322 0.83 22C Comp Ex 1 14C
0:1 N/A N/A N/A 23C Comp Ex 2 15C 1:0 47 277 1.69 * = Made from 600
m.sup.2/g silica ** = Discarded APS = Average Particle Size PSD =
Particle Size Distribution based on D10, D50, D90 percentile
[0346]
8 TABLE VII 7 8 Organo 2 3 Aluminum 9 10 11 12 13 Support-
Corresponding 4 5 6 Compound Pre-Cat Cat-Syst Cat Metal (M) 1
Activator Ex or Silica:Clay Calcination mmol/g- .mu.mol/g Prep
Activity Activity 14 Run Source Comp Ex (Weight Temp Time Support-
Support- Method KgPE/ gPE .times. 10.sup.-5/ B.D. No. (Run No.) No.
Ratio) .degree. C. (hr) Type Activator No. Activator No. gCat-h
g/M/hr g/cc 24 16 Ex 3 80:20 UC N/A 1 2 1 100 1 1.31 1.5 0.30 25 16
Ex 3 80:20 UC N/A 1 2 1 99 1 1.30 1.5 0.30 26 16 Ex 3 80:20 UC N/A
1 2 1 49 1 0.56 1.3 0.33 27 16 Ex 3 80:20 UC N/A 1 3 1 99 1 0.93
1.0 0.31 28 16 Ex 3 80:20 UC N/A 1 3 1 50 1 1.15 2.6 0.34 29 16 Ex
3 80:20 UC N/A 1 3 1 49 1 1.16 2.6 0.34 30 16 Ex 3 80:20 UC N/A 1 4
1 99 1 1.13 1.3 0.29 31 16 Ex 3 80:20 UC N/A 1 4 1 74 1 1.10 1.6
0.30 32 16 Ex 3 80:20 UC N/A 1 4 1 49 1 1.16 2.6 0.26 33 16 Ex 3
80:20 UC N/A 1 5 1 99 1 1.44 1.6 0.30 34 16 Ex 3 80:20 UC N/A 1 5 1
74 1 1.38 2.0 0.33 35 16 Ex 3 80:20 UC N/A 1 5 1 49 1 1.22 2.7 0.33
36 16 Ex 3 80:20 UC N/A 1 5 1 49 2 0.64 1.4 0.30 37 16 Ex 3 80:20
UC N/A 2 5 1 74 2 <0.5*** <0.5*** N/A 38 16 Ex 3 80:20 UC N/A
2 5 1 49 1 <0.5*** <0.5*** N/A 39 16 Ex 3 80:20 UC N/A 1 6 1
49 1 1.06 2.2 0.32 40 16 Ex 3 80:20 UC N/A 1 6 1 49 1 1.06 2.2 0.32
41 17 Ex 3 65:35 UC N/A 1 4.5 1 74 1 1.04 1.5 0.28 42 17 Ex 3 65:35
UC N/A 1 4 1 49 1 0.80 1.8 0.29 43 17 Ex 3 50:50 UC N/A 1 4 1 49 1
0.89 2.0 0.25 44 17 Ex 3 50:50 150 4 1 2 1 49 1 0.52 1.2 N/A 45C 7
Ex 7 1:0 UC N/A 1 2 1 120 1 <0.5 Neg. N/A (Fines) 46C 7 Ex 7 1:0
UC N/A 1 1 1 120 1 <0.5 Neg. N/A (Fines) 47 16 Ex 3 80:20 UC N/A
1 2 2 24 1 1.67 7.7 0.38 48 16 Ex 3 80:20 UC N/A 1 2 2 24 3 1.98
20.0 N/A 49 16 Ex 3 80:20 UC N/A 1 2 2 12 1 0.32 2.9 0.28 50 16 Ex
3 80:20 UC N/A 1 3 2 36 1 1.53 4.7 0.29 51 16 Ex 3 80:20 UC N/A 1 3
2 24 1 1.78 8.2 0.37 52 16 Ex 3 80:20 UC N/A 1 3 2 12 1 0.54 5.0
0.28 53 16 Ex 3 80:20 UC N/A 1 4 2 36 1 1.17 3.6 0.31 54 16 Ex 3
80:20 UC N/A 1 4 2 24 1 1.30 6.0 0.36 55 16 Ex 3 80:20 UC N/A 1 4 2
12 1 0.63 5.8 0.29 56 16 Ex 3 80:20 UC N/A 1 5 2 72 1 1.27 2.0 0.29
57 16 Ex 3 80:20 UC N/A 1 5 2 52 1 0.81 0.93 0.30 58 16 Ex 3 80:20
UC N/A 1 5 2 48 1 1.16 2.7 0.27 59 16 Ex 3 80:20 UC N/A 1 6 2 48 1
2.16 5.0 0.34 60 16 Ex 3 80:20 UC N/A 1 6 2 48 3 1.25 11.0 0.26 61
16 Ex 3 80:20 UC N/A 1 6 2 24 1 1.94 8.9 0.28 62 20 Ex 3 80:20 500
4 1 5 2 36 3 2.03 32.0 0.29 63 21 Ex 3 50:50 500 4 1 5 2 36 3 1.80
21.2 0.27 64 21 Ex 3 50:50 500 4 1 6 2 36 3 1.93 24.2 0.27 65 16 Ex
3 80:20 UC N/A 1 4 3 41 1 0.52 2.7 0.30 66 16 Ex 3 80:20 UC N/A 1 4
3 27 1 0.46 3.5 0.31 67 16 Ex 3 80:20 UC N/A 1 5 3 41 1 0.40 2.1
0.31 68 16 Ex 3 80:20 UC N/A 1 6 4 24 1 0.38 3.4 0.27 69 16 Ex 3
80:20 UC N/A 1 4 4 48 1 0.38 1.7 0.29 70 16 Ex 3 80:20 UC N/A 1 4 4
36 1 0.38 2.3 0.30 71 16 Ex 3 80:20 UC N/A 1 4 4 24 1 0.32 2.8 N/A
72 16 Ex 3 80:20 UC N/A 1 3 4 36 1 0.36 2.1 0.30 73 17 Ex 3 65:35
UC N/A 1 7 4 21 1 0.43 4.5 0.34 74 17 Ex 3 65:35 UC N/A 1 6 4 36 1
0.65 3.9 0.31 75 17 Ex 3 65:35 UC N/A 1 3 4 24 1 0.51 4.6 0.32 76
18 Ex 3 50:50 UC N/A 1 7 4 35 1 0.45 2.7 0.33 77 18 Ex 3 50:50 UC
N/A 1 7 4 24 1 0.33 2.2 0.35 78 18 Ex 3 50:50 UC N/A 1 4.6 4 30 1
0.33 2.2 0.30 79 19 Ex 3 25:75 UC N/A 1 10 4 28 1 0.51 2.3 0.30 80
19 Ex 3 25:75 UC N/A 1 7 4 24 1 0.58 5.2 0.35 81C 22C Comp 0:1 250
4 1 5 2 24 1 0.29 1.3 N/A Ex 1 82C 23C Comp 1:0 250 4 1 5 2 24 1
0*** 0*** N/A Ex 2 83C** Comp Comp 80:20 UC N/A 1 6 2 24 1 0.13 0.6
0.14 Ex 3 Ex 3 84C Comp Comp 1:0 UC N/A 1 2 1 120 1 0 G 0 N/A Ex 3
Ex 3 85C Gel White Ex 1. 0:1 UC N/A 1 1 2 100 1 0 0 N/A Clay PtG 86
21 Ex 3 50:50 250 4 1 5 2 24 1 2.42 11.1 0.24 **= Non-Agglomerated
physical blend ***= 3 ml of catalyst aliquot was used for testing
and the polymerization was terminated after 15 min. due to the very
low catalyst activity. UC = uncalcined N/A = not applicable
Organo-Al Type 1 = Al-iBu.sub.3 Organo-Al Type 2 = Al-Me.sub.3
Catalyst 1 = (n-BuCp).sub.2ZrCl.sub.2 purchased from Boulder
Scientific. Catalyst 2 = rac-ethylene bis(indenyl)zirconium
dichloride purchased from Boulder Scientific. Catalyst 3 =
(Cp*SiMe.sub.2N-t-Bu)TiCl.sub.2 prepared according to the
procedures described in PCT Appl. WO 9200333 (Exxon) and EP Appl.
EP 416815 Catalyst 4 = (Cp*SiMe.sub.2N-t-Bu)Ti(pentadiene) prepared
using the procedures described in Organometallics 1995, 14,
3132.
[0347] 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.
* * * * *