Title: Monoamide based catalyst compositions for the polymerization of olefins
Abstract: Novel catalyst monoamide precursor compositions and the corresponding single site-like catalysts for olefin polymerization.
Patent Number: 7,001,863 Issued on 02/21/2006 to Murray
| Inventors:
|
Murray; Rex Eugene (Cross Lanes, WV)
|
| Assignee:
|
Univation Technologies, LLC (Houston, TX)
|
| Appl. No.:
|
022668 |
| Filed:
|
December 18, 2001 |
| Current U.S. Class: |
502/155; 502/167; 526/161; 526/171 |
| Current Intern'l Class: |
B01J 31/38 (20060101); C08F 4/44 (20060101) |
| Field of Search: |
502/155,167
526/161,171
|
References Cited [Referenced By]
U.S. Patent Documents
| 6472342 | Oct., 2002 | Agapiou et al.
| |
| 6475946 | Nov., 2002 | Rix.
| |
| 6479422 | Nov., 2002 | Eilerts.
| |
| 6482903 | Nov., 2002 | Agapiou et al.
| |
| 6489497 | Dec., 2002 | Brookhart et al.
| |
| 6511936 | Jan., 2003 | Theopold et al.
| |
| 6521561 | Feb., 2003 | Jacobsen et al.
| |
| 6544919 | Apr., 2003 | Tagge et al.
| |
| 6559091 | May., 2003 | Moody et al.
| |
| 6579823 | Jun., 2003 | Moody et al.
| |
| 6579998 | Jun., 2003 | Sita et al.
| |
| 6586358 | Jul., 2003 | Llatas et al.
| |
| 6593266 | Jul., 2003 | Matsui et al.
| |
| 6632769 | Oct., 2003 | Wenzel et al.
| |
| 6632770 | Oct., 2003 | Holtcamp.
| |
| 6660677 | Dec., 2003 | Mackenzie et al.
| |
| 6660679 | Dec., 2003 | Holtcamp et al.
| |
| 6660815 | Dec., 2003 | Agapiou et al.
| |
| 6670297 | Dec., 2003 | Brookhart et al.
| |
| 6686491 | Feb., 2004 | Cavell et al.
| |
| Foreign Patent Documents |
| 42 02 889 | Aug., 1993 | DE.
| |
| 0 320 169 | Jun., 1989 | EP.
| |
| 0 509 233 | Oct., 1992 | EP.
| |
| 0 349 886 | Sep., 1995 | EP.
| |
| 0 761 694 | Mar., 1997 | EP.
| |
| 0 803 520 | Oct., 1997 | EP.
| |
| 0 950 667 | Oct., 1999 | EP.
| |
| WO 92/1216/2 | Jul., 1992 | WO.
| |
| WO 95/3349/7 | Dec., 1995 | WO.
| |
| WO 96/2301/0 | Aug., 1996 | WO.
| |
| WO 96/3320/2 | Oct., 1996 | WO.
| |
| WO 97/0229/8 | Jan., 1997 | WO.
| |
| WO 97/4543/4 | Dec., 1997 | WO.
| |
| WO 02/4624/6 | Jun., 2002 | WO.
| |
Other References
Gibson et al., "Synthesis and structural characterisation of aluminum imino-amide
and pyridyl-amide complexes: bulky monoanionic N,N chelate ligands via methyl group
transfer" Journal of Organometallic Chemistry 550, (1998) 453-456.
Fuhrmann et al., "Octahedral Group 4 Metal Complexes That Contain Amine, Amido,
and Aminopyridinato Ligands: Synthesis, Structure, and Application in α-Olefin
Oligo- and Polymerization" Inorg. Chem 1996, 35, 6742-6745 (Feb.).
George J.P. Briotovsek et al., "Novel Olefin Polymerization Catalysts Based
on Iron and Cobalt" Chem. Commun., 1998 849-850 (May).
Deelman et al., "Lithium Derivatives of Novel Monoaniomic Di-N,N'-chelating
Pyridyl- and Quinolyl-l-azaallyl Ligands" Organometalics 1997, 16, 1247-1252 (Aug.).
Deelman et al., "Novel monanionic di-N,N'-centered chelating ligands and the
C1and C2 symmetrical zirconium complexes"
Journal of Organometallic Chemistry 513 (1996) 281-285 (Nov.).
Hitchcock et al., "Transformaton of the Bis(trimethylsilyl)methyl
into Aza-allyl and β-Diketinimato Ligands; the X-Ray Structures of [Li{N(R)C(Bu1)CH(R)}]2
and [Zr{N(R)C(Bu1)CHC(Ph)N(R)}CI3](R=SiMe3)"
J. Chem. Soc., Chem. Commun. (1994) 2637-2638 (Aug.).
Hitchcock et al., "Transformaton of the Bis(trimethylsilyl)methyl
into a β-Diketinimato Ligand; the X-Ray Structure of [Li(L'L')]2,
SnCi(Me)2 (L'L')and SnCi(Me)2
(LL), (L'L'=N(R)C(Ph)C(H)C(Ph)NR,LL=N(H)C(Ph)NH,
R—SiMe3)" J. Chem. Soc., Chem. Commun. (1994) 1699-1700 (May).
Clarke, et al., "Structural Investigations of the Dipyrromethene Complexes
of Calcium(II), Nickel(II) and Cooper(II)
Inorganica Chimica Acta. 166 (1989) 221-231 (Jun.).
Tjaden et al. "Synthesis, Structures, and Reactivity of (R6-acen)ZrR'2
and(R6-acen)Zr(R')30 Complexes
(R=H, F; R'=CH2CHe3, CH2Ph)"
Organometallics 1995, 14, 371-386 (Jul.).
Corazza et al., cis-and trans-Dichloro-derivatives of Six- and Seven-co ordinate
Zirconium and Hafnium bonded to Quadridentate Schiff-base Ligands. Crystal Structures
of [Zr(acen)Cl2(thf)], [M(salphen)Cl2(thf)]
0.5thf, [M(acen)Cl2, (M=Zr or Hf), and
[Zr(msal)Cl2] acen=N,N'=ethylenebis(acetylacetoneiminate),
salphen=N,N'-o-phenylenebis(salicylideneiminate), msal=N-methylsalicylideneiminate,
and thf=tetrahydrofuran] J. Chem. Soc. Dalton Trans. (1990) 1335-1344 (Aug.).
Cozzi et al., "Oxazoline Early Transiton Metal Complexes: Functionalizable
Achiral Titanium(IV), Titanium(III), Zirconium(IV),
Vanadium(III), and Chiral Zirconium(IV) Bis(oxazoline)
complexes" Inorg. Chem (1995), 34, 2921-2930, (Dec.).
Korine et al., "Bis(Trimethylsilyl)benzamidinate zirconium dichlorides.
Active catalysts for ethylene polymerization" Journal of Organometallic Chemistry
503 (1995) 307-314 (Mar.).
Gomez et al., "Mono-η-cyclopendtadienyl-benzamidinato chloro compounds
of titanium, zirconium and hafnium" Journal of Organometallic Chemistry 491
(1995) 153-158 (Aug.).
Flores, et al., "[N,N'-Bis(trimethylsilyl)benzamidinato]titanium
and-zirconium Compounds. Synthesis and Application as Precursors for the Syndiospecific
Polymerization of Styrene" Organometallics 1995, 14, 1827-1833 (Oct.).
Dias et al., "N-Methyl-2(methylamino)troponiminate Complexes
of Tin(II), Gallium(III), and Indium(III).
Syntheses of [(ME)2ATI]2Gal and [(Me)2ATI]2InCl
Using the Tin(III) Reagent [(Me)2ATI]2Sn"
Inorg. Chem. 1996, 35, 6546-6551 (Jun.).
Cotton et al., "Structural Studies of formamidine compounds: from neutral
to anionic and cationic species" Polyhedron vol. 16 No. 3 pp. 541-550, 1997 (Apr.).
Gornitzka et al., "Coordinationo of the Bis(pyridyl)methyl Substituent
to Group 1 and 13 Metals" Organometallics 1994, 13, 4398-4405 (May).
Roesky et al., "Benzamidnatokomplexe mit Haupt- and Nebengruppen-Elementen—Strukturen
von PhC(NSiMe3)2TiCl2 and
PhC(NSiMe3)2MoO2" Chem. Ber
121, 1403-1406 (1988) (Feb.).
Cloke et al., "Zirconium Complexes incorporating the New Tridentate Diamide
Ligand [(Me3Si)N{CH2CH2N(SiMe3)}2]2-(L);
the Crystal Structures of [Zr(BH4)2L]
and [ZrCl{CH(SiMe3)2}L]" J. Chem Soc.
Dalton Trans (Jul.) 25-30, 1995.
Linden et al., "Polymerization of α-Olefins and Butadiene and Catalytic
Cyclotrimerization of 1-Alkynes by a New Class of Group IV Catalysts. Control of
Molecular Weight and Polymer Microstructure via Ligand Turning in Sterically Hindered
Chelating Phenoxide Titanium and Zirconium Species" J. Am. Chem. Soc. 1995,
117, 3008-3021 (Jul.).
Brand et al. "Facile Reduction of a Dialkyl Zirconium(IV) Octaethylporphyrin(OEP)
Complex by H2: Crystal Structure and Spectroscopic Characterization
of [(OEP)ZrCH2SiMe3]" Angew. Chem.
Int. Ed. Engl. 1994 33, No. 1 95-97 (Jul.).
Solari et al., "Functionalizedable 5,5,10,10,15,15,20,20-Octaethylporphyrinogen
Complexes of Early Transition Metals: Synthesis and Crystal Structure of Titanium-,
Vanadium- and Chromium- (III) Derivatives and a Two-electron Oxidation
of the Porphyrinogen Skeleton" J. Chem. Soc. Dalton Trans 1994 2015-2017 (Apr.).
Uhrhammer et al., "Cationic d0 Metal Alkyls Incorporating
Tetraaza-Macrocycle Ancillary Ligands. Synthesis and Reactivity of (Me8taa)M(R)+
and (Me4taen)M(R)+(M=Zr,
Hf) Complexes" J. Am. Chem. Soc. 1993, 115, 8493-8494 (Apr.).
Giannini, et al., "Tetraaza[14]annulenezirconium (iv) Complexes
with Butadiene Ligands and their Relationship with Bis(cyclopentadienyl)zirconium(IV)
Complexes." Angew. Chem. Int. Ed. Engl. 1994, 33 No. 21 (May).
Kol, et al., "Synthesis of Molybdenum and Tungsten Complexes That Contain
Triamidoamine Ligands of the Type (C6F5NCH2CH2)3N
and Activation of Dinitrogen by Molybdenum" J. Am. Chem. Soc. 1994, 116, 4382-4390, (Oct.).
Bei et al., "Synthesis, Structures, Bonding, and Ethylene Reactivity of Group
4 Metal Alkyl Complexes Incorporating 8-Quinolinolato Ligands" Organometallics
1997, 16, 3282-3302 (Mar.).
Tsukahara, et al., "Neutral and Cationic Zirconium Benzyl Complexes Containing
Bidentate Pyridine-Alkoxide Ligands. Synthesis and Olefin Polymerization Chemistry
of (pyCR2O)2Zr(CH2Ph)2
and(pyCR2O)2Zr(CH2Ph)30Complexes"
Organometallics 1997, 16, 3303-3313 (Mar.).
Kim et al., "Synthesis, Structures, Dynamics, and Olefin Polymerization Behavior
of Group 4 Metal (pyCAr2O)2M(NR2)2
Complexes Containing Bidentate Pyridine-Alkoxide Ancillary Ligands" Organometallics
1997, 16, 3314-3323 (Mar.).
Durfee et al., "Formation and Characterization of η2-Imine
and η2-Azobenzene Derivatives of Titanium Containing Ancillary
Aryloxide Ligation" Organometallics, vol. 9, No. 1, 1990, pp. 75-80, (Jan.).
Lappert et al., "Recent studies on metal and metalloid bid(trimethylsilyl)methyls
and the transformation of the bis(trimethylsilyl) methyl into the
azaallyl and β-diketinimato ligands" Journal of Organometallic Chemistry
500, (1995) 203-217, (Sep.).
|
Primary Examiner: Harlan; Robert D.
Attorney, Agent or Firm: Faulkner; Kevin M.
Claims
What is claimed is:
1. A catalyst precursor composition selected from the group consisting of those
represented by:
##STR30##
wherein T is a bridging group containing 2 or more bridging atoms;
M is zirconium;
Z is a coordination ligand;
each L is a monovalent, bivalent, or trivalent anionic ligand;
n is an integer from 1 to 6;
m is an integer from 1 to 3;
k has the value of 2 when X is nitrogen or phosphorus, and k has the value of
1 when X is oxygen or sulfur;
X and Y are heteroatoms each independently selected from nitrogen, phosphorus,
oxygen or sulfur;
R is a non-bulky substituent selected from straight and branched chain alkyl
groups, provided that when R is a branched or chained alkyl group, the branch point
is at least 3 atoms removed from X; and
R′ is a bulky substituent selected from alkyl, alkenyl, cycloalkyl, alkylaryl,
arylalkyl, polymeric groups and heteroatom containing groups thereof; wherein there
is branching within three atoms of Y and wherein R′ comprises from 3 to
50 non-hydrogen atoms.
2. The catalyst precursor composition of claim 1 wherein at least one of the
bridging atoms of T is a carbon atom and wherein T contains from about 1 to 50
non-hydrogen atoms.
3. The catalyst precursor composition of claim 1 wherein T contains a dimethyl
group adjacent to Y.
4. The catalyst precursor composition of claim 1 wherein T is selected from the
group consisting of:
##STR31##
##STR32##
##STR33##
wherein X and Y are provided for convenience and are not part of the bridging group.
5. The catalyst precursor composition of claim 1 wherein Z is selected from at
least one of triphenylphosphine, tris(C
1-C
6 alkyl) phosphine,
tricycloalkyl phosphine, diphenyl alkyl phosphine, dialkyl phenyl phosphine, trialkylamine,
arylamine, a substituted or unsubstituted C
2 to C
20 alkene,
an ester group, a C
1 to C
4 alkoxy group, an amine group,
carboxylic acid, and di(C
1 to C
3) alkyl ether, an an η
4-diene,
tetrahydrofuran, and a nitrile.
6. The catalyst precursor composition of claim 1 wherein each L is an anionic
ligand independently selected from those containing from about 1 to 50 non-hydrogen
atoms and selected from the group consisting of halogen containing groups; hydrogen;
alkyl; aryl; alkenyl; alkylaryl; arylalkyl; hydrocarboxy; amides, phosphides; sulfides;
silyalkyls; diketones; borohydrides; and carboxylantes.
7. The catalyst precursor compositon of claim 1 wherein each L is an anionic
ligand independently selected from those containing from about 1 to 20 non-hydrogen
atoms and selected from the group consisting of alkyl, arylalkyl, and halogen containing groups.
8. The catalyst precursor composition of claim 1 wherein n is an integer from
1 to 4.
9. The catalyst precursor composition of claim 1 wherein both X and Y are nitrogen.
10. The catalyst precursor composition of claim 1 wherein R is a non-bulky C
1
to C
20 alkyl group.
11. The catalyst precursor composition of claim 10 wherein R is a C
1
to C
10 straight chain alkyl group.
12. The catalyst precursor composition of claim 1 wherein R′ is selected
from alkyl, alkenyl, cycloalkyl, heterocyclic, alkylaryl, arylalkyl, and polymeric.
13. The catalyst precursor composition of claim 12 wherein the R′ substituent
contains from about 3 to 50 non-hydrogen atoms.
14. The catalyst precursor composition of claim 13 wherein the R′ substituent
has one or more of its carbon or hydrogen positions are substituted with an element
selected from Groups 14 to 17 of the Periodic Table of the Elements.
15. The catalyst precursor composition of claim 1 having a formula selected from:
##STR34##
16. The catalyst precursor composition of claim 1 which is represented by a formula
selected from:
##STR35##
Description
FIELD OF THE INVENTION
The present invention relates to novel monoamide based catalyst precursor and
catalyst compositions useful for the polymerization of olefins and other monomers.
BACKGROUND OF THE INVENTION
A variety of metallocenes and other single site-like catalysts have been developed
to produce olefin polymers. Metallocenes are organometallic coordination complexes
containing one or more pi-bonded moieties (i.e., cyclopentadienyl groups) in association
with a metal atom. Catalyst compositions containing metallocenes and other single
site-like catalysts are highly useful in the preparation of polyolefins, producing
relatively homogeneous copolymers at excellent polymerization rates while allowing
one to tailor closely the final properties of the polymer as desired.
Recently, work relating to certain nitrogen-containing, single site-like
catalyst precursors has been published. PCT application No. WO 96/23101 relates
to di(imine) metal complexes that are transition metal complexes of bidentate ligands
selected from the group consisting of:
##STR1##
wherein said transition metal is selected from the group consisting of Ti,
Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd;
R2 and R5 are each independently hydrocarbyl or substituted
hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has
at least two carbon atoms bound to it;
R3 and R4 are each independently, hydrogen, hydrocarbyl,
substituted hydrocarbyl, or R3 and R4 taken together are
hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
R44 is a hydrocarbyl or substituted hydrocarbyl, and R28
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and
R28 taken together form a ring;
R45 is a hydrocarbyl or substituted hydrocarbyl, and R29
is hydrogen, hydrocarbyl or substituted hydrocarbyl or R45 and
R29 taken together form a ring;
each R30 is independently hydrogen, hydrocarbyl or substituted
hydrocarbyl, or two of R30 taken together form a ring;
each R31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R46 and R47 are each independently hydrocarbyl or
substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen
atom has at least two carbon atoms bound to it;
R48 and R49 are each independently hydrogen, hydrocarbyl,
or substituted hydrocarbyl;
R20 and R23 are each independently hydrocarbyl, or
substituted hydrocarbyl;
R21 and R22 are independently hydrogen, hydrocarbyl,
or substituted hydrocarbyl; and
n is 2 or 3;
and provided that:
- the transition metal also has bonded to it a ligand that may be displaced
by or added to the olefin monomer being polymerized; and
when the transition metal is Pd, said bidentate ligand is (V), (VII) or (VIII).
Also, U.S. Pat. No. 6,096,676, which is incorporated herein by reference, teaches
a catalyst precursor having the formula:
##STR2##
wherein M is a Group IVB metal;
each L is a monovalent, bivalent, or trivalent anion;
X and Y are each heteroatoms, such as nitrogen;
each Cyclo is a cyclic moiety;
each R1 is a group containing 1 to 50 atoms selected from the
group consisting of hydrogen and Group IIIA to Group VIIA elements, and two or
more adjacent R1 groups may be joined to form a cyclic moiety;
each R2 is a group containing 1 to 50 atoms selected from the
group consisting of hydrogen and Group IIIA to Group VIIA elements and two or more
adjacent R2 groups may be joined to form a cyclic moiety;
W is a bridging group; and
each m is independently an integer from 0 to 5;
Also taught is a catalyst composition comprising this catalyst precursor and
an activating co-catalyst, as well as a process for the polymerization of olefins
using this catalyst composition.
Although there are a variety of single site catalysts taught in the prior
art, some of which are commercially available, there still exist a need in the
art for improved catalysts and catalyst precursors that are capable of producing
polyolefins having predetermined properties.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided catalyst precursors
selected from the formulae:
##STR3##
wherein T is a bridging group containing 2 or more linking atoms;
M is a metallic element selected from Groups 1 to 15, and the Lanthanide
series of the Periodic Table of the Elements;
Z is a coordination ligand;
each L is a monovalent, bivalent, or trivalent anionic ligand;
n is an integer from 1 to 6;
m is an integer from 1 to 3;
k has the value of 2 when X is nitrogen, and k has the value of 1 when X
is oxygen or sulfur;
X and Y are heteroatoms each independently selected from nitrogen, phosphorus,
oxygen and sulfur;
R is a non-bulky substituent that has relatively low steric hindrance with
respect to the X substituent and is a straight or branched chain alkyl group; and
R′ is a bulky substituent with respect to Y and is selected from
alkyl, alkenyl, cycloalkyl, heterocyclic (both heteroalkyl and heteroaryl), alkylaryl,
arylalkyl, and polymeric groups.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst precursors of the present invention will be represented by one of
the formulae:
##STR4##
wherein T is a bridging group containing 2 or more bridging atoms, wherein
at least one of the bridging atoms is at least one Group 14 element, preferably
a carbon atom, and wherein T can also contain one or more elements selected from
Groups 13 to 16 of the Periodic Table of the Elements. It is preferred that all
of the bridging atoms be carbon atoms. The total number of non-hydrogen atoms can
be from about 1 to 50, preferably from about 1-20, and more preferably less than
about 10. The most preferred T groups are those where there is a dimethyl grouping
adjacent to Y.
Non-limiting examples of preferred bridging groups include:
##STR5##
##STR6##
##STR7##
The X and Y substituents are included for convenience.
M is a metallic element selected from Groups 1 to 15, preferably from Groups 3
to 13, more preferably from the transition metals of Groups 3 to 7, and the Lanthanide
series of the Periodic Table of the Elements. The Periodic Table of the Elements
referred to herein is that table that appears in the inside front cover of Lange's
Handbook of Chemistry, 15
th Edition, 1999, McGraw Hill Handbooks.
Z is a coordination ligand. Preferred coordination ligands include triphenylphosphine,
tris(C
1-C
6 alkyl) phosphine, tricycloalkyl phosphine, diphenyl
alkyl phosphine, dialkyl phenyl phosphine, trialkylamine, arylamine such as pyridine,
substituted or unsubstituted C
2 to C
20 alkenes (e.g. ethylene,
propylene, butene, hexene, octane, decene, dodecene, allyl, and the like) in which
the substituent is a halogen atom (preferably chloro), an ester group, a C
1
to C
4 alkoxy group, an amine group (—NR
2 where
each R individually is a C
1 to C
3 alkyl), carboxylic acid,
di(C
1 to C
4) alkyl ether, tetrahydrofuran (THF), a nitrile
such a acetonitrile, an η
4-diene, and the like.
Each L is a monovalent, bivalent, or trivalent anionic ligand, preferably containing
from about 1 to 50 non-hydrogen atoms, more preferably from about 1 to 20 non-hydrogen
atoms and is independently selected from the group consisting of halogen containing
groups; hydrogen; alkyl; aryl; alkenyl; alkylaryl; arylalkyl; hydrocarboxy; amides,
phosphides; sulfides; silyalkyls; diketones; borohydrides; and carboxylates. More
preferred are alkyl, arylalkyl, and halogen containing groups.
n is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3.
X and Y are each independently selected from nitrogen, sulfur, oxygen, and phosphorus;
more preferably both X and Y are nitrogen.
R is a non-bulky substituent that has relatively low steric hindrance with respect
to the X substituent. By low steric hindrance we mean that there will be no branching
within 3 atoms of X. Non-limiting examples of non-bulky substituents include C1
to C
30 straight and branched chain alkyl groups, preferably a C
1
to C
20 straight chain group; and more preferably an n-octyl group.
If the non-bulky group is branched, the branch point must be at least 3 atoms removed
from X.
R′ is a bulky substituent. That is, a sterically hindering group
with respect to the Y substituent and thus there can be branching within 3 atoms
of Y. R′ can be selected from alkyl, alkenyl, cycloalkyl, heterocyclic (both
heteroalkyl and heteroaryl), alkylaryl, arylalkyl, and polymeric, including inorganics
such as the P—N ring structures set forth below and inorganic-organic hybrid
structures, such as those set forth below. It is preferred that the R′ substituent
contain from about 3 to 50, more preferably from about 3 to 30 non-hydrogen atoms,
and most preferably from about 4 to 20 atoms. Also, one or more of the carbon or
hydrogen positions can be substituted with an element other than carbon and hydrogen,
preferably an element selected from Groups 14 to 17, more preferably a Group 14
element such as silicon, a Group 15 element such as nitrogen, a Group 16 element
such as oxygen, or a Group 17 halogen.
In a preferred embodiment two or three of W, R and R′ are co-joined to
form a ring structure.
Non-limiting examples of R′ include:
##STR8##
##STR9##
##STR10##
##STR11##
It is preferred that the total number of non-hydrogen atoms for the sum of all
R" groups be up to about 40 atoms. It is also preferred that the R" be selected
from hydrogen, halogen, halogen-containing groups, and C
1 to C
30
alkyl, aryl, alklyaryl, arylalkyl, cycloalkyl, and heterocyclic groups as
defined above; more preferably R" is selected from C
2 to C
20 alkyl,
aryl, alklyaryl, cycloalkyl, or heterocyclic; and most preferably R" is a C
5
to C
20 arylalkyl group.
The catalyst precursors may be prepared by any suitable synthesis method and
the method of synthesis is not critical to the present invention. One useful method
of preparing the catalyst precursors of the present invention is by reacting a
suitable metal compound, preferably one having a displaceable anionic ligand, with
a heteroatom-containing ligand of this invention. Non-limiting examples of suitable
metal compounds include organometallics, metal halids, sulfonates, carboxylates,
phosphates, organoborates (including fluoro-containing and other subclasses), acetonacetonates,
sulfides, sulfates, tetrafluoroborates, nitrates, perchlorates, phenoxides, alkoxides,
silicates, arsenates, borohydrides, naphthenates, cyclooctadienes, diene conjugated
complexes, thiocynates, cyanates, and the metal cyanides. Preferred are the organometallics
and the metal halides. More preferred are the organometallics.
As previously mentioned, the metal of the organometal compound may be selected
from Groups 1 to 16, preferably it is a transition metal selected from Groups 3
to 13 elements and Lanthanide series elements. It is also preferred that the metal
be selected from Groups 3 to 7 elements. It is particularly preferred that the
metal be a Group 4 metal, more particularly preferred is zirconium and hafnium,
and most particularly preferred is zirconium.
The transition metal compound can, for example, be a metal hydrocarbyl such as:
a metal alkyl, a metal aryl, a metal arylalkyl; a metal silylalkyl; a metal diene,
a metal amide; or a metal phosphide. Preferably, the transition metal compound
is a zirconium or hafnium hydrocarbyl. More preferably, the transition metal compound
is a zirconium arylalkyl. Most preferably, the transition metal compound is tetrabenzylzirconium.
Examples of useful and preferred transition metal compounds include:
(i) tetramethylzirconium, tetraethylzirconium, zirconiumdichloride (η4-1,4-diphenyl-1,3-butadiene),
bis (triethylphosphine) and zirconiumdichloride (η4-1,4-diphenyl-1,3-butadiene)
bis (tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]zirconium, tetrakis[dimethylamino]zirconium,
dichlorodibenzylzirconium, chlorotribenzylzirconium, trichlorobenzylzirconium,
bis[dimethylamino]bis[benzyl]zirconium, and tetrabenzylzirconium;
(ii) tetramethyltitanium, tetraethyltitanium, titaniumdichloride (η4-1,4-diphenyl-1,3-butadiene),
bis (triethylphosphine) and titaniumdichloride (η4-1,4-diphenyl-1,3-butadiene)
bis (tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]titanium, tetrakis[dimethylamino]titanium,
dichlorodibenzyltitanium, chlorotribenzyltitanium, trichlorobenzyltitanium, bis[dimethylamino]bis[benzyl]titanium,
and tetrabenzyltitanium; and
(iii) tetramethylhafnium, tetraethylhafnium, hafniumdichloride (η4-1,4-diphenyl-1,3-butadiene),
bis (triethylphosphine) and hafniumdichloride (η4-1,4-diphenyl-1,3-butadiene)
bis (tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]hafnium, tetrakis[dimethylamino]hafnium,
dichlorodibenzylhafnium, chlorotribenzylhafnium, trichlorobenzylhafnium, bis[dimethylamino]bis[benzyl]hafnium,
and tetrabenzylhafnium.
Non-limiting examples of preferred catalyst precursors of the present
invention when both X and Y are nitrogen are:
##STR12##
Non-limiting examples of catalyst precursors of the present invention
when X is oxygen and Y is nitrogen are:
##STR13##
This invention further relates to a polymer produced therefrom, particularly
to unique polyethylene resins.
The catalyst precursors can be prepared by any suitable synthesis method and
the method of synthesis is not critical to the present invention. One useful method
of preparing the catalyst precursors of the present invention is represented by
the following reaction scheme:
##STR14##
Single site-like catalysts can be prepared from the catalyst precursors of
the present invention by reacting them, under suitable conditions, with a transition
metal compound.
The metal of the transition metal compound may be selected from Group 3 to 13
elements and Lanthanide series elements. Preferably, the metal is a Group 4 element.
More preferably the metal is zirconium.
The transition metal compound for example may be a metal hydrocarbyl such as
a metal alkyl, metal aryl, or metal arylalkyl. Metal silylalkyls, metal amides,
or metal phosphides may also be used. Preferably, the transition metal compound
is a zirconium hydrocarbyl. More preferably, the transition metal compound is a
zirconium arylalkyl. Most preferably, the transition metal compound is tetrabenzylzirconium.
Examples of useful transition metal compounds are tetramethylzirconium,
tetraethylzirconium, tetrakis[trimethylsilylmethyl]zirconium, tetrakis [dimethylamino]zirconium,
dichlorodibenzylzirconium, chlorotribenzylzirconium, trichlorobenzylzirconium,
bis[dimethylamino]bis[benzyl]zirconium, and tetrabenzylzirconium.
Examples of useful transition metal compounds are tetramethyltitanium, tetraethyltitanium,
tetrakis[trimethylsilylmethyl]-titanium, tetrakis[dimethylamino]titanium, dichlorodibenzyltitanium,
chlorotribenzyltitanium, trichlorobenzyltitanium, bis[dimethylamino]bis[benzyl]titanium,
and tetrabenzyltitanium.
Examples of useful transition metal compounds are tetramethylhafnium, tetraethylhafnium,
tetrakis[trimethylsilylmethyl]hafnium, tetrakis[dimethylamino]hafnium, dichlorodibenzylhafnium,
chlorotribenzylhafnium, trichlorobenzylhafnium, bis[dimethylamino]bis[benzyl]hafnium,
and tetrabenzylhafnium.
For example, when the transition metal compound is tetrabenzylzirconium, the
corresponding catalyst precursor can be represented by:
##STR15##
Specific examples produce toluene as HL:
##STR16##
Activators and Activation Methods for Catalyst Compounds
The polymerization catalyst compounds of the invention are typically activated
in various ways to yield compounds having a vacant coordination site that will
coordinate, insert, and polymerize olefin(s). For the purposes of this patent specification
and appended claims, the term "activator" is defined to be any compound which can
activate any one of the catalyst compounds described above by converting the neutral
catalyst compound to a catalytically active catalyst compound cation. Non-limiting
activators, for example, include alumoxanes, aluminum alkyls, ionizing activators,
which may be neutral or ionic, and conventional-type cocatalysts.
A. Alumoxane and Aluminum Alkyl Activators
In one embodiment, alumoxanes activators are utilized as an activator in the
catalyst
composition of the invention. Alumoxanes are generally oligomeric compounds containing
—Al(R)—O— subunits, where R is an alkyl group. Examples of alumoxanes
include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane
and isobutylalumoxane. Alumoxanes may be produced by the hydrolysis of the respective
trialkylaluminum compound. MMAO may be produced by the hydrolysis of trimethylaluminum
and a higher trialkylaluminum such as triisobutylaluminum. MMAO's are generally
more soluble in aliphatic solvents and more stable during storage. There are a
variety of methods for preparing alumoxane and modified alumoxanes, non-limiting
examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352,
5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,
5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253,
5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European
publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665,
and PCT publications WO 94/10180 and WO 99/15534, all of which are herein fully
incorporated by reference. A another alumoxane is a modified methyl alumoxane (MMAO)
cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the
trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat.
No. 5,041,584).
Aluminum Alkyl or organoaluminum compounds which may be utilized as activators
include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
tri-n-octylaluminum and the like.
B. Ionizing Activators
It is within the scope of this invention to use an ionizing or stoichiometric
activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl)
boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl
boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric
acid (U.S. Pat. No. 5,942,459) or combination thereof. It is also within the scope
of this invention to use neutral or ionic activators alone or in combination with
alumoxane or modified alumoxane activators.
Examples of neutral stoichiometric activators include tri-substituted boron,
tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent
groups are each independently selected from alkyls, alkenyls, halogen, substituted
alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the three groups are
independently selected from halogen, mono or multicyclic (including halosubstituted)
aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl
groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy
groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms
(including substituted aryls). More preferably, the three groups are alkyls having
1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Even more preferably,
the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably,
the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.
Ionic stoichiometric activator compounds may contain an active proton, or some
other cation associated with, but not coordinated to, or only loosely coordinated
to, the remaining ion of the ionizing compound. Such compounds and the like are
described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375,
EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,
5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patent
application Ser. No. 08/285,380, filed Aug. 3, 1994, all of which are herein fully
incorporated by reference.
In a preferred embodiment, the stoichiometric activators include a cation and
an anion component, and may be represented by the following formula:
(L-H)
d+(A
d-) (X)
wherein L is an neutral Lewis base;
H is hydrogen;
(L-H)+ is a Bronsted acid;
Ad- is a non-coordinating anion having the charge d-;
d is an integer from 1 to 3.
The cation component, (L-H)
d+ may include Bronsted acids
such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating
or abstracting a moiety, such as an akyl or aryl, from the bulky ligand metallocene
or Group 15 containing transition metal catalyst precursor, resulting in a cationic
transition metal species.
The activating cation (L-H)
d+ may be a Bronsted acid, capable
of donating a proton to the transition metal catalytic precursor resulting in a
transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums
and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine,
diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,
methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,
phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine,
oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and
dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene
and mixtures thereof. The activating cation (L-H)
d+ may also
be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums
and mixtures, preferably carboniums and ferroceniums. Most preferably (L-H)
d+
is triphenyl carbonium.
The anion component A
d- include those having the formula [M
k+Q
n]
d-
wherein k is an integer from 1 to 3; n is an integer from 2-6; n-k=d; M is an element
selected from Group 13 of the Periodic Table of the Elements, preferably boron
or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido,
halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,
substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having
up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q
a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20
carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably
each Q is a pentafluoryl aryl group. Examples of suitable A
d- also include
diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated
herein by reference.
Most preferably, the ionic stoichiometric activator (L-H)
d+(A
d-)
is N,N-dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.
In one embodiment, an activation method using ionizing ionic compounds not containing
an active proton but capable of producing a bulky ligand metallocene catalyst cation
and their non-coordinating anion are also contemplated, and are described in EP-A-0
426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568, which are all herein incorporated
by reference.
Supports, Carriers and General Supporting Techniques
The catalyst system of the invention preferably includes a support material or
carrier, or a supported activator. For example, the catalyst compound of the invention
is deposited on, contacted with, vaporized with, bonded to, or incorporated within,
adsorbed or absorbed in, or on, a support or carrier.
A. Support Material
The support material is any of the conventional support materials. Preferably
the supported material is a porous support material, for example, talc, inorganic
oxides and inorganic chlorides. Other support materials include resinous support
materials such as polystyrene, functionalized or crosslinked organic supports,
such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites,
clays, or any other organic or inorganic support material and the like, or mixtures thereof.
The preferred support materials are inorganic oxides that include those Group
2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica, fumed
silica, alumina (WO 99/60033), silica-alumina and mixtures thereof. Other useful
supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No.
5,965,477), montmorillonite (European Patent EP-B1 0 511 665), phyllosilicate,
zeolites, talc, clays (U.S. Pat. No. 6,034,187) and the like. Also, combinations
of these support materials may be used, for example, silica-chromium, silica-alumina,
silica-titania and the like. Additional support materials may include those porous
acrylic polymers described in EP 0 767 184 B1, which is incorporated herein by
reference. Other support materials include nanocomposites as described in PCT WO
99/47598, aerogels as described in WO 99/48605, spherulites as described in U.S.
Pat. No. 5,972,510 and polymeric beads as described in WO 99/50311, which are all
herein incorporated by reference. A preferred support is fumed silica available
under the trade name Cabosil™ TS-610, available from Cabot Corporation.
Fumed silica is typically a silica with particles 7 to 30 nanometers in size that
has been treated with dimethylsilyldichloride such that a majority of the surface
hydroxyl groups are capped.
It is preferred that the support material, most preferably an inorganic oxide,
has a surface area in the range of from about 10 to about 700 m
2/g,
pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle
size in the range of from about 5 to about 500 μm. More preferably, the surface
area of the support material is in the range of from about 50 to about 500 m
2/g,
pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from
about 10 to about 200 μm. Most preferably the surface area of the support
material is in the range is from about 100 to about 400 m
2/g, pore volume
from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about
100 μm. The average pore size of the carrier of the invention typically has
pore size in the range of from 10 to 1000 Å, preferably 50 to about 500
Å, and most preferably 75 to about 350 Å.
The support materials may be treated chemically, for example with a fluoride
compound as described in WO 00/12565, which is herein incorporated by reference.
Other supported activators are described in for example WO 00/13792 that refers
to supported boron containing solid acid complex.
In a preferred method of forming a supported catalyst composition component,
the
amount of liquid in which the activator is present is in an amount that is less
than four times the pore volume of the support material, more preferably less than
three times, even more preferably less than two times; preferred ranges being from
1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range. In
an alternative embodiment, the amount of liquid in which the activator is present
is from one to less than one times the pore volume of the support material utilized
in forming the supported activator.
Procedures for measuring the total pore volume of a porous support are
well known in the art. Details of one of these procedures is discussed in Volume
1,
Experimental Methods in Catalytic Research (Academic Press, 1968) (specifically
see pages 67-96). This preferred procedure involves the use of a classical BET
apparatus for nitrogen absorption. Another method well known in the art is described
in Innes,
Total Porosity and Particle Density of Fluid Catalysts By Liquid Titration,
Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).
B. Supported Activators
In one embodiment, the catalyst composition includes a supported activator. Many
supported activators are described in various patents and publications which include:
U.S. Pat. No. 5,728,855 directed to the forming a supported oligomeric alkylaluminoxane
formed by treating a trialkylaluminum with carbon dioxide prior to hydrolysis;
U.S. Pat. Nos. 5,831,109 and 5,777,143 discusses a supported methylalumoxane made
using a non-hydrolytic process; U.S. Pat. No. 5,731,451 relates to a process for
making a supported alumoxane by oxygenation with a trialkylsiloxy moiety; U.S.
Pat. No. 5,856,255 discusses forming a supported auxiliary catalyst (alumoxane
or organoboron compound) at elevated temperatures and pressures; U.S. Pat. No.
5,739,368 discusses a process of heat treating alumoxane and placing it on a support;
EP-A-0 545 152 relates to adding a metallocene to a supported alumoxane and adding
more methylalumoxane; U.S. Pat. Nos. 5,756,416 and 6,028,151 discuss a catalyst
composition of a alumoxane impregnated support and a metallocene and a bulky aluminum
alkyl and methylalumoxane; EP-B1-0 662 979 discusses the use of a metallocene with
a catalyst support of silica reacted with alumoxane; PCT WO 96/16092 relates to
a heated support treated with alumoxane and washing to remove unfixed alumoxane;
U.S. Pat. Nos. 4,912,075, 4,937,301, 5,008,228, 5,086,025, 5,147,949, 4,871,705,
5,229,478, 4,935,397, 4,937,217 and 5,057,475, and PCT WO 94/26793 all directed
to adding a metallocene to a supported activator; U.S. Pat. No. 5,902,766 relates
to a supported activator having a specified distribution of alumoxane on the silica
particles; U.S. Pat. No. 5,468,702 relates to aging a supported activator and adding
a metallocene; U.S. Pat. No. 5,968,864 discusses treating a solid with alumoxane
and introducing a metallocene; EP 0 747 430 A1 relates to a process using a metallocene
on a supported methylalumoxane and trimethylaluminum; EP 0 969 019 A1 discusses
the use of a metallocene and a supported activator; EP-B2-0 170 059 relates to
a polymerization process using a metallocene and a organo-aluminuim compound, which
is formed by reacting aluminum trialkyl with a water containing support; U.S. Pat.
No. 5,212,232 discusses the use of a supported alumoxane and a metallocene for
producing styrene based polymers; U.S. Pat. No. 5,026,797 discusses a polymerization
process using a solid component of a zirconium compound and a water-insoluble porous
inorganic oxide preliminarily treated with alumoxane; U.S. Pat. No. 5,910,463 relates
to a process for preparing a catalyst support by combining a dehydrated support
material, an alumoxane and a polyfunctional organic crosslinker; U.S. Pat. Nos.
5,332,706, 5,473,028, 5,602,067 and 5,420,220 discusses a process for making a
supported activator where the volume of alumoxane solution is less than the pore
volume of the support material; WO 98/02246 discusses silica treated with a solution
containing a source of aluminum and a metallocene; WO 99/03580 relates to the use
of a supported alumoxane and a metallocene; EP-A1-0 953 581 discloses a heterogeneous
catalytic system of a supported alumoxane and a metallocene; U.S. Pat. No. 5,015,749
discusses a process for preparing a polyhydrocarbyl-alumoxane using a porous organic
or inorganic imbiber material; U.S. Pat. Nos. 5,446,001 and 5,534,474 relates to
a process for preparing one or more alkylaluminoxanes immobilized on a solid, particulate
inert support; and EP-A1-0 819 706 relates to a process for preparing a solid silica
treated with alumoxane. Also, the following articles, also fully incorporated herein
by reference for purposes of disclosing useful supported activators and methods
for their preparation, include: W. Kaminsky, et al., "Polymerization of Styrene
with Supported Half-Sandwich Complexes", Journal of Polymer Science Vol. 37, 2959-2968
(1999) describes a process of adsorbing a methylalumoxane to a support followed
by the adsorption of a metallocene; Junting Xu, et al. "Characterization of isotactic
polypropylene prepared with dimethylsilyl bis(1-indenyl)zirconium dichloride supported
on methylaluminoxane pretreated silica", European Polymer Journal 35 (1999) 1289-1294,
discusses the use of silica treated with methylalumoxane and a metallocene; Stephen
O'Brien, et al., "EXAFS analysis of a chiral alkene polymerization catalyst incorporated
in the mesoporous silicate MCM-41" Chem. Commun. 1905-1906 (1997) discloses an
immobilized alumoxane on a modified mesoporous silica; and F. Bonini, et al., "Propylene
Polymerization through Supported Metallocene/MAO Catalysts: Kinetic Analysis and
Modeling" Journal of Polymer Science, Vol. 33 2393-2402 (1995) discusses using
a methylalumoxane supported silica with a metallocene. Any of the methods discussed
in these references are useful for producing the supported activator component
utilized in the catalyst composition of the invention and all are incorporated
herein by reference.
In another embodiment, the supported activator, such as supported alumoxane,
is
aged for a period of time prior to use herein. For reference please refer to U.S.
Pat. Nos. 5,468,702 and 5,602,217, incorporated herein by reference.
In an embodiment, the supported activator is in a dried state or a solid. In
another
embodiment, the supported activator is in a substantially dry state or a slurry,
preferably in a mineral oil slurry.
In another embodiment, two or more separately supported activators are used,
or
alternatively, two or more different activators on a single support are used.
In another embodiment, the support material, preferably partially or totally
dehydrated
support material, preferably 200° C. to 600° C. dehydrated silica, is
then contacted with an organoaluminum or alumoxane compound. Preferably in an embodiment
where an organoaluminum compound is used, the activator is formed in situ on and
in the support material as a result of the reaction of, for example, trimethylaluminum
and water.
In another embodiment, Lewis base-containing supports are reacted with a Lewis
acidic activator to form a support bonded Lewis acid compound. The Lewis base hydroxyl
groups of silica are exemplary of metal/metalloid oxides where this method of bonding
to a support occurs. This embodiment is described in U.S. patent application Ser.
No. 09/191,922, filed Nov. 13, 1998, which is herein incorporated by reference.
Other embodiments of supporting an activator are described in U.S. Pat. No.
5,427,991, where supported non-coordinating anions derived from trisperfluorophenyl
boron are described; U.S. Pat. No. 5,643,847 discusses the reaction of Group 13
Lewis acid compounds with metal oxides such as silica and illustrates the reaction
of trisperfluorophenyl boron with silanol groups (the hydroxyl groups of silicon)
resulting in bound anions capable of protonating transition metal organometallic
catalyst compounds to form catalytically active cations counter-balanced by the
bound anions; immobilized Group IIIA Lewis acid catalysts suitable for carbocationic
polymerizations are described in U.S. Pat. No. 5,288,677; and James C. W. Chien,
Jour. Poly. Sci.: Pt A: Poly. Chem, Vol. 29, 1603-1607 (1991), describes the olefin
polymerization utility of methylalumoxane (MAO) reacted with silica (SiO
2)
and metallocenes and describes a covalent bonding of the aluminum atom to the silica
through an oxygen atom in the surface hydroxyl groups of the silica.
In a preferred embodiment, a supported activator is formed by preparing in an
agitated, and temperature and pressure controlled vessel a solution of the activator
and a suitable solvent, then adding the support material at temperatures from 0°
C. to 100° C., contacting the support with the activator solution for up to
24 hours, then using a combination of heat and pressure to remove the solvent to
produce a free flowing powder. Temperatures can range from 40 to 120° C. and
pressures from 5 psia to 20 psia (34.5 to 138 kPa). An inert gas sweep can also
be used in assist in removing solvent. Alternate orders of addition, such as slurrying
the support material in an appropriate solvent then adding the activator, can be used.
Polymerization Process
The catalyst systems prepared and the method of catalyst system addition described
above are suitable for use in any prepolymerization and/or polymerization process
over a wide range of temperatures and pressures. The temperatures may be in the
range of from -60° C. to about 280° C., preferably from 50° C. to
about 200° C., and the pressures employed may be in the range from 1 atmosphere
to about 500 atmospheres or higher.
Po
