Hafnium transition metal catalyst compounds, catalyst systems and their use in a polymerization process

The present invention relates to a Group 15 containing hafnium catalyst compound, a catalyst system and a supported catalyst system thereof and to a process for polymerizing olefin(s) utilizing them.

FIELD OF THE INVENTION
 The present invention relates to a Group 15 containing hafnium transition
 metal catalyst compound, a catalysts system thereof and its use in the
 polymerization of olefin(s).
 BACKGROUND OF THE INVENTION
 Advances in polymerization and catalysis have resulted in the capability to
 produce many new polymers having improved physical and chemical properties
 useful in a wide variety of superior products and applications. With the
 development of new catalysts the choice of polymerization-type (solution,
 slurry, high pressure or gas phase) for producing a particular polymer has
 been greatly expanded. Also, advances in polymerization technology have
 provided more efficient, highly productive and economically enhanced
 processes. Especially illustrative of these advances is the development of
 technology utilizing bulky ligand metallocene-type catalyst systems.
 More recently, developments have lead to the discovery of anionic,
 multidentate heteroatom ligands as discussed by the following articles:
 (1) Kempe et al., "Aminopyridinato Ligands--New Directions and
 Limitations", 80.sup.th Canadian Society for Chemistry Meeting, Windsor,
 Ontario, Canada, Jun. 1-4, 1997; (2) Kempe et al., Inorg. Chem. 1996 vol
 35 6742; (3) Jordan et al. of polyolefin catalysts based on
 hydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F., Organometallics
 1997, 16, 3282); (4) Horton, et.al., "Cationic Alkylzirconium Complexes
 Based on a Tridentate Diamide Ligand: New Alkene Polymerization
 Catalysts", Organometallics, 1996, 15, 2672-2674 relates to tridentate
 zirconium complexes; (5) Baumann, et al., "Synthesis of Titanium and
 Zirconium Complexes that Contain the Tridentate Diamido Ligand
 [((t-Bu-d.sub.6)N--O--C.sub.6 H.sub.4).sub.2 O].sup.2- {[NON}.sup.2-) and
 the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2", Journal of
 the American Chemical Society, Vol. 119, pp. 3830-3831; (6) Cloke et al.,
 "Zirconium Complexes incorporating the New Tridentate Diamide Ligand
 [(Me.sub.3 Si)N{CH.sub.2 CH.sub.2 N(SiMe.sub.3)}.sub.2 ].sup.2- (L); the
 Crystal Structure of [Zr(BH.sub.4).sub.2 L] and [ZrCl{CH(SiMe.sub.3).sub.2
 }L]", J. Chem. Soc. Dalton Trans, pp. 25-30, 1995; (7) Clark et al.,
 "Titanium (IV) complexes incorporating the aminodiainide ligand
 [(SiMe.sub.3)N{CH.sub.2 CH.sub.2 N(SiMe.sub.3)}.sub.2 ].sup.2-( L); the
 X-ray crystal structure of [TiMe.sub.2 (L)] and [TiCl{CH(SiMe.sub.3).sub.2
 }(L)]", Journal of Organometallic Chemistry, Vol 50, pp. 333-340, 1995;
 (8) Scollard et al., "Living Polymerization of alpha-olefins by Chelating
 Diamide Complexes of Titanium", J. Am. Chem. Soc., Vol 118, No. 41, pp.
 10008-10009, 1996; and (9) Guerin et al., "Conformationally Rigid Diamide
 Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives",
 Organometallics, Vol 15, No. 24, pp. 5085-5089, 1996.
 Furthermore, U.S. Pat. No. 5,576,460 describes a preparation of arylamine
 ligands and U.S. Pat. No. 5,889,128 discloses a process for the living
 polymerization of olefins using initiators having a metal atom and a
 ligand having two group 15 atoms and a group 16 atom or three group 15
 atoms. EP 893 454 A1 also describes preferably titanium transition metal
 amide compounds. In addition, U.S. Pat. No. 5,318,935 discusses amido
 transition metal compounds and catalyst systems especially for the
 producing isotactic polypropylene. Polymerization catalysts containing
 bidentate and tridentate ligands are further discussed in U.S. Pat. No.
 5,506,184.
 While all these compounds have been described in the art, there is still a
 need for an improved catalyst compound.
 SUMMARY OF THE INVENTION
 This invention provides for an improved catalyst compound, a catalyst
 system and for its use in a polymerizing process.
 In one embodiment, the invention is directed to a Group 15 containing
 hafnium catalyst compound, a catalyst system including the Group 15
 containing catalyst compound and to their use in the polymerization of
 olefin(s).
 In another embodiment, the invention is directed to a Group 15 containing
 bidentate or tridentate ligated hafnium transition metal catalyst
 compound, a catalyst system including the bidentate or tridentate ligated
 hafnium metal catalyst compound and to their use in the polymerization of
 olefin(s).
 In another embodiment, the invention is directed to a catalyst compound
 having a hafnium transition metal bound to at least one leaving group and
 also bound to at least two Group 15 atoms, at least one of which is also
 bound to a Group 15 or 16 atom through another group, a catalyst system of
 this hafnium transition metal compound and to their use in the
 polymerization of olefin(s).
 In still another embodiment, the invention is directed to a method for
 supporting the multidentate hafnium based catalysts system, and to the
 supported catalyst system itself.
 In another embodiment, the invention is directed to a process for
 polymerizing olefin(s), particularly in a gas phase or slurry phase
 process, utilizing any one of the catalyst systems or supports catalyst
 systems discussed above.
 DETAILED DESCRIPTION OF THE INVENTION
 Introduction
 It has unexpectedly been found that the hafnium based Group 15 containing
 catalyst compounds exhibit much higher catalyst productivity as compared
 to their zirconium or titanium analogs. As a result of this discovery it
 is now possible to provide a highly active polymerization with
 commercially acceptable level of productivity. Furthermore, it has also
 been discovered that these Group 15 containing hafnium catalyst compounds
 of the invention provide for an improved supported catalysts system,
 particularly for use in slurry phase or gas phase polymerizations. It is
 well known in the art that supporting catalyst compounds typically results
 in a lowering of the overall catalyst productivity. This in fact is the
 case with the zirconium analogs of the Group 15 containing hafnium
 compounds of the invention. As a result of this detrimental effect, the
 zirconium analogs are not well suited to being supported. However, as a
 result of the substantially higher activity of the hafnium based
 multidentate catalyst compounds of this invention, these catalysts
 compounds are supportable and retain commercially useful productivities.
 Group 15 Containing Hafnium Catalyst Compound and Catalyst Systems
 In one embodiment, the hafnium based catalyst compounds of the invention
 are Group 15 bidentate or tridentate ligated hafnium transition metal
 compound, the preferred Group 15 elements are nitrogen and/or phosphorous,
 most preferably nitrogen.
 The Group 15 containing hafnium catalyst compounds of the invention
 generally include a hafnium metal atom bound to at least one leaving group
 and also bound to at least two Group 15 atoms, at least one of which is
 also bound to a Group 15 or 16 atom through another group.
 In one preferred embodiment, at least one of the Group 15 atoms is also
 bound to a Group 15 or 16 atom through another group, which may be a
 hydrocarbon group, preferably a hydrocarbon group having 1 to 20 carbon
 atoms, a heteroatom containing group, preferably silicon, germanium, tin,
 lead, or phosphorus. In this embodiment, it is further preferred that the
 Group 15 or 16 atom be bound to nothing or a hydrogen, a Group 14 atom
 containing group, a halogen, or a heteroatom containing group.
 Additionally in these embodiment, it is preferred that each of the two
 Group 15 atoms are also bound to a cyclic group that may optionally be
 bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a
 heteroatom containing group.
 In an embodiment of the invention, the Group 15 containing hafnium compound
 of the invention is represented by the formulae:
 ##STR1##
 wherein
 M is hafnium; each X is independently a leaving group, preferably, an
 anionic leaving group, and more preferably hydrogen, a hydrocarbyl group,
 a heteroatom or a halogen, and most preferably an alkyl;
 y is 0 or 1 (when y is 0 group L' is absent);
 n is the oxidation state of M, preferably +2, +3 or +4, and more preferably
 +4;
 m is the formal charge of the YZL or the YZL' ligand, preferably 0, -1, -2
 or -3, and more preferably -2;
 L is a Group 15 or 16 element, preferably nitrogen;
 L' is a Group 15 or 16 element or Group 14 containing group, preferably
 carbon, silicon or germanium;
 Y is a Group 15 element, preferably nitrogen or phosphorus, and more
 preferably nitrogen;
 Z is a Group 15 element, preferably nitrogen or phosphorus, and more
 preferably nitrogen;
 R' and R.sup.2 are independently a C.sub.1 to C.sub.20 hydrocarbon group, a
 heteroatom containing group having up to twenty carbon atoms, silicon,
 germanium, tin, lead, or phosphorus, preferably a C.sub.2 to C.sub.20
 alkyl, aryl or arylalkyl group, more preferably a linear, branched or
 cyclic C.sub.2 to C.sub.20 alkyl group, most preferably a C.sub.2 to
 C.sub.6 hydrocarbon group;
 R.sup.3 is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom
 containing group, preferably a linear, cyclic or branched alkyl group
 having 1 to 20 carbon atoms, more preferably R.sup.3 is absent, hydrogen
 or an alkyl group, and most preferably hydrogen;
 R.sup.4 and R.sup.5 are independently an alkyl group, an aryl group,
 substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl
 group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or
 multiple ring system, preferably having up to 20 carbon atoms, more
 preferably between 3 and 10 carbon atoms, and even more preferably a
 C.sub.1 to C.sub.20 hydrocarbon group, a C.sub.1 to C.sub.20 aryl group or
 a C.sub.1 to C.sub.20 arylalkyl group, or a heteroatom containing group,
 for example PR.sub.3, where R is an alkyl group;
 R.sup.1 and R.sup.2 may be interconnected to each other, and/or R.sup.4 and
 R.sup.5 may be interconnected to each other;
 R.sup.6 and R.sup.7 are independently absent, or hydrogen, an alkyl group,
 halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or
 branched alkyl group having 1 to 20 carbon atoms, more preferably absent;
 and
 R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen,
 a heteroatom containing group.
 By "formal charge of the YZL or YZL' ligand", it is meant the charge of the
 entire ligand absent the metal and the leaving groups X.
 By "R.sup.1 and R.sup.2 may also be interconnected" it is meant that
 R.sup.1 and R.sup.2 may be directly bound to each other or may be bound to
 each other through other groups. By "R.sup.4 and R.sup.5 may also be
 interconnected" it is meant that R.sup.4 and R.sup.5 may be directly bound
 to each other or may be bound to each other through other groups.
 An alkyl group may be a linear, branched alkyl radicals, or alkenyl
 radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl
 radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio
 radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl
 radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,
 acyloxy radicals, acylamino radicals, aroylamino radicals, straight,
 branched or cyclic, alkylene radicals, or combination thereof. An
 arylalkyl group is defined to be a substituted aryl group.
 In a preferred embodiment R.sup.4 and R.sup.5 are independently a group
 represented by the following formula:
 ##STR2##
 wherein R.sup.8 to R.sup.12 are each independently hydrogen, a C.sub.1 to
 C.sub.40 alkyl group, a halide, a heteroatom, a heteroatom containing
 group containing up to 40 carbon atoms, preferably a C.sub.1 to C.sub.20
 linear or branched alkyl group, preferably a methyl, ethyl, propyl or
 butyl group, any two R groups may form a cyclic group and/or a
 heterocyclic group. The cyclic groups may be aromatic. In a preferred
 embodiment R.sup.9, R.sup.10 and R.sup.12 are independently a methyl,
 ethyl, propyl or butyl group (including all isomers), in a preferred
 embodiment R.sup.9, R.sup.10 and R.sup.12 are methyl groups, and R.sup.8
 and R.sup.11 are hydrogen.
 In a particularly preferred embodiment R.sup.4 and R.sup.5 are both a group
 represented by the following formula:
 ##STR3##
 In this embodiment, M is hafnium; each of L, Y, and Z is nitrogen; each of
 R.sup.1 and R.sup.2 is a hydrocarbyl group, preferably --CH.sub.2
 --CH.sub.2 --; R.sup.3 is hydrogen; and R.sup.6 and R.sup.7 are absent.
 In a particularly preferred embodiment the Group 15 containing metal
 compound is represented by the formula:
 ##STR4##
 Ph equals phenyl. For convenience the above formula will be referred to as
 Compound (1) (Hf--HN3).
 The Group 15 containing hafnium catalyst compounds of the invention are
 prepared by methods known in the art, such as those disclosed in EP 0 893
 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S. Pat. No.
 5,889,128 which are all herein incorporated by reference. U.S. application
 Ser. No. 09/312,878, filed May 17, 1999, discloses a gas or slurry phase
 polymerization process using a supported bisamide catalyst, which is also
 incorporated herein by reference. A preferred direct synthesis of these
 compounds comprises reacting the neutral ligand, (see for example YZL or
 YZL' of Formula I or II) with HfX.sub.n, is the oxidation state of Hf,
 each X is an anionic group, such as halide, in a non-coordinating or
 weakly coordinating solvent, such as ether, toluene, xylene, benzene,
 methylene chloride, and/or hexane or other solvent having a boiling point
 above 60.degree. C., at about 20.degree. C. to about 150.degree. C.
 (preferably 20.degree. C. to 100.degree. C.), preferably for 24 hours or
 more, then treating the mixture with an excess (such as four or more
 equivalents) of an alkylating agent, such as methyl magnesium bromide in
 ether. The magnesium salts are removed by filtration, and the metal
 complex isolated by standard techniques.
 In one embodiment the Group 15 containing hafnium catalyst compound is
 prepared by a method comprising reacting a neutral ligand, (see for
 example YZL or YZL' of formula 1 or 2) with a compound represented by the
 formula HfX.sub.n ( where n is the oxidation state of Hf, each X is an
 anionic leaving group) in a non-coordinating or weakly coordinating
 solvent, at about 20.degree. C. or above, preferably at about 20.degree.
 C. to about 100.degree. C., then treating the mixture with an excess of an
 alkylating agent, then recovering the metal complex. In a preferred
 embodiment the solvent has a boiling point above 60.degree. C., such as
 toluene, xylene, benzene, and/or hexane. In another embodiment the solvent
 comprises ether and/or methylene chloride, either being preferable.
 Activator and Activation Methods
 The above described Group 15 containing hafnium catalyst compounds are
 typically activated in various ways to yield catalyst compounds having a
 vacant coordination site that will coordinate, insert, and polymerize
 olefin(s).
 For the purposes of this patent specification and appended claims, the term
 "activator" is defined to be any compound or component or method which can
 activate any of the Group 15 containing bidentate or tridentate ligated
 hafnium catalyst compounds of the invention as described above.
 Non-limiting activators, for example may include a Lewis acid or a
 non-coordinating ionic activator or ionizing activator or any other
 compound including Lewis bases, aluminum alkyls, conventional-type
 cocatalysts and combinations thereof that can convert a neutral Group 15
 containing hafnium catalyst compound to a catalytically active Group 15
 containing hafnium cation. It is within the scope of this invention to use
 alumoxane or modified alumoxane as an activator, and/or to also use
 ionizing activators, neutral or ionic, such as tri (n-butyl) ammonium
 tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid
 precursor or a trisperfluoronaphtyl boron metalloid precursor,
 polyhalogenated heteroborane anions (WO 98/43983) or combination thereof,
 that would ionize the neutral catalyst compound. While most of the
 publications discussed herein refer to a bulky ligand metallocene-type
 catalyst, it contemplated that the activators and activation methods
 utilized for these bully-ligand metallocene-type catalyst compounds are
 applicable to the Group 15 containing hafnium catalyst compounds of this
 invention.
 In one embodiment, an activation method using ionizing ionic compounds not
 containing an active proton but capable of producing both a catalyst
 cation and a non-coordinating anion are also contemplated, and are
 described in EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568,
 which are all herein incorporated by reference.
 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 publication WO 94/10180, all
 of which are herein fully incorporated by reference.
 Organoaluminum compounds as activators include trimethylaluminum,
 triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,
 tri-n-octylaluminum and the like.
 Ionizing compounds may contain an active proton, or some other cation
 associated with but not coordinated to or only loosely coordinated to the
 remaining ion of the ionizing compound. Such compounds and the like are
 described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0
 495 375, EP-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.
 Other activators include those described in PCT publication WO 98/07515
 such as tris (2,2',2"-nonafluorobiphenyl) fluoroaluminate, which
 publication is fully incorporated herein by reference. Combinations of
 activators are also contemplated by the invention, for example, alumoxanes
 and ionizing activators in combinations, see for example, EP-B1 0 573 120,
 PCT publications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157
 and 5,453,410 all of which are herein fully incorporated by reference. WO
 98/09996 incorporated herein by reference describes activating catalyst
 compounds with perchlorates, periodates and iodates including their
 hydrates. WO 98/30602 and WO 98/30603 incorporated by reference describe
 the use of lithium (2,2'-bisphenyl-ditrimethylsilicate).4THF as an
 activator for a catalyst compound. WO 99/18135 incorporated herein by
 reference describes the use of organo-boron-aluminum activators. EP-B1-0
 781 299 describes using a silylium salt in combination with a
 non-coordinating compatible anion. Also, methods of activation such as
 using radiation (see EP-B1-0 615 981 herein incorporated by reference),
 electrochemical oxidation, and the like are also contemplated as
 activating methods for the purposes of rendering the neutral catalyst
 compound or precursor to a catalyst cation capable of polymerizing
 olefins. Other activators or methods for activating a catalyst compound
 are described in for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and
 5,869,723 and WO 98/32775, WO 99/42467
 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazoli
 de), which are herein incorporated by reference.
 In another embodiment, the invention provides for one or more Group 15
 containing hafnium catalyst compounds used in combination with one or more
 activators discussed above.
 It is further contemplated by the invention that other catalysts including
 bulky ligand metallocene-type catalyst compounds and/or conventional-type
 catalyst compounds can be combined with the Group 15 containing hafnium
 catalyst compounds of this invention.
 Supports, Carriers and General Supporting Techniques
 The above described Group 15 containing hafnium catalyst compounds and
 catalyst systems may be combined with one or more support materials or
 carriers using one of the support methods well known in the art or as
 described below. For example, in a most preferred embodiment, a Group 15
 containing hafnium catalyst compound or catalyst system is in a supported
 form, for example deposited on, contacted with, vaporized with, bonded to,
 or incorporated within, adsorbed or absorbed in, or on, a support or
 carrier.
 The terms "support" or "carrier" are used interchangeably and are any
 support material, preferably a porous support material, including
 inorganic or organic support materials. Non-limiting examples of inorganic
 support materials include inorganic oxides and inorganic chlorides. Other
 carriers include resinous support materials such as polystyrene,
 functionalized or crosslinked organic supports, such as polystyrene
 divinyl benzene polyolefins or polymeric compounds or any other organic or
 inorganic support material and the like, or mixtures thereof.
 The preferred carriers are inorganic oxides that include those Group 2, 3,
 4, 5, 13 or 14 metal oxides. The preferred supports include silica,
 alumina, silica-alumina, and mixtures thereof. Other useful supports
 include magnesia, titania, zirconia, magnesium chloride, montmorillonite
 (EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays 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.
 It is preferred that the carrier, most preferably an inorganic oxide, has a
 surface area in the range of from about 10 to about 100 m.sup.2 /g, pore
 volume in the range of from about 0.1 to about 4.0 cc/g and average
 particle size in the range of from about 5 to about 500 .mu.m. More
 preferably, the surface area of the carrier is in the range of from about
 50 to about 500 m.sup.2 /g, pore volume of from about 0.5 to about 3.5
 cc/g and average particle size of from about 10 to about 200 .mu.m. Most
 preferably the surface area of the carrier is in the range is from about
 100 to about 400 m.sup.2 /g, pore volume from about 0.8 to about 5.0 cc/g
 and average particle size is from about 5 to about 100 .mu.m. The average
 pore size of the carrier of the invention typically has pore size in the
 range of from 10 to 1000 .ANG., preferably 50 to about 500 .ANG., and most
 preferably 75 to about 450 .ANG..
 Examples of supporting catalyst systems again replacing the bulky ligand
 metallocene-type catalyst compound with the Group 15 containing hafnium
 catalyst compounds of the invention are described in U.S. Pat. Nos.
 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,
 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,
 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,
 5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,
 5,723,402, 5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and
 5,939,348 and U.S. application Ser. No. 271,598 filed Jul. 7, 1994 and
 Ser. No. 788,736 filed Jan. 23, 1997 and PCT publications WO 95/32995, WO
 95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494 all of which
 are herein fully incorporated by reference.
 There are various other methods in the art for supporting a polymerization
 catalyst compound or catalyst system of the invention. For example, the
 Group 15 containing hafnium catalyst compounds of the invention may
 contain a polymer bound ligand as described in U.S. Pat. Nos. 5,473,202
 and 5,770,755, which is herein fully incorporated by reference; the Group
 15 containing hafnium catalyst compounds of the invention may be spray
 dried as described in U.S. Pat. No. 5,648,310, which is herein fully
 incorporated by reference; the support used with the Group 15 containing
 hafnium catalyst compounds of the invention is functionalized as described
 in European publication EP-A-0 802 203, which is herein fully incorporated
 by reference, or at least one substituent or leaving group is selected as
 described in U.S. Pat. No. 5,688,880, which is herein fully incorporated
 by reference.
 In a preferred embodiment, the invention provides for a Group 15 containing
 hafnium catalyst system that includes an antistatic agent or surface
 modifier that is used in the preparation of the supported catalyst system
 as described in PCT publication WO 96/11960, which is herein fully
 incorporated by reference. The catalyst systems of the invention can be
 prepared in the presence of an olefin, for example hexene-1.
 In a preferred embodiment, the Group 15 containing hafnium catalyst system
 can be combined with a carboxylic acid salt of a metal ester, for example
 aluminum carboxylates such as aluminum mono, di- and tri-stearates,
 aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S.
 application Ser. No. 09/113,216, filed Jul. 10, 1998.
 A preferred method for producing a supported Group 15 containing hafnium
 catalyst system is described below and is described in U.S. application
 Ser. No. 265,533, filed Jun. 24, 1994 and Ser. No. 265,532, filed Jun. 24,
 1994 and PCT publications WO 96/00245 and WO 96/00243 both published Jan.
 4, 1996, all of which are herein fully incorporated by reference. In this
 preferred method, the Group 15 containing hafnium catalyst compound is
 slurried in a liquid to form a solution and a separate solution is formed
 containing an activator and a liquid. The liquid may be any compatible
 solvent or other liquid capable of forming a solution or the like with the
 Group 15 containing hafnium catalyst compounds and/or activator of the
 invention. In the most preferred embodiment the liquid is a cyclic
 aliphatic or aromatic hydrocarbon, most preferably toluene. The Group 15
 containing hafnium catalyst compounds and activator solutions are mixed
 together and added to a porous support such that the total volume of Group
 15 containing hafnium catalyst compound solution and the activator
 solution or the Group 15 containing hafnium catalyst compound solution and
 activator solution is less than four times the pore volume of the porous
 support, more preferably less than three times, even more preferably less
 than two times; preferred ranges being from 1.1 times to 3.5 times range
 and most preferably in the 1.2 to 3 times range.
 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).
 The most preferred methods for supporting the Group 15 metal hafnium
 compounds of the invention are described in U.S. application Ser. No.
 09/312,878, filed May 17, 1999, which is fully incorporated herein by
 reference.
 The mole ratio of the metal of the activator component to the metal of the
 supported Group 15 containing hafnium catalyst compound are in the range
 of between 0.3:1 to 1000:1, preferably 20:1 to 800:1, and most preferably
 50:1 to 500:1. Where the activator is an ionizing activator such as those
 based on the anion tetrakis(pentafluorophenyl)boron, the mole ratio of the
 metal of the activator component to the metal component of the Group 15
 containing hafnium catalyst compound is preferably in the range of between
 0.3:1 to 3:1.
 In one embodiment of the invention, olefin(s), preferably C.sub.2 to
 C.sub.30 olefin(s) or alpha-olefin(s), preferably ethylene or propylene or
 combinations thereof are prepolymerized in the presence of a supported
 Group 15 containing hafnium catalyst system of the invention prior to the
 main polymerization. The prepolymerization can be carried out batchwise or
 continuously in gas, solution or slurry phase including at elevated
 pressures. The prepolymerization can take place with any olefin monomer or
 combination and/or in the presence of any molecular weight controlling
 agent such as hydrogen. For examples of prepolymerization procedures, see
 U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and
 5,705,578 and European publication EP-B-0279 863 and PCT Publication WO
 97/44371 all of which are herein fully incorporated by reference.
 Polymerization Process
 The catalyst systems, supported catalyst systems or compositions of the
 invention 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.degree. C. to
 about 280.degree. C., preferably from 50.degree. C. to about 200.degree.
 C., and the pressures employed may be in the range from 1 atmosphere to
 about 500 atmospheres or higher.
 Polymerization processes include solution, gas phase, slurry phase and a
 high pressure process or a combination thereof. Particularly preferred is
 a gas phase or slurry phase polymerization of one or more olefins at least
 one of which is ethylene or propylene.
 In one embodiment, the process of this invention is directed toward a
 solution, high pressure, slurry or gas phase polymerization process of one
 or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to
 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is
 particularly well suited to the polymerization of two or more olefin
 monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,
 hexene-1, octene-1 and decene-1.
 Other monomers useful in the process of the invention include ethylenically
 unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or
 nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
 Non-limiting monomers useful in the invention may include norbornene,
 norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes,
 alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and
 cyclopentene.
 In the most preferred embodiment of the process of the invention, a
 copolymer of ethylene is produced, where with ethylene, a comonomer having
 at least one alpha-olefin having from 4 to 15 carbon atoms, preferably
 from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms,
 is polymerized in a gas phase process.
 In another embodiment of the process of the invention, ethylene or
 propylene is polymerized with at least two different comonomers,
 optionally one of which may be a diene, to form a terpolymer.
 In one embodiment, the invention is directed to a polymerization process,
 particularly a gas phase or slurry phase process, for polymerizing
 propylene alone or with one or more other monomers including ethylene,
 and/or other olefins having from 4 to 12 carbon atoms.
 Typically in a gas phase polymerization process a continuous cycle is
 employed where in one part of the cycle of a reactor system, a cycling gas
 stream, otherwise known as a recycle stream or fluidizing medium, is
 heated in the reactor by the heat of polymerization. This heat is removed
 from the recycle composition in another part of the cycle by a cooling
 system external to the reactor. Generally, in a gas fluidized bed process
 for producing polymers, a gaseous stream containing one or more monomers
 is continuously cycled through a fluidized bed in the presence of a
 catalyst under reactive conditions. The gaseous stream is withdrawn from
 the fluidized bed and recycled back into the reactor. Simultaneously,
 polymer product is withdrawn from the reactor and fresh monomer is added
 to replace the polymerized monomer. (See for example U.S. Pat. Nos.
 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922,
 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, all of which are
 fully incorporated herein by reference.)
 The reactor pressure in a gas phase process may vary from about 100 psig
 (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from
 about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in
 the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
 The reactor temperature in a gas phase process may vary from about
 30.degree. C. to about 120.degree. C., preferably from about 60.degree. C.
 to about 115.degree. C., more preferably in the range of from about
 70.degree. C. to 110.degree. C., and most preferably in the range of from
 about 70.degree. C. to about 95.degree. C.
 Other gas phase processes contemplated by the process of the invention
 include series or multistage polymerization processes. Also gas phase
 processes contemplated by the invention include those described in U.S.
 Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications
 EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all of
 which are herein fully incorporated by reference.
 In a preferred embodiment, the reactor utilized in the present invention is
 capable and the process of the invention is producing greater than 500 lbs
 of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or
 higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more
 preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably
 greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater
 than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than
 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000
 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
 A slurry polymerization process generally uses pressures in the range of
 from about 1 to about 50 atmospheres and even greater and temperatures in
 the range of 0.degree. C. to about 120.degree. C. In a slurry
 polymerization, a suspension of solid, particulate polymer is formed in a
 liquid polymerization diluent medium to which ethylene and comonomers and
 often hydrogen along with catalyst are added. The suspension including
 diluent is intermittently or continuously removed from the reactor where
 the volatile components are separated from the polymer and recycled,
 optionally after a distillation, to the reactor. The liquid diluent
 employed in the polymerization medium is typically an alkane having from 3
 to 7 carbon atoms, preferably a branched alkane. The medium employed
 should be liquid under the conditions of polymerization and relatively
 inert. When a propane medium is used the process must be operated above
 the reaction diluent critical temperature and pressure. Preferably, a
 hexane or an isobutane medium is employed.
 A preferred polymerization technique of the invention is referred to as a
 particle form polymerization, or a slurry process where the temperature is
 kept below the temperature at which the polymer goes into solution. Such
 technique is well known in the art, and described in for instance U.S.
 Pat. No. 3,248,179 which is fully incorporated herein by reference. Other
 slurry processes include those employing a loop reactor and those
 utilizing a plurality of stirred reactors in series, parallel, or
 combinations thereof. Non-limiting examples of slurry processes include
 continuous loop or stirred tank processes. Also, other examples of slurry
 processes are described in U.S. Pat. No. 4,613,484, which is herein fully
 incorporated by reference.
 In an embodiment the reactor used in the slurry process of the invention is
 capable of and the process of the invention is producing greater than 2000
 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000
 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540
 Kg/hr). In another embodiment the slurry reactor used in the process of
 the invention is producing greater than 15,000 lbs of polymer per hour
 (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to
 about 100,000 lbs/hr (45,500 Kg/hr).
 Examples of solution processes are described in U.S. Pat. Nos. 4,271,060,
 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, which are fully
 incorporated herein by reference.
 A preferred process of the invention is where the process, preferably a
 slurry or gas phase process is operated in the presence of Group 15
 containing hafnium catalyst system of the invention and in the absence of
 or essentially free of any scavengers, such as triethylaluminum,
 trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and
 diethyl aluminum chloride, dibutyl zinc and the like. This preferred
 process is described in PCT publication WO 96/08520 and U.S. Pat. Nos.
 5,712,352 and 5,763,543, which are herein fully incorporated by reference.
 In an embodiment, the method of the invention provides for injecting an
 unsupported Group 15 containing hafnium catalyst system into a reactor,
 particularly a gas phase reactor. In one embodiment the Group 15
 containing hafnium polymerization catalyst is used in the unsupported
 form, preferably in a liquid form such as described in U.S. Pat. Nos.
 5,317,036 and 5,693,727 and European publication EP-A-0 593 083, all of
 which are herein incorporated by reference. The polymerization catalyst in
 liquid form can be fed with an activator together or separately to a
 reactor using the injection methods described in PCT publication WO
 97/46599, which is fully incorporated herein by reference. Where an
 unsupported Group 15 containing hafnium catalyst compound is used the mole
 ratio of the metal of the activator component to the metal of the Group 15
 containing hafnium catalyst compound is in the range of between 0.3:1 to
 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to 2000:1.
 Polymer Products
 The polymers produced by the process of the invention can be used in a wide
 variety of products and end-use applications. The polymers produced by the
 process of the invention include linear low density polyethylene,
 elastomers, plastomers, high density polyethylenes, medium density
 polyethylenes, low density polyethylenes, polypropylene and polypropylene
 copolymers.
 The polymers, typically ethylene based polymers, have a density in the
 range of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from 0.88
 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to
 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95
 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc,
 and most preferably greater than 0.915 g/cc, preferably greater than 0.920
 g/cc, and most preferably greater than 0.925 g/cc. Density is measured in
 accordance with ASTM-D-1238.
 The polymers produced by the process of the invention typically have a
 molecular weight distribution, a weight average molecular weight to number
 average molecular weight (M.sub.w /M.sub.n) of greater than 1.5 to about
 15, particularly greater than 2 to about 10, more preferably greater than
 about 2.2 to less than about 8, and most preferably from 2.5 to 8.
 Also, the polymers of the invention typically have a narrow composition
 distribution as measured by Composition Distribution Breadth Index (CDBI).
 Further details of determining the CDBI of a copolymer are known to those
 skilled in the art. See, for example, PCT Patent Application WO 93/03093,
 published Feb. 18, 1993, which is fully incorporated herein by reference.
 The polymers of the invention in one embodiment have CDBI's generally in
 the range of greater than 50% to 100%, preferably 99%, preferably in the
 range of 55% to 85%, and more preferably 60% to 80%, even more preferably
 greater than 60%, still even more preferably greater than 65%.
 In another embodiment, polymers produced using a catalyst system of the
 invention have a CDBI less than 50%, more preferably less than 40%, and
 most preferably less than 30%.
 The polymers of the present invention in one embodiment have a melt index
 (MI) or (I.sub.2) as measured by ASTM-D-1238-E in the range from no
 measurable flow to 1000 dg/min, more preferably from about 0.01 dg/min to
 about 100 dg/min, even more preferably from about 0.1 dg/min to about 50
 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.
 The polymers of the invention in an embodiment have a melt index ratio
 (I.sub.21 /I.sub.2) (I.sub.21 is measured by ASTM-D-1238-F) of from 10 to
 less than 25, more preferably from about 15 to less than 25.
 The polymers of the invention in a preferred embodiment have a melt index
 ratio (I.sub.21 /I.sub.2) (I.sub.21 is measured by ASTM-D-1238-F) of from
 preferably greater than 25, more preferably greater than 30, even more
 preferably greater that 40, still even more preferably greater than 50 and
 most preferably greater than 65. In an embodiment, the polymer of the
 invention may have a narrow molecular weight distribution and a broad
 composition distribution or vice-versa, and may be those polymers
 described in U.S. Pat. No. 5,798,427 incorporated herein by reference.
 In yet another embodiment, propylene based polymers are produced in the
 process of the invention. These polymers include atactic polypropylene,
 isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.
 Other propylene polymers include propylene block or impact copolymers.
 Propylene polymers of these types are well known in the art see for
 example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and
 5,459,117, all of which are herein incorporated by reference.
 The Group 15 containing hafnium metal compound, when used alone, produces a
 high weight average molecular weight M.sub.w polymer (such as for example
 above 100,000, preferably above 150,000, preferably above 200,000,
 preferably above 250,000, more preferably above 300,000).
 The polymers of the invention may be blended and/or coextruded with any
 other polymer. Non-limiting examples of other polymers include linear low
 density polyethylenes, elastomers, plastomers, high pressure low density
 polyethylene, high density polyethylenes, polypropylenes and the like.
 Polymers produced by the process of the invention and blends thereof are
 useful in such forming operations as film, sheet, and fiber extrusion and
 co-extrusion as well as blow molding, injection molding and rotary
 molding. Films include blown or cast films formed by coextrusion or by
 lamination useful as shrink film, cling film, stretch film, sealing films,
 oriented films, snack packaging, heavy duty bags, grocery sacks, baked and
 frozen food packaging, medical packaging, industrial liners, membranes,
 etc. in food-contact and non-food contact applications. Fibers include
 melt spinning, solution spinning and melt blown fiber operations for use
 in woven or non-woven form to make filters, diaper fabrics, medical
 garments, geotextiles, etc. Extruded articles include medical tubing, wire
 and cable coatings, pipe, geomembranes, and pond liners. Molded articles
 include single and multi-layered constructions in the form of bottles,
 tanks, large hollow articles, rigid food containers and toys, etc.

EXAMPLES
 In order to provide a better understanding of the present invention
 including representative advantages thereof, the following examples are
 offered.
 Example 1
 Preparation of [(2,4,6-Me.sub.3 C.sub.6 H.sub.2)NHCH.sub.2 CH.sub.2]2 NH
 (Ligand)
 A 2 L one-armed Schlenk flask was charged with a magnetic stir bar,
 diethylenetriamine (23.450 g, 0.227 mol), mesityl bromide (90.51 g, 0.455
 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14 mmol),
 racemic-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (2.123 g, 3.41 mmol),
 sodium tert-butoxide (65.535 g, 0.682 mol), and toluene (800 mL). The
 reaction mixture was heated to 95C. and stirred. After 4 days the reaction
 was complete, as judged by proton NMR spectroscopy. All solvent was
 removed under vacuum and the residues dissolved in diethyl ether (1 L).
 The ether was washed three times with water (1 L) and saturated aqueous
 NaCl (500 mL) and dried over magnesium sulfate. Removal of the ether in
 vacuo yielded a red oil which was dried at 70 C. for 12 h under vacuum
 (yield: 71.10 g, 92%). .sup.1 H NMR .delta.6.83 (s, 4), 3.39 (br s, 2),
 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).
 .sup.13 C NMR .delta.143.74, 131.35, 129.83, 129.55, 50.17, 48.56, 20.70,
 18.51.
 Comparative Example 2
 Preparation of {[(2,4,6-Me.sub.3 C.sub.6 H.sub.2)NCH.sub.2 CH.sub.2]2
 NH}Zr(CH.sub.2 Ph).sub.2 (Zr--HN3)
 A 500 mL round bottom flask was charged with a magnetic stir bar,
 tetrabenzyl zirconium (41.729 g, 91.56 mmol), and 300 mL of toluene under
 dry, oxygen-free nitrogen. Solid triamine ligand above (32.773 g, 96.52
 mmol) was added with stirring over 1 minute (the desired compound
 precipitates). The volume of the slurry was reduced to 100 mL and 300 mL
 of pentane added with stirring. The solid yellow-orange product was
 collected by filtration and dried under vacuum (44.811 g, 80% yield).
 .sup.1 H NMR (C.sub.6 D.sub.6) .delta.7.22-6.81 (m, 12), 5.90 (d, 2), 3.38
 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41 (s, 6),
 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).
 Example 3
 Preparation of {[(2,4,6Me.sub.3 C.sub.6 H.sub.2)NCH.sub.2 CH.sub.2]2
 NH}Hf(CH.sub.2 Ph).sub.2 (Hf--HN3)
 A 250 mL round bottom flask was charged with a magnetic stir bar,
 tetrabenzyl hafnium (4.063 g, 7.482 mmol), and 150 mL of toluene under
 dry, oxygen-free nitrogen. Solid triamine ligand above (2.545 g, 7.495
 mmol) was added with stirring over 1 minute (the desired compound
 precipitates). The volume of the slurry was reduced to 30 mL and 120 mL of
 pentane added with stirring. The solid pale yellow product was collected
 by filtration and dried under vacuum (4.562 g, 87% yield). .sup.1 H NMR
 (C.sub.6 D.sub.6) .delta.7.21-6.79 (m, 12), 6.16 (d, 2), 3.39 (m, 2), 3.14
 (m, 2), 2.65 (s, 6), 2.40 (s, 6), 2.35 (m,2), 2.23 (m, 2), 2.19 (s, 6)
 1.60 (s, 2), 1.26 (s, 2), NH obscured.
 Comparative Example 4
 Preparation of Catalyst A
 To 1.335 g of MAO (4.450 g of a 30 weight percent solution in toluene,
 Albemarle) and 4.691 g of toluene in a 100 mL round bottom flask was added
 0.117 g of Zr--HN3 prepared in Comparative Example 2. The solution was
 stirred for 15 minutes. 3.550 g of silica (Crossfield ES-70, calcined at
 600.degree. C., available from Crosfield Limited, Warrington, England) was
 added followed by mixing. The mixture was dried overnight under vacuum.
 Dry Witco Aluminum Stearate #22 (AlSt #22) (CH.sub.3 (CH.sub.2).sub.16
 COO).sub.2 Al--OH available from Witco Corporation, Memphis, Tenn. (0.300
 g, 6 weight percent) was added with mixing to yielding 5.160 g of finished
 catalyst with a loading of 0.35 weight percent zirconium and an Al/Zr
 ratio of 120:1.
 Example 5
 Preparation of Catalyst B
 To 1.321 g of MAO (4.405 g of a 30 weight percent solution in toluene,
 Albemarle) and 4.717 g of toluene in a 100 mL round bottom flask was added
 0.133 g of Hf--HN3 prepared in Example 3. The solution was stirred for 15
 minutes. 3.546 g of silica (Crossfield ES-70, calcined at 600.degree. C.
 available from Crosfield Limited, Warrington, England) was added followed
 by mixing. The mixture was dried overnight under vacuum. Dry Witco
 Aluminum Stearate #22 (AlSt #22) (CH.sub.3 (CH.sub.2).sub.16 COO).sub.2
 Al--OH available from Witco Corporation, Memphis, Tenn. (0.300 g, 6 weight
 percent) was added with mixing to yielding 5.040 g of finished catalyst
 with a loading of 0.67 weight percent hafnium and an Al/Hf ratio of 120:1.
 Comparative Example 6
 Polymerization with Catalyst A
 Polymerization was performed in the slurry-phase in a 1-liter autoclave
 reactor equipped with a mechanical stirrer, an external water jacket for
 temperature control, a septum inlet and vent line, and a regulated supply
 of dry nitrogen and ethylene. The reactor was dried and degassed at
 160.degree. C. Isobutane (400 mL) was added as a diluent and 0.7 mL of a
 25 weight percent trioctyl aluminum solution in hexane was added as a
 scavenger using a gas tight syringe. The reactor was heated to 90.degree.
 C. 0.100 g of finished Catalyst A (Zr--HN3) above was added with ethylene
 pressure and the reactor was pressurized with 137 psi (945 kPa) of
 ethylene. The polymerization was continued for 30 minutes while
 maintaining the reactor at 90.degree. C. and 137 psi (945 kPa) by constant
 ethylene flow. The reaction was stopped by rapid cooling and vented. 21.0
 g of polyethylene was obtained (FI=no flow, activity=1198 g
 polyethylene/mmol catalyst.multidot.atm.multidot.h).
 Example 7
 Polymerization with Catalyst B
 Polymerization was performed in the slurry-phase in a 1-liter autoclave
 reactor equipped with a mechanical stirrer, an external water jacket for
 temperature control, a septum inlet and vent line, and a regulated supply
 of dry nitrogen and ethylene. The reactor was dried and degassed at
 160.degree. C. Isobutane (400 mL) was added as a diluent and 0.7 mL of a
 25 weight percent trioctyl aluminum solution in hexane was added as a
 scavenger using a gas tight syringe. The reactor was heated to 90.degree.
 C. 0.100 g of finished Catalyst B (Hf--HN3) above was added with ethylene
 pressure and the reactor was pressurized with 146 psi (1007 kPa) of
 ethylene. The polymerization was continued for 30 minutes while
 maintaining the reactor at 90.degree. C. and 146 psi (1007 kPa) by
 constant ethylene flow. The reaction was stopped by rapid cooling and
 vented. 36.7 g of polyethylene was obtained (FI=no flow, activity=1990 g
 polyethylene/mmol catalyst.multidot.atm.multidot.h).
 From the data presented above under similar conditions the Group 15
 containing hafnium catalyst compound of the invention has almost double
 the productivity as its zirconium analog.
 While the present invention has been described and illustrated by reference
 to particular embodiments, those of ordinary skill in the art will
 appreciate that the invention lends itself to variations not necessarily
 illustrated herein. For example, it is contemplated that two or more
 supported Group 15 containing catalyst compositions of the invention can
 be used. Also it is contemplated that a Group 15 containing hafnium
 catalyst compound can be used with a Group 15 containing titanium or
 zirconium catalyst compound. For this reason, then, reference should be
 made solely to the appended claims for purposes of determining the true
 scope of the present invention.