AU2003233649B2 - Solid, particulated, spray dried, heterogenous catalyst composition - Google Patents

Description

WO 03/102037 PCT/US03/16266 SOLID, PARTICULATED, SPRAY DRIED, HETEROGENOUS CATALYST COMPOSITION Cross Reference Statement This application claims the benefit of U.S. Provisional Application No. 60/385,796, filed June 3, 2002.

Background of the Invention The present invention relates to a solid, particulated, heterogeneous, catalyst composition comprising a Ziegler-Natta portion and a metallocene portion prepared by the technique of spray drying. The catalyst composition is useful for producing polyolefins, especially by polymerization of one or more olefin or diolefin monomers under slurry or gas phase polymerization conditions.

Catalyst compositions comprising a metallocene component, a Ziegler-Natta component and a support are disclosed in US-A's 5,747,405, 5,539,076, 5,395,810, 5,266,544, 5,183,867, 4,659,685; EP-A's 676,418, 717,755, 705,848, 747,402; and WO's 98/02245, 96/13532, 95/13871.

Spray drying Ziegler-Natta catalysts or metallocene catalysts, optionally in the presence of a filler such as silica, is disclosed by US-A's 5,567,665, 5,604,172, 5,652,314, 5,648,310, 5,672,669, and 5,674,795.

Summary of the Invention The invention provides a. solid, particulated, heterogeneous, catalyst composition for the polymerization of addition polymerizable monomers comprising: a) a Group 4 metallocene compound; b) a solid Group 4 metal-magnesium halide complex comprising moieties of at least magnesium, a Group 4 transition metal, and a halide; c) finely divided, inert filler, and d) an optional binder capable of joining components a) and b) and optionally c) into a particulated, heterogeneous, agglomerate without adversely affecting the catalytic properties thereof.

The invention also provides a process for preparing a solid, particulated, heterogeneous, catalyst composition for the polymerization of addition polymerizable monomers comprising forming a mixture comprising: a) a Group 4 metallocene compound; b) a solid Group 4 metal-magnesium halide complex comprising moieties of at least magnesium, a Group 4 transition metal, and a halide; c) finely divided inert filler, WO 03/102037 PCT/US03/16266 d) an optional binder capable of joining components a) and b) and optionally c) into a particulated, heterogeneous, agglomerate without adversely affecting the catalytic properties thereof; and e) an organic, volitile, liquid diluent; and spray drying the mixture to remove diluent and leave the product in the form of solid, agglomerated particles.

The invention further provides a process for producing polymers of addition polymerizable monomers, especially olefins, most especially ethylene homopolymers or copolymers, comprising: contacting ethylene and optionally a higher alpha-olefin monomer and/or a diene under polymerization conditions with a catalyst composition according to the present invention under gas phase or slurry polymerization conditions, desirably in the presence of one or more activating cocatalysts. The polymers resulting from the use of the present invented heterogeneous catalyst compositions typically possess broad molecular weights and/or bimodal molecular weight distributions compared to polymers formed by use of the individual catalyst components or by blending polymers prepared by either component of the catalyst composition alone.

Brief Description of the Drawing Figure 1 is a scanning tunneling electron micrograph (STEM) of representative particles of the solid, particulated, heterogeneous, catalyst composition prepared according to Example 4.

Detailed Description Of Preferred Embodiments All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1999. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. For purposes of United States patent practice, the contents of any patent, patent application or publication identified herein are hereby incorporated by reference in their entirety, especially with respect to the disclosure of structures, synthetic techniques and general knowledge in the art. The term "comprising" when used herein with respect to a composition, mixture or process is not intended to exclude the additional presence of any other compound, component or step. The term "aromatic" or "aryl" refers to a polyatomic, cyclic, ring system containing (45+2) re-electrons, wherein 6 is an integer greater than or equal to 1.

The Group 4 metallocene compound used as component a) is an organometallic coordination complex containing at least one x-bonded moiety in association with a Group 4 metal.

Particularly desirable are zirconium containing metal complexes (zirconocenes) containing from 1 WO 03/102037 PCT/US03/16266 to 3 x-bonded anionic or neutral ligand groups, which may be cyclic or non-cyclic delocalized tnbonded anionic ligand groups. Exemplary of such x-bonded anionic ligand groups are conjugated or nonconjugated, cyclic or non-cyclic dienyl groups, allyl groups, boratabenzene groups, phosphole, and arene groups. By the term "it-bonded" is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized i -bond.

Each atom in the delocalized -i-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and such hydrocarbyl- or hydrocarbyl-substituted metalloid radicals further substituted with a Group 15 or 16 heteroatom containing moiety. Included within the term "hydrocarbyl" are C1- 2 0 straight, branched and cyclic alkyl radicals, C 6 20 aromatic radicals, C7- 20 alkyl-substituted aromatic radicals, and C 7 20 aryl-substituted alkyl radicals. In addition two or more such radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may form a metallocycle with the metal. Suitable hydrocarbyl-substituted organometalloid radicals include mono-, di- and tri-substituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amine, phosphine, ether or thioether moieties or divalent derivatives thereof, e. g. amide, phosphide, ether or thioether groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group or to the hydrocarbylsubstituted metalloid containing group.

Examples of suitable anionic, delocalized i-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, phosphole, and boratabenzene groups, as well as hydrocarbyl- silyl- (including mono-, di-, or tri(hydrocarbyl)silyl) substituted derivatives thereof. Preferred anionic, delocalized 7t-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethyl(trimethylsilyl)-cyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.

The boratabenzenes are anionic ligands that are boron containing analogues to benzene.

They are previously known in the art having been described by G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). Preferred boratabenzenes correspond to the formula: WO 03/102037 PCT/US03/16266 R" R" R" B- R" R' R" wherein R" is selected from the group consisting of hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of such delocalized t-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analogues to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula:

R"

R"

R"

wherein R" is selected from the group consisting of hydrocarbyl, silyl, N,N-dihydrocarbylamino, or germyl, said R" having up to 20 non-hydrogen atoms, and optionally one or more R" groups may be bonded together forming a multicyclic fused ring system, or form a bridging group connected to the metal. In complexes involving divalent derivatives of such delocalized i-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system.

Phosphinimine/ cyclopentadienyl complexes are disclosed in EP-A-890581 and correspond to the formula 3 wherein: is a monovalent ligand, illustrated by hydrogen, halogen, or hydrocarbyl, or two groups together form a divalent ligand, is a Group 4 metal, Cp is cyclopentadienyl, or similar delocalized n-bonded group, L' is a monovalent ligand group, illustrated by hydrogen, halogen or hydrocarbyl, b is a number from 1 to 3; and n is 1 or 2.

A suitable class of catalysts are transition metal complexes corresponding to the formula: LptMXmX'nX",, or a dimer thereof wherein: Lp is an anionic, delocalized, T-bonded group that is bound to M, containing up to 50 non- WO 03/102037 PCT/US03/16266 hydrogen atoms, optionally two Lp groups may be joined together forming a bridged structure, and further optionally one Lp may be bound to X; M is a metal of Group 4 of the Periodic Table of the Elements in the +3 or +4 formal oxidation state; X is an optional, divalent group of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle with M; X' is an optional neutral ligand having up to 20 non-hydrogen atoms; X" each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally, two X" groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M, or, optionally 2 X" groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is n-bonded to M (whereupon M is in the +2 oxidation state), or further optionally one or more X" and one or more X' groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto by means of Lewis base functionality; t is 0, 1 or 2; mis 0 or 1; n is a number from 0 to 3; p is an integer from 0 to 3; and the sum, t+m+p, is equal to the formal oxidation state of M, except when 2 X" groups together form a neutral conjugated or non-conjugated diene that is n-bonded to M, in which case the sum t+m is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two Lp groups. The latter complexes include those containing a bridging group linking the two Lp groups. Preferred bridging groups are those corresponding to the formula (ER* 2

B(NR**

2 or B(NR** 2 2 wherein E is silicon, germanium, tin, or carbon, R* independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R* having up to carbon or silicon atoms, independently each occurrence is a group selected from silyl, hydrocarbyl, and combinations thereof, said having up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, R* independently each occurrence is methyl, ethyl, propyl, benzyl, butyl, phenyl, methoxy, ethoxy, or phenoxy, and is methyl, ethyl, propyl, benzyl or butyl.

Examples of the complexes containing two Lp groups are compounds corresponding to the formula: WO 03/102037 PCT/US03/16266 3

R

3

R

3 R R 3

R

3 R

R

3

R*

2 E) R** 2

NB

R

3 3 R3 R3 3 r3 R3 R3 (II) (III) wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;

R

3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R 3 having up to 20 nonhydrogen atoms, or adjacent R 3 groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, and X" independently each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X" groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a mcomplex with M, whereupon M is in the +2 formal oxidation state, and E and x are as previously defined, preferably (ER* 2 )x is dimethylsilandiyl or ethylene, and BNR** 2 is di(isopropyl)aminoborandiyl.

The foregoing metal complexes are especially suited for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex possesses C, symmetry or possesses a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized re-bonded systems, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include rac bis-indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232, 233-47, (1982).

Exemplary bridged ligands containing two n-bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien- -yl)silane, dimethylbis(2-t-butylcyclopentadien-1-yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden-l-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane, dimethylbis(fluoren-1-yl)silane, WO 03/102037 WO 03/02037PCT/US03/16266 dimethylbis(tetrahydrofluoren- 1-yl)silane, diinethylbis(2-mnethyl-4-phenylinden-1-yl)-silane, dimethylbis(2-methylinden-1-yl)silane, di(isopropyl)aminobis(cyclopentadien-l1-yl)borandiyl, di(isopropyl)aminobis(2-methyl-4-phenylinden- 1-yl)-borandiyl, di(isopropyl)aminobis(2methylinden- 1-yl)borandiyl, dimethyl(cyclopentadienyl)(fluoren- 1-yl)silane, dimethyl(cyclopentadienyl)(octahydrofluoren-1 -yl)silane, dimethyl(cyclopentadienyl)(tetrahydrofluoren- 1 -yl)silane, 1, 2, 2-tetramethy)-l, 2bis(cyclopentadienyl)disilane, 2-bis(eyclopentadienyl)ethane, and dimethyl(cyclopentadienyl)- 1- (fluoren- 1-yl)methane.

Preferred X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silyihydrocarbyl and aminohydrocarbyl groups, or two N' groups together form a divalent derivative of a conjugated diene or else together they form a neutral, it-bonded, conjugated diene.

Most preferred Y' groups are C 1 2 o hydrocarbyl groups.

Complexes containing two Lp groups including bridged complexes suitable for use in the present invention include: bis(cyclopentadienyl)zirconiumdimetliyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)zirconium methyl benzyl, bis(cyclopentadienyl)zirconium methyl phenyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadienyl)titanium-allyl, bis(cyclopentadienyl)zirconiummethylmethoxide, bis(cyclopentadienyl)zirconiummetliylchloride, bis(pentamethylcyclopentadienyl)zirconiumdimethyl, bis(pentamethylcyclopentadienyl)titaniumdimethyl, bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconiumdimethyl, bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl), bis(indenyl)zirconiummethyltrimethylsilyl, bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl, bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl, bis(pentamethylcyclopentadienyl)zirconiumdibenzyl, bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide, bis~pentainetliylcyclopenitadienyl)zirconiuilmethlylchloride, bis(methylethylcyclopentadienyl)zirconiumdimethyl, bis(butylcyclopentadienyl)zirconiumdibenzyl, WO 03/102037 WO 03/02037PCT/US03/16266 bis(t-butylcyclopentadienyl)zirconiumdimethyl, bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl, bis(methylpropylcyclopentadienyl)zirconiuamdibenzyl, bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl, dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl, dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III) allyl dimethylsilyl-bis(t-butylcyclopentadieny)zirconiumdibenzyl, dimethylsilyl-bis(n-butylcyclopentadienyl)zirconium bis(trimethylsilyl), (methylene-bis(tetramethylcyclopentadienyl)titaniuam(III) 2-(dimethylamino)benzyl, (methylene-bis(n-butylcyclopentadienyl)titanium(Ill) 2-(dimethylamino)benzyl, dimethylsilyl-bis(indenyl)zirconiumbenzylchloride, dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl, dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl, dimethylsilyl-bis(2-methylindenyl)zirconium-1 ,4-diphenyl- 1,3-butadiene, dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II) 1 ,4-diphenyl- 1,3-butadiene, dimethylsilyl-bis(tetrahydroindenyl)zirconium(II) 1 ,4-diphenyl- 1,3-butadiene, di(isopropylamino)borandiylbis(2-methyl-4-phenylindenyl)zirconium dimethyl, dimethylsilyl-bis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl), (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzy, and dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

A further class of metal complexes utilized in the present invention corresponds to the preceding formula LpiMXmX'nX"p, or a dimer thereof, wherein X is a divalent group of up to non-hydrogen atoms that together with Lp forms a metallocycle with M.

Preferred divalent X groups include groups containing up to 30 non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to the delocalized 7c-bonded group, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M.

A preferred class of such Group 4 metal coordination complexes used according to the present invention corresponds to the formula: WO 03/102037 WO 03/02037PCT/US03/16266 R2 M X" 2 P2 P2 wherein: M is titanium or zirconium, preferably titanium in the or +4 formal oxidation state;

W

3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R2 having up to 20 nonhydrogen atoms, or adjacent R2 groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, each X" is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to non-hydrogen atoms, or two X" groups together form a neutral C 5 3 0 conjugated diene or a divalent derivative thereof; Y is and Z is SiR* 2 CR*z, SiR* 2 SiR*2, CR* 2

CR*

2 CR* CR*, CR* 2 SiR* 2 GeR*2, or B(NR** 2 wherein R* and are as previously defined.

Illustrative Group 4 metal complexes of the latter formula that may be employed in the practice of the present invention include: cyclopentadienyltitaniumtrimethyl, indenyltitaniumtrimethyl, octahydrofluorenyltitaniumtrimethyl, tetrahydroindenyltitaniumtrimethyl, tetrahydrofluorenyltitaniumtrimethyl, (tert-butylamido)(1, 1 -dimethyl-2,3,4,9,1O-1j-1 ,4,5 ,6,7 ,8-bexahydronaphthalenyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)( 1, 1,2,3-tetramethyl-2,3,4,9, 1 0-i-i ,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl, (ter-t-butylamido)(tetramethyl-q 5 -cyclopentndienyl) dimethylsilanetitanium dibenzyl, (tert-butylamido)(tetramethyl-q 5 -cyclopentadiony)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-rl 5 -cyclopentadienyl)- 1,2-ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-1 5 -indenyl)dimethylsilanetitanium dimethyl, WO 03/102037 WO 03/02037PCT/US03/16266 (tert-butylamido)(tetramethy-- 5 -cyclopentadieny)dimethysilane titanium (III) 2-(dimethylamino)benzyl; (ter-t-butylamido)(tetramethyl--q 5 -cyclopentadienyl)dimethylsilanetitanium (III) allyl, (tert-b-Ltylamido)(tetramethyl-q.-cyclopentadieny1)dimethylsilanetitaniuim (III) 2,4-dimethylpentadieny1, (tert-butylarnido)(tetramethyl--I 5 -cyclopentadienyl)dimethylsilanetitanium (II) 1 ,4-diphenyl- 1,3-butadiene, (tert-butylamido)(tetramethy-q 5 _Cyclopentadieny1)dimethylsilanetitaniumn (II) 1 ,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 1 ,4-diplaenyl- 1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (TV) 2,3-dimethyl-1,3-buatadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (MV isoprene, (tert-butylamido)(2-methlylindenyl)dimethylsilanetitaniun (IV) 1 ,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1I,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) isoprene (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dimethyl (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dibenzyl (tert-butylamido)(2,3-dimetbylindenyl)dimethylsilanetitani-um (IV) 1 ,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (HI) I ,3-pentadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) I ,4-diphenyl- 1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 1 ,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (TV) dimethyl, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dibenzyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (HI) 1 ,4-diphenyl-1 ,3-butadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 1 ,3-pentadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (11) 2,4-hexacliene, (tert-butylamido)(tetramethy1 5 -cyclopentadieny1)dimethylsilanetitanium (IV) 1 ,3-butadiene, (te-rt-butylamido)(tetramnethyl-j 5 -cyclopentadienyl)dimethylsilanetitanium (MV 2,3-dimethyl- 1,3butadiene, (tert-butylamido)(tetramethy-r 5 -cyclopentadienyl)dimethylsilanetitanium (IV)isoprene, (tert-butylamido)(tetramethyl-Tl 5 -cyclopentadieny1)dimethylsilanetitanium (11) 1 ,4-dibenzyl- 1,3butadiene, (tert-butylamido)(tetramethylri 5 _Cyclopentadienyl)dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido)(tetramethy-i 5 -cyclopentadieny)dimethylsilanetitaniun (11) 3-methyl-I ,3pentadiene, WO 03/102037 WO 03/02037PCT/US03/16266 (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(1,1I-dimethyl-2,3,4,9,1 0--1 ,4,5,6,7 ,8-hexahydronaphthalen-4yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(1 1 ,2,3-tetramethyl-2,3,4,9, 10-rj-1 ,4,5,6,7,8-hexahydronaphthalen-4yl)dimethylsilanetitaniumdimethyl (tert-butylainido)(tetramethy1-, 5 -cyclopentadienyl methyiphenylsilanetitanium.(V dimethyl, (tert-butylamido)(tetramethy1_1 5 -cyclopentadienyl methyiphenylsilanetitanium (11) 1 ,4-diphenyl-l,3-butadiene, 1 -(tert-butylamido)-2-(tetramethyl--5cyclopentadieny1)ethanediyltitanium (IV) dimethyl, 1 -(tert-butylamido)-2-(tetramethyl-iI 5 -cyclopentadienyl)ethanediyl titanium (ID) 1 ,4-diphenyl- 1,3butadiene, (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium 2,3-dimethyl- 1,3-butadiene, (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) isoprene (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IN) dimethyl (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) dibenzyl (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitanium (IV) 1 ,3-butadiene, (tert-butylainido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitaniumi (1I) 1 ,3-pentadienie, (tert-butylamido)(3-(N-pyrrolyl)indenyl)dimethylsilanetitaniuni (11) 1 ,4-diphenyl 1 ,3-butadiene, and (tert-butylamido)(3-N-pyrrolidinylinden- 1-yl)dimethylsilanetitanium (IV) dimethyl.

Other catalysts, especially catalysts containing other Group 4 metals, will, of course, be apparent to those skilled in the art. Most highly preferred metal complexes for use herein are the following metal complexes: (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium dimethyl, (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,3-pentadiene, (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (II) 1,4 diphenyl-1 ,3-butadiene, (cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium dimethyl, cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (11) 1 ,3-pentadiene, cyclohexylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium (11) 1,4 diphenyl- 1,3butadiene, (cyclododecylamido)dimethyl(tetramnethylcyclopentadienyl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(tetramethylcyclopentadienyt)silanetitanium (II) 1 ,3-pentadiene, (cyclododecylamido)dimethyl(tetramnetbylcyclopentadienyl)silanetitanium (11)1,4 diphenyl- 1,3butadiene, WO 03/102037 WO 03/02037PCT/US03/16266 (t-butylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium dimethyl, (t-butylamnido)dimothyl(2-methyl-s-indacen-1 -yl)silanetitanium (11) I ,3-pentadienc, (t-butylamido)dimethyl(2-methyl-s-indacen-1 -yl)silanetitanium (11) 1,4 diphenyl-1,3-butadiene, (cyclohexylamido)dimethy1(2-methy1-s-indacen-1-y)silanetitanium dimethyl, cyclohexylamido)dimethyl(2-methyl-s-indacen-1 -yl)silanetitaniurn (II) 1 ,3-pentadiene, cyclohexylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4 diphenyl-1 ,3-butadiene, (cyclododecylamido)dimethyl(2-methyl-s-indacen- 1-yl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(2-methyl-s-indacen- 1-yl)silanetitanium(II) 1 ,3-pentadiene, (cyclododecylamido)dimethyl(2-methyl-s-indacen-1-yl)silanetitanium(II) 1,4 cliphenyl- 1,3butadiene, (t-butylamido)dimethiyl(3,4-(cyclopenta(lophenanthren- 1 -yl)silanetitanium dimethyl, (t-butylamido)dimethyl(3,4-(cyclopenta(Ophenanthren-1 -yl)silanetitanium(II) 1,3-pentadiene, (t-butylamido)dimethyl(3,4-(cyclopenta(Ophenanthren-1 -yl)silanetitanium(ll) 1,4 diphenyl- 1,3butadiene, (cyclohexylamido)dimethyl(3,4-(cyclopentaQophenanthren- 1 -yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(3,4-(cyclopentaQophenantbren- 1-yl)silanetitanium(fl) 1 ,3-pentadiene, cyclohexylarnido)dimethyl(3,4-(cyclopenta(lophenanthren- 1-yl)silanetitanium(II) 1,4 diphenyl-1 ,3butadiene, (cyclododecylamido)dimethyl(3,4-(cyclopenta(Tophenanthren- 1-yl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(3,4-(cyclopenta(l)phenanthren- 1-yl)silanetitanium(II) 1,3-pentadiene, (cyclododecylamido)dimethyl(3,4-(cyclopenta(benanthren-l1-yl)silanetitanium(L1) 1,4-diphenyl- 1 ,3-butadiene, (t-butylamnido)dimethyl(2-methyl-4-phenylinden-1 -yl)silanetitanium dimethyl, (t-butylamido)dimethyl(2-methyl-4-phenylinden-1-yl)silanetitanium(II) 1 ,3-pentadiene, (t-butylamido)dimeth-yl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1,4 diphenyl-1,3-butadiene, (cyclohexylamido)dimethyl(2-mnethyl-4-phenylinden- 1 -yl)silanetitanium dimethyl, cyclohexylamido)dimethyl(2-methyl-4-phenylinden-1I-yl)silanetitanium(II) 1 ,3-pentadiene, cyclohexylainido)dimethyl(2-methyl-4-phenylinden- I-yl)silanetitanium(II) 1,4 diphenyl- 1,3butadiene, (cyclododecylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium dimethyl, (cycle dodecylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1,3-pentadiene, (cyclododecylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1,4-diphenyl-1 ,3butadiene, (t-butylamido)dimethyl(2-methyl-4-phenylinden- 1-yI)silanetitaniurn dimethyl, (t-butylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium (II) 1 ,3-pentadiene, WO 03/102037 WO 03/02037PCT/US03/16266 (t-butylamido)dimethyl(2-methyl-4-phenylinden- 1-y1)silanetitanium (1I) 1,4 diphenyl-1,3-butadiene, (cyclohexylarnido)dimethyl(2-methyl-4-phenylinden-1 -yl)silanetitanium dimethyl, cyclohexylamido)dimeflayl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1 ,3-pentadiene, cyclohexylamnido)dimethyl(2-methyl-4-phenyinden-1 -yl)silanetitanium(II) 1,4 diphenyl-1 ,3butadiene, (cyclododecylamido)dimethyl(2-methyl-4-phenylinden-1 -yl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1 ,3-pentadiene, (cyclododecylamido)dimethyl(2-methyl-4-phenylinden- 1-yl)silanetitanium(II) 1,4 diphenyl- 1,3butadiene, (t-butylamido)dimethyl(3-(l-pyrrolidinyl)indei- 1-yl)silanetitanium dimethyl, (t-butylamido)dimethyl(3-(1 -pyrrolidinyl)inden- 1-yl)silanetitanium(II) 1 ,3-pentadiene, (t-butylamido)dimethyl(3-(1-pyrrolidinyl)inden- 1-yl)silanetitanium(II) 1,4 diphenyl- 1,3-butadiene, (cyclohexylamido)dimethyl(3-(1-pyrrolidinyl)inden- 1-yl)silanetitanium dimethyl, cyclohexylarnido)di-inethyl(3-(1-pyrrolidinyl)inden-l1-yl)silanetitanium(II) 1 ,3-pentadiene, cyclohexylamido)dimetliyl(3-(1-pyrrolidinyl)inden- 1-yl)silanetitanium(ll) 1,4 diphenyl- 1,3butadiene, (cyclododecylamido)dimethyl(3-( 1-pyrrolidinyl)inden-1-yl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(3-(l1-pyrrolidinyl)inden-1-yl)silanetitanium(H) 1 ,3-pentadiene, (cyclododecylamido)dimethyl(3-( 1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1,4 diphenyl- 1,3butadiene, (t-butylamido)dimethyl(3-(1 -pyrrolidinyl)inden- 1-yl)silanetitanium dimethyl, (t-butylamido)dimethyl(3-(l1-pyrrolidinyl)inden- 1-yl)silanetitanium (II) 1 ,3-pentadiene, (t-butylamido)dimethyl(3-( 1-pyrrolidinyl)inden- 1-y1)silantitanium (11) 1,4 diphenyl- 1,3-butadiene, (cyclohexylamido)dimethyl(3-(1 -pyrrolidinyl)inden- 1 -yl)silanetitanium dimethyl, cyclohexylarniido)dimethyl(3-(1 -pyrrolidinyl)inden- 1-yl)silanetitanium(II) 1 ,3-pentadiene, cyclohexylamido)dimetliyl(3-( 1-pyrrolidinyl)inden- 1-yl)silanetitanium(Il) 1,4 diphenyl- 1,3butadiene, (cyclododecylamido)dimethyl(3 -pyrrolidinyl)inden-1-yl)silanetitanium dimethyl, (cyclododecylamido)dimethyl(3-( 1-pyrrolidinyl)inden-1-yl)silanetitanium(II) 1 ,3-pentadiene, (cyclododecylamido)dimethyl(3-( 1-pyrrolidinyl)inden-1 -y1)silanetitanium(LI) 1,4 diphenyl-1 ,3butadiene, I ,2-ethanebis(inden-1 -yl)zirconium dimethyl, I ,2-elhanebis(inden- 1-yl)zirconiiurnl(II) 1 ,3-pentadieno, 1 ,2-ethanebis(inden-1 -yl)zirconium(II) 1,4 diphenyl- 1,3-butadiene, 1 ,2-ethanebis(2-methyl-4-phenylinden-1 -yl)zirconium dimethyl, WO 03/102037 WO 03/02037PCT/US03/16266 1 ,2-ethanebis(2-methyl-4-phenylinden-l-yl)zirconium(II) 1I,3-pentadiene, 1,2-ethanebis(2-methyl-4-phenylinden-1-yl)zirconium(llI) 1,4 diphenyl- 1,3-butadiene, dimethylsilanebis(inden-1 -yl)zirconium dimethyl, dimethylsilanebis(inden-1 -yl)zirconium(II) 1 ,3-pentadiene, dimethylsilanebis(inden-1 -yl)zirconium(II) 1,4 diphenyl- 1,3-butadiene, dimethylsilanebis(2-methay1-4-phenylinden- l-yl)zirconium dimethyl, dimethylsilanebis(2-methyl-4-phenylinden-1 -yl)zirconium(ll) 1,3-pentadiene, and dimethylsilanebis(2-methyl-4-phenylinden-1 -yl)zirconium(Jl) 1,4 diphenyl- 1,3-butadiene.

Additional examples of Group 4 metallocene compounds for use as component a) include: bis(cyclopentadienyl)titaninm dimethyl, bis(cyclopentadienyl)titaninm diphenyl, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)halhium dimethyl, bis(cyclopentadienyl)titanium di-neopentyl, bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium ethyl chloride, bis(cyclopentadienyl)titanium phenyl. chloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium ethyl chloride, bis(cyclopentadienyl)zirconim. phenyl chloride, bis(cyclopentadienyl)titanium methyl bromide;, cyclopentadienyl. titanium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl. zirconium trimethyl, cyclopentadienyl hafniumn triphenyl, cyclopentadienyl hafnium. trineopentyl, cyclopentadienyl hafnium trimethyl; pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichioride; bis(pentamethylcyclopentadienyl) titanium diphenyl, WO 03/102037 WO 03/02037PCT/US03/16266 methylenebis(cyclopentadienyl)titanium; bis(indenyl)titanium dimethyl, bis(indenyl)titanium dichloride, bis(methylcyclopentadienyl)titanium dimethyl, bis( 1,2-dimethylcyclopentadienlyl)zirconium dichioridle, bis( 1,2-dimethylcyclopentadienyl)zirconium dimethyl, bis( 1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, di(4-tolyl)methylene(cyclopentadienyl)(fluorenyl) zirconium dichloride, di(isopropyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(4-n-butylphenyl)methylene(cyclopentadienyl)(fluoreny) zirconium dichloride, di(tertbutyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl) zirconium dichloride, dichloride, isopropylidene(cyclopentadienyl)(fluorenyl) hafnium dichloride, di(4-tolyl)methylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, diisopropylmetliylene(cyclopentadienyt)(fluorenyt)hafhium dichloride, di(isobutyt)methylene(cyclopentadieny1)(fluorenyl)hafnium dichloride, di-t-butylmethylene(cyclopentadienyl)(fluorenyl)hafhiumn dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)hafhium dichloride, dichloride, isopropyl(cyclopentadienyl)(fluorenyl)titani-um dichloride, diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride, diisopropylmethylene(2,5 dimethylcyclopentadienyl tluorenyl)titanium dichioride, ethylencbis(indenyl)ziroonium dichloride, ,6,7-H-tetrahydroinden- 1 -yl)zirconiumn dichloride, dimethylsilylenebis(indenyl)zirconinm dichloride, dimethylsilylenebis(4,5,6,7-H-tetrahydroindenyl)zirconium dichloride, di(4-tolyl)silylene bis(1 -indenyl) zirconium dichloride, WO 03/102037 PCT/US03/16266 di(4-tolyl)silylene bis(4,5,6,7-H-tetrahydro-l-indenyl)zirconium dichloride, ethylidene (1-indenyl)(tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis(2-methyl-4-t-butyl-l-cyclopentadienyl) zirconium dichloride, ethylene bis(l-indenyl) hafnium dichloride, ethylene bis(4,5,6,7-H-tetrahydro-l-indenyl) hafnium dichloride, dimethylsilylene bis(inden-l-yl) hafnium dichloride, dimethylsilylene bis(4,5,6,7-H-tetrahydroinden-l -yl)hafnium dichloride, di(4-tolyl)silylene bis(inden-l-yl) hafnium dichloride, di(4-n-butylphenyl)silylene bis(4,5,6,7-tetrahydroinden-1-yl) hafnium dichloride, ethylidene(inden-1-yl-2,3,4,5-tetramethyl-l-cyclopentadienyl) hafnium dichloride, ethylene bis(inden-l-yl) titanium dichloride, ethylene bis(4,5,6,7-H-tetrahydro-l-indenyl) titanium dichloride, dimethylsilylenebis(2-methyl-4-phenylinden-1-yl)zirconium dimethyl, dimethylsilylene bis(2-methyl-4-phenylinden-l-yl)zirconium dichloride, and ethylidene(inden-1 -yl)(2,3,4,5-tetramethylcyclopentadien- l-yl) zirconium dichloride.

The Group 4 metallocenes for use in the present invention are known compounds or they may be made by one of several known methods, such as, J. Organomet. Chem., 435, 299 (1992) and Organometallics, 8, 2107 (1989). One method comprises first reacting two equivalents of an optionally substituted cyclopentadiene with a metallic deprotonating agent such as an alkyllithium or potassium hydride in an organic solvent such as tetrahydrofuran, followed by reaction of this solution with a solution of one equivalent of a doubly-halogenated compound such as dichlorodimethylsilane. The resulting ligand is then isolated by conventional methods such as distillation or precipitation, reacted again with two equivalents of a metallic deprotonating agent, and then reacted with one equivalent of a tetrachloride of a Group 4 metal, optionally coordinated with donor ligand molecule such as tetrahydrofuran, in an organic solvent.

Suitable solid Group 4 metal-magnesium halide complexes for use as component b) preferably include solid, particulated magnesium and Group 4 metal-containing halide complexes, especially, solid magnesium and zirconium-containing complexes or solid magnesium and hafniumcontaining complexes. In addition to halide moieties, the complex preferably comprises one or more alkoxide and/or aryloxide moieties, especially such moieties selected from the group consisting of ethoxide, n-butoxide and o-cresolate moieties.

The magnesium and Group 4 metal-containing halide complex preferably is prepared by conventional coprecipitation, solid-solid metathesis, or physical comminuting techniques previously known in the art for preparing Ziegler-Natta procatalysts comprising a Group 4 metal halide supported on crystalites of magnesium dihalide. Preferably the solid magnesium and Group 4 WO 03/102037 PCT/US03/16266 metal-containing halide complex is prepared by halogenating a solid, particulated precursor containing magnesium and Group 4 metal moieties, alkoxide and/or aryloxide moieties, halide moieties, and optionally an internal electron donor compound, with a halogenating agent, especially halides of metals of Groups 4-13 of the Periodic Table of the Elements, especially chlorides of titanium, vanadium and aluminum, most preferably, TiC14, VC1 4 R"'AlC1 2 (where is C-z 1 2 hydrocarbyl, preferably C 14 alkyl), mixtures thereof, and/or mixtures of one or more compounds with SiC14 to prepare a solid, particulated, magnesium and Group 4 metal-containing halide complex. Preferred solid, particulated, magnesium and Group 4 metal-containing halide complexes are those wherein the halide moieties are chloride moieties.

Any solid, magnesium and Group 4 metal-containing halide complex (interchangeably referred to herein as a precursor) can be used in the present invention, and any means known to halogenate such a precursor can be used to prepare the solid, magnesium and Group 4 metalcontaining halide complex (interchangeably referred to herein as the procatalyst) when preparing the catalyst compositions of the invention. Examples of suitable techniques are disclosed in US-A's 5,034,361; 5,082,907; 5,151,399; 5,229,342; 5,106,806; 5,146,028; 5,066,737; 5,124,298, and 5,077,357, and elsewhere.

When magnesium dialkoxides or diaryloxides, such as magnesium diethoxide or magnesium di(o-cresolate) are used as the starting materials to form the precursor according to the precipitation technique, the magnesium compound and a Group 4 metal alkoxide or a Group 4 metal alkoxide halide are preferably combined in an inert diluent along with a small quantity of a Group 4 metal halide, especially TiC1 4 TiC1 3 ZrC1 4 TiC13*1/3A1C1 3 or a mixture thereof. Suitable diluents include aromatic hydrocarbons or halohydrocarbons, or mixtures thereof with one or more alcohols.

A small quantity of one or more solubilizing agents, (referred to as a "clipping agent") may be employed as needed to assist in solubilizing one or more of the metal compounds. Examples of such clipping agents include o-cresol, p-cresol, mixtures of o-cresol and p-cresol, 3-methoxyphenol, 4-dimethylaminophenol, 2,6-di-tert-butyl-4-methylphenol, p-chlorophenol, methylsalicylate, HCHO, CO, B(OEt) 3 SO2, Al(OEt) 3 Si(OR) 4 R'Si(OR) 3 and P(OR) 3 as well as sources of the following anions, C0 3 Br", (O 2 COEt)'. In the above compounds, R and R' represent hydrocarbon groups, preferably alkyl groups, containing from 1-10 carbon atoms, and preferably R and R' are the same or different and are methyl or ethyl. Suitable sources for the foregoing anionic clipping agents include MgBr 2 carbonized magnesium ethoxide (magnesium ethyl carbonate), and calcium carbonate. The use of clipping agents in the preparation of a solid, particulated, magnesium and Group 4 metal containing precursor complex by the foregoing solid/solid metathesis process is disclosed in US-A's 5,124,298 and 5,077,357, and elsewhere.

Preferred diluents for the foregoing precipitation process are halogenated hydrocarbons, WO 03/102037 PCT/US03/16266 especially chlorobenzene or chlorotoluene. The metal compounds, optional clipping agent(s), and diluent are combined with heating in a digest step. Preferred'temperatures are from 25 to 120 0

C,

more preferably from 30 to 90 A small quantity of a precipitating agent, preferably an aliphatic alcohol, especially ethanol, n-butanol, or a mixture thereof is employed to initially assist in solubilizing the resulting metal complex. Upon removal of the alcohol from the mixture in a controlled manner, a uniformly shaped, solid, particulated magnesium and Group 4 metal containing precursor complex is obtained. The precursor may be rinsed one or more times, desirably with an aliphatic hydrocarbon, and ultimately devolatilized to remove volatile contaminants if desired.

Next the magnesium and Group 4 metal containing precursor complex is halogenated in one or more metathesis steps as previously disclosed, to cause formation of solid, relatively uniform sized particles of the desired complex in combination with relatively low surface area, low porosity magnesium chloride crystallites. Techniques for such process are well known and disclosed for example in US-A-5,034,361; 5,082,907; 5,151,399; 5,229,342; 5,106,806; 5,146,028; 5,066,737; 5,077,357; 4,442,276; 4,540,679; 4,547,476; 4,460,701; 4,816,433; 4,829,037; 4,927,797; 4,990,479; 5,066,738; 5,028,671; 5,153,158; 5,247,031; 5,247,032, and elsewhere.

One suitable method for converting the precursor into a solid, particulated magnesium and Group 4 metal halide complex for use herein is by reacting the precursor with a halogenating agent, such as titanium tetrachloride, aluminum trichloride or an alkylaluminumhalide, an optional hydrocarbon or halohydrocarbon, and an optional electron donor, in the presence of liquid diluent, such as a hydrocarbon or halohydrocarbon. A preferred halogenating agent is TiC14 or ethylaluminumdichloride. Following the chlorination, no or very little residual aluminumalkyl functionality is believed to remain in the Group 4 metal- magnesium halide complex, in as much as this complex by itself is inactive for the polymerization of olefins.

Suitable hydrocarbons or halohydrocarbons preferably contain up to 12 carbon atoms inclusive, more preferably up to 9 carbon atoms inclusive. Exemplary hydrocarbons include pentane, octane, benzene, toluene, xylene, alkylbenzenes, and the like. Exemplary aliphatic halohydrocarbons include methylene chloride, methylene bromide, chloroform, carbon tetrachloride, 1,2-dibromoethane, 1,1,2-trichloroethane, trichlorocyclohexane, dichlorofluoromethane and tetrachlorooctane. Exemplary aromatic halohydrocarbons include chlorobenzene, bromobenzene, dichlorobenzenes and chlorotoluenes. Of the aliphatic halohydrocarbons, compounds containing at least two chloride substituents are preferred, with carbon tetrachloride and 1,1,2-trichloroethane being most preferred. Of the aromatic halohydrocarbons, chlorobenzene or chlorotoluene is particularly preferred.

WO 03/102037 PCT/US03/16266 The optional electron donors are Lewis base compounds that are free from active hydrogens in which the precursor compound is partially or fully soluble. Its use is highly desirable in order to form tactic polymers, and in the polymerization of ethylene to form a narrow molecular weight distribution product, if desired. Electron donors desirably operate by binding to certain of the active catalyst sites to alter the total reactivity of the catalyst and to limit the catalyst crystallite growth leading to small crystallite size in the resulting product and correspondingly high surface area. Suitable electron donors are those compounds that are conventionally employed in the formation of Ziegler-Natta procatalysts. Particularly preferred electron donors include ethers, esters, amines, imines, nitriles, phosphines, stibines, and arsines. The more preferred electron donors, however are aliphatic and aromatic carboxylic acid (poly)esters or (poly)ether derivatives thereof, particularly alkyl esters of aromatic monocarboxylic or dicarboxylic acids and ether derivatives thereof. Examples of such electron donors are methylbenzoate, ethylbenzoate, ethyl-pethoxybenzoate, ethyl-p-methylbenzoate, diethylphthalate, dimethylnaphthalene-dicarboxylate, diisobutylphthalate, diisopropyl terephthalate, and mixtures thereof. Most preferred electron donors are ethylbenzoate, p-ethoxyethylbenzoate, and diisobutylphthalate.

The manner in which the precursor complex, the optional hydrocarbon or halohydrocarbon, optional electron donor and halogenating agent are contacted is not critical. In one embodiment, the halogenating agent is added to a mixture of the electron donor and precursor. More preferably, however, the electron donor first is mixed with the tetravalent titanium halide and optional halohydrocarbon and the resulting mixture is used to contact the precursor complex in one or more contactings at elevated temperatures from 70 to 120 0 C, preferably from 80 to 115°C.

The solid product that results may be contacted with a further quantity of halogenating compound, if desired, and in addition with a halohydrocarbon. The two procedures may be combined or employed separately. Moreover, it often is useful to also include an acid chloride, such as benzoyl chloride or phthaloyl chloride, separately or in combination with the foregoing post treatments, to further facilitate the replacement of alkoxide moieties with halide moieties in the solid, particulated, magnesium and Group 4 metal halide complex. The resulting product may then be washed one or more times with an aliphatic hydrocarbon or hydrocarbon mixture such as isooctane to remove soluble Group 4 metal species.

In a preferred embodiment, the mixture of precursor, halogenating agent, optional electron donor and optional halohydrocarbon is maintained at an elevated temperature, for example, a temperature from 70 to 150 0 C, for a period of time, during one or more of the foregoing metathesis steps. Best results are obtained if the materials are contacted initially at or about ambient temperature and then heated. Sufficient halogenating agent is provided to convert at least a portion and preferably at least a substantial portion of the alkoxide moieties of the precursor to halide WO 03/102037 PCT/US03/16266 groups. This replacement is conducted in one or more contacting operations, each of which is conducted over a period of time ranging from a few minutes to a few hours and it is preferred to have a halohydrocarbon present during each contacting. Sufficient electron donor preferably is provided so that the molar ratio of electron donor to the magnesium present in the magnesium and Group 4 metal halide complex is from about 0.01:1 to about 1:1, preferably from about 0.05:1 to about 0.5:1.

After formation of the magnesium and Group 4 metal halide complex, it is separated from the reaction medium, preferably by filtering to produce a moist filter cake. The moist filter cake desirably is then rinsed to remove unreacted halogenating agent and may be dried to remove residual liquid, if desired. In a preferred embodiment, the moist, rinsed filter cake is then extracted one or more times, as previously disclosed, to reduce the Group 4 metal content to a stable level.

The extraction involves contacting the magnesium and Group 4 metal halide complex, preferably a filter cake, with a liquid diluent and maintaining or increasing the temperature of the mixture to above room temperature for a time from several minutes to several hours, and separating the resulting solid. It is particularly preferred to contact the mixture at a temperature greater than preferably greater than 85°C, more preferably greater than 115°C, and most preferably greater than 120°C to about 300°C, more preferably to about 200°C, and most preferably to about 150°C.

The magnesium and Group 4 metal halide complex preferably employed in the present invention suitably has a Group 4 metal content of from 0.5 to 15 percent by weight, preferably from 0.8 percent to 12 percent by weight, and most preferably from 1 to 10 percent by weight. The weight ratio of Group 4 metal to magnesium is suitably between 1:1 and 1:20, preferably between 1:4 and 1:15, and most preferably between about 1:5 and 1:10.

A preferred Group 4 metal- magnesium halide complex for use herein corresponds to the formula MgdTiZrhAli(ORe)eX*f(ED)g wherein R, independently each occurrence is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or CORf wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; X* independently each occurrence is an anionic ligand group, preferably C1-4 alkyl, chloride, bromide, or iodide, most preferably chloride; ED is an electron donor; Ti includes a mixture of both +3 and +4 oxidation state cations, d is a number from 1 to 50; e is a number from 0 to 5; f is a number from 2 to 100; g is a number from 0 to 10, h is a number from 0 to 2 and i is a number from 0 to The type of solid Group 4 metal- magnesium complex employed in the catalyst composition of the invention may be selected to provide desired polymer characteristics. In a preferred embodiment, a Group 4 metal- magnesium complex is selected that provides broad molecular weight distribution polymers, especially ethylene homopolymers and copolymers of ethylene and WO 03/102037 PCT/US03/16266 one or more C 3 1 2 olefins or diolefins having a unique high molecular weight fraction. Such complexes have been uniquely identified for use herein containing both +3 and +4 oxidation state Ti cations, Mg 2 A1 3 alkoxide and/or aryloxide moieties, halide moieties, and little or no internal electron donor. Highly preferably, such Group 4 metal- magnesium complexes correspond to the formula: Mg 2 5 1 0 Ti 3 1 -2Ti+ 4 12

A+

3 1 -1 0 o(ORe)I- 1 X*-o 100 wherein R e and X* are as previously defined, and preferably are C 1 4 alkyl and chloride respectively. They are prepared in one embodiment by combining one or more magnesium dialkoxides or diaryloxides, one or more titanium tetraalkoxides, a mixture of titanium tetrahalides and titanium trihalides (the latter optionally complexed with a Lewis acid such as aluminum trichloride), precipitating the resulting complex in the form of solid particles, optionally with the use of one or more clipping agents to solubilize the various components and/or one or more precipitating agents, such as alcohols, the removal of which selectively precipitates the resulting solid complex, and finally halogenating the solid particles one or more times to form MgC2 crystallites in situ. A preferred halogenating agent is an alkylaluminum dichloride, especially ethylaluminum dichloride.

Although the Group 4 metal- magnesium halide complex may be formed and recovered as a solid particulated material, it should be emphasized that as used in the present invention, the substance is generally redispersed in an organic solvent during formation of the present catalyst composition. Accordingly, recovering and removing solvent from the solid complex is not critical to the present invention and it may instead be be employed directly from the foregoing reaction in the form of a slurry or dispersion without previous recovery and drying.

Any solid particulate material that is non-reactive with the other components of the catalyst system and subsequent polymerization mixture, can be employed as component Suitable materials include both organic or inorganic compounds, especially metal oxides, metal nitrides, metal carbonates, metalloid oxides, organic polymers, silicon polymers, and mixtures thereof, that naturally possess or are treated to possess low water and surface hydroxyl or other reactive functionality content. Preferably total hydroxyl content (including both physisorbed water and surface hydroxyl functionality) should preferably be less than 0.1 mmol/g, more preferably less than 0.01 mmol/g. Examples of substrate materials include: silica, boron nitride, titanium dioxide, zinc oxide, cross-linked polystyrene, glass microspheres, and calcium carbonate. Preferably the filler also is characterized by hydrophobic surface groups or other groups that render the substance compatible with hydrocarbons. Such materials are readily dispersed in hydrocarbon diluents that are preferably employed in the present invented process. Hydrophobic silicas are preferred because they are readily dispersed in hydrocarbon diluents and possess good thixotropic properties, thereby WO 03/102037 PCT/US03/16266 imparting high viscosity to the resulting slurry and, upon spray drying, good strength to the resulting spray-dried particles. The solid particulate material employed as filler should have an average particle size no greater than 50 micrometers, preferably no greater than 10 micrometers.

Suitable fillers include fumed silicas, such as are made by adding tetrachlorosilane to an oxidizing flame, that have been rendered hydrophobic as well as inert to further chemical reaction with the remaining catalyst components, especially the Group 4 metal- magnesium complex, by reaction with a silane, halosilane, trialkylaluminum, trihydrocarbylborane, or similar reagent, to remove reactive hydroxyl and other surface functionality and impart hydrophobicity to the resulting product. Such hydrophobic fillers are interchangeably referred to herein as passivated fillers.

Desirably, the hydrophobic filler is miscible with organic hydrocarbon liquids, especially aliphatic, cycloaliphatic, or aromatic hydrocarbons, and able to form a stable dispersion of the various components of the catalyst composition during the spray-drying process. Due to the surface functionality of the passivated, hydrophobic filler, it is compatible with organic liquids and acts as a thixotropic agent, modifying the viscosity of a dispersion of the catalyst components in a diluent and inhibiting separation or settling out of the individual components leading to product variability, as well as imparting improved droplet formation and sizing during the spray drying operation. The hydrophobic filler additionally serves to disperse or dilute the catalyst components, especially the solid Group 4 metal-magnesium halide complex to reduce the localized polymerization activity of the catalyst thereby preventing localized overheating of polymer particles and consequent sheeting of the reactor walls as well as aiding in accurate measuring and dispensing of uniform catalyst charges to the reactor. Suitable filler materials generally have low porosity. They preferably have a surface area from 50 to 500 m 2 more preferably from 100 to 400 m 2 and a bulk density from 0.1 to 10 g/ml, preferably 1 to 8 g/ml.

Preferred fillers are highly dessicated, low hydroxyl content, fumed silicas prepared by calcining or heating a finely particulated solid silica or silica precursor to temperatures from 250 to 600 °C for a time from several minutes to several hours followed by reacting the silica with the foregoing passivating agents, especially dichlorodimethylsilane, to impart hydrophobic properties to the resulting product. Highly desirable passivated, hydrophobic filler materials are dichlorodimethylsilane treated, fumed silicas, containing from 0.001 to 1.0 mmol/g of silane functional groups therein.

Fillers having a relatively low porosity are preferred for use herein due to the fact that the metallocene component is not sequestered within the particle voids but instead remains on the surface of the particle in close proximity with the solid Group 4 metal-magnesium complex, which, being a solid, would be unable to enter the pores of a relatively more porous substance. In practice, the present invention contains regions containing localized concentrations of the metallocene and WO 03/102037 PCT/US03/16266 Group 4 metal-magnesium halide complex intermixed with the essentially inert, filler. This desirably leads to dilution of the catalyst activity thereby preventing localized excess heat formation due to excessive polymerization activity.

The binder, component d) is employed, if needed, to join the metallocene and Group 4 metal-magnesium halide components, and optionally the support, together in order that the resulting polymerization product is a homogeneous mixture of polymer products. Due to the fact that the metallocene is generally oleophilic whereas the Group 4 metal-metallocene halide complex is relatively hydrophilic, a suitable means to retain the two types of catalyst in close proximity or intimate contact during the polymerization process is highly desirable. If separation does occur, polymer particles of different properties are formed by the two catalyst sites, and subsequent handling or conveying can result in segregation of different polymers. For example, if one catalyst type results in formation of small particles of a relatively high molecular weight polymer, the resulting product may contain an inordinate quantity of high molecular weight "fines" which settle under the effect of gravity during shipment or conveying, thereby leading to product inhomogenity.

Accordingly, the use of a binder assists in preventing separation of components a) and b) and optionally c) under polymerization conditions. In one embodiment a suitable binder constitutes functionality that coordinates or preferably binds to functionality on both the metallocene and the solid Group 4 metal- magnesium complex. Alternatively, the metallocene and complex may be judiciously selected with ligands that accomplish the foregoing purpose without the need for a separately added binder. As an example, an ionic metallocene complex or one that is rendered ionic by activation with a cation containing activator is more compatible with the Group 4 metalmagnesium halide component and less readily extracted from a mixture comprising both components. Similarly, amine or amide containing metallocene compounds are able to form Lewis base adducts with magnesium- or Group 4 metal- species of component Likewise, the binder may also comprise a functional group or portion thereof comprising the cocatalyst used in the ultimate polymerization. An example would be compounds that possess Lewis acid functionality or Bronsted acid functionality in combination with a non-coordinating anion or other activating functionality.

The binder may also assist agglomeration of the components of the present heterogeneous catalyst composition into a particle. By the term "heterogeneous" is meant that identifiable regions comprising the metallocene combined with the solid, Group 4 metal- magnesium halide composition remain in the resulting spray dried catalyst composition after catalyst formation. Such regions are separated by, or dispersed between, regions or particles of the filler.

In one embodiment of the invention, the binder is an oligomeric or polymeric, linear or cyclic aluminoxane or a trialkylaluminum modified derivative thereof. Such compounds may be WO 03/102037 PCT/US03/16266 formed by the reaction of a tetraalkyldialuminoxane containing C 2 or higher alkyl groups with an amount of trimethylaluminum that is less than a stoichiometric excess. The synthesis of modified aluminoxanes may also be achieved by the reaction ofmethylalumoxane with a trialkyl aluminum compound containing C 2 or higher alkyl groups, especially butyl groups. Further modified methylalumoxanes, which contain both methyl groups and higher alkyl groups, may be synthesized by the reaction of a polyalkylalumoxane containing C 2 or higher alkyl groups with trimethylaluminum and then with water as disclosed in, for example, US-A-5,041,584.

Alumoxanes are preferred binders in as much as they also may participate as cocatalysts in the ultimate polymerization, and only serve to loosely or reversibly bind the various catalyst components. As a result, the catalyst composition readily disintegrates during the polymerization process, thereby continually exposing fresh catalyst sites comprising a mixture of components a) and b) to the polymerization environment. The quantity of alumoxane binder used in order to form the desired agglomeration of catalyst components is generally less than that necessary for activation of either catalyst component alone for olefin polymerization. The spray dried catalyst composition may also contain additional organic or inorganic compounds which serve as binders so long as particle integrity and catalytic activity is not adversely affected. The binder may also serve an additional function, such as stabilizing the final polyolefin product against oxidation, or improving the gas phase fluidization of nascent polymer particles. Suitable additional binders include waxes, silicon compounds, or other suitable substances. Generally, the molar quantity of binder employed based on the weight of solid Group 4 metal- magnesium complex component is from 1:1 to 10:1.

The amounts of Group 4 metallocene, Group 4 metal-magnesium halide complex, and filler employed in the composition of the invention will vary widely depending on the ultimate polymer properties desired. For example, if a greater amount of a low molecular weight component having a narrow MWD is desired, then more metallocene compound component can be used. If a greater amount of a higher molecular weight component having a broader MWD is desired, then more of the Group 4 metal-magnesium halide complex component is used. Desirably the molar ratio of metallocene component to Group 4 metal- magnesium halide complex (based on Group 4 metal in each component) ranges from 0.05:1 to 1:0.05, preferably from 0.1:1 to 1:0.1.

The metallocene, solid Group 4 metal- magnesium halide complex, and optional binder are believed to be incorporated into the solid, heterogeneous catalyst composition in the form of occlusions of the same located interfacially or interstitially between agglomerates of the filler, which are optionally bound into the agglomerate particles through use of the same or a different binder. Alternatively, the metallocene, Group 4 metal- magnesium complex, and/or the optional binder may be covalently or ionically bound to the filler particles if desired, but this is not required for operation of the invention.

WO 03/102037 PCT/US03/16266 When propylene is polymerized, the catalyst composition of the present invention may also employ a selectivity control agent or SCA. Suitable SCA's for use herein include organosilicon compounds containing at least one hydrocarbyloxy group, esters of monocarboxylic or dicarboxylic acids, preferably aromatic monocarboxylic or dicarboxylic acids, and/or alkyl ether- or polyalkylether- derivatives thereof. Examples of suitable silane compounds include methyl cyclohexyl dimethoxysilane (MCHDMS), diphenyldimethoxy-silane (DPDMS), dicyclopentyl dimethoxysilane (DCPDMS), isobutyltrimethoxysilane (IBTMS), and n-propyl trimethoxysilane (NPTMS). Examples of suitable non-silane SCA's include p-methoxyethylbenzoate and pethoxyethylbenzoate.

The catalyst composition is prepared by forming a well stirred suspension of the filler, one or more Group 4 metallocene compounds, and the solid Group 4 metal-magnesium halide complex in one or more suitable diluents, and then spray drying the suspension. In one method of preparing the suspension, the solid Group 4 metal halide complex is added to a solution or dispersion of the metallocene and optional binder in an inert diluent to form a first suspension. At least the solid Group 4 metal-magnesium halide complex should remain in the form of solid particles and not be substantially dissolved in the diluent mixture. The first suspension is stirred for a time from 1/10 hour to 10 hours, and then the filler is added thereto either in the form of a solid or dispersed in a liquid diluent. The resulting final suspension is stirred for a further time from 1 second to 3 hours and then spray dried to remove the diluent. The same or different diluents may be used for forming the various suspensions and solutions.

Preferably, spray drying is performed by passing the suspension through an optionally heated orifice under pressure where it is optionally heated to a temperature above ambient, preferably from 30 to 100 OC, and subsequently spraying the mixture into a stream of heated inert drying gas, such as nitrogen, argon, or propane to evaporate the diluent and produce relatively nonporous, solid particles of the resulting catalyst composition. The volumetric flow of the drying gas is preferably considerably larger than the volumetric flow of the suspension. Alternatively, droplet formation of the suspension may be accomplished using atomizing nozzles, centrifugal high speed disc atomizers, or other suitable means known in the art for spray drying relatively viscous suspensions.

The diluent employed in forming the suspension is typically a material which is capable of dissolving or suspending the metallocene compound and optionally the binder, and suspending but not dissolving the Group 4 metal- magnesium halide complex and filler materials, and which is readily volatilized during the spray drying process. For example, hydrocarbons such as linear or branched alkanes such as hexane, pentane and isopentane; aromatics such as toluene and xylene; and halogenated hydrocarbons such as dichloromethane, and/or mixtures thereof are usefully WO 03/102037 PCT/US03/16266 employed as the diluent. Preferred diluents have normal boiling points from 0-75 OC.

The amount of filler employed in forming the suspension is desirably from 0.1 to preferably 1 to 15, and most preferably 2 to 10 percent by weight, based on the total weight of the suspension prior to spray drying. After spray-drying, the filler is present in the resulting solid catalyst particles in an amount of from 0.5 to 50, preferably 10 to 30 percent by weight. Further desirably, after spray drying, the compositions of the invention are in the form of relatively uniform, relatively non-porous, relatively low surface area, particles having a 50 t h percentile particle size D 5 0 as determined by a laser diffraction particle size measuring instrument such as those made by Malvern Corporation, from 5 to 200 iun, preferably from 10 to 30 uim. Additionally, the particles preferably have a 90 percentile particle size, D 90 of 20 to 300 gm, preferably 15 to 50 jm.

The resulting catalyst composition may be mixed with a suitable protective material such as mineral oil for ease of storage and supply to the polymerization reactor. In a further embodiment, the dispersion of components c) and optionally d) in a diluent is sprayed into a gas-phase olefin polymerization reactor or into the collection, charging, or recycle sections thereof, forming the spray dried particulated catalyst composition of the invention in situ during the polymerization process, thereby avoiding the need for catalyst recovery and transfer.

The catalyst composition may be used in the polymerization of ethylene and optionally higher olefin monomers, preferably having 3 to 8 carbon atoms, and further optionally one or more diene compounds into ethylene homopolymers and copolymers. Suitable dienes especially include hexadiene, dicyclopentadiene, butadiene, isoprene, norbomene, and ethylidiene norbornene.

The polymerization process may be conducted in the gas phase in a stirred or fluidized bed reactor, or in a slurry phase reactor using equipment and procedures well known in the art.

Ethylene monomer and optionally one or more higher olefin monomers and/or one or more dienes are contacted with an effective amount of catalyst composition at a temperature and a pressure sufficient to initiate polymerization. The process may be carried out in a single reactor or in two or more reactors in series. The process is conducted substantially in the absence of catalyst poisons such as moisture, oxygen, carbon dioxide, carbon monoxide and acetylenic compounds, since only minor amounts of such materials have been found to affect the polymerization adversely. The process also may be conducted in a slurry reactor employing a diluent that does not dissolve at least some of the components of the polymerization.

The cocatalyst which is capable of activating the Group 4 metallocene and Group 4 metalmagnesium complex catalyst components for polymerization is also employed in the polymerizaiton. Examples of suitable cocatalysts include: aluminum compounds containing at least one aluminum-oxygen bond, such as branched or cyclic oligomeric poly(hydrocarbylaluminum oxide)s which contain repeating units of the general formula where is hydrogen, an WO 03/102037 PCT/US03/16266 alkyl group containing from 1 to about 12 carbon atoms, an aryl group of from 6 to 20 carbons, or an alkaryl group of from 7 to 20 carbons, or a haloaryl group of from 6 to 20 carbons; ionic salts of the general formula: [BAR 4 where A is a cationic Lewis or Bronsted acid capable of abstracting a ligand group from the metallocene catalyst, B is boron, and AR is an inertly substituted aromatic group of from 6 to 20 carbons, preferably a fluorinated aromatic group, most preferably a perfluorophenyl group; and boron compounds of the general formula BAR 3 where A R is as defined above.

Preferably, the cocatalyst is a branched or cyclic oligomeric poly(hydrocarbyl-aluminum oxide), also known as an alumoxane. More preferably, the cocatalyst is methylaluminoxane (MAO), also known as methalumoxane, or modified methylaluminoxane (MMAO).

Aluminoxanes are well known in the art and comprise oligomeric linear alkyl aluminoxane represented by the formula: and oligomeric cyclic alkyl aluminoxanes of the formula: (Al(R"')O)q wherein s is 1-40, preferably 10-20; q is 3-40, preferably 3-20; and independently each occurrence is C1- 1 2 hydrocarbyl, preferably C 14 alkyl, and most preferably methyl or a mixture of methyl and butyl.

The amount of metallocene catalyst and cocatalyst usefully employed in the catalyst composition may vary over a wide range. When the cocatalyst is a linear, branched or cyclic oligomeric or polymeric alumoxane, the mole ratio of aluminum atoms to metal atoms contained in the metallocene catalyst compound is generally in the range of from about 2:1 to about 10,000:1, preferably in the range of from about 10:1 to about 1,000:1, and most preferably in the range of from about 100:1 to about 700:1. Based on the the amount of both components a) and the molar quantity of alumoxane cocatalyst to total Group 4 metal is preferably from 5:1 to 100,000:1, more preferably from 50:1 to 10,000:1, and most preferably from 200:1 to 1000:1. Other cocatalysts are generally employed in a molar ratio compared to metallocene component from about 1:1 to about 10:1.

Conventional additives including, chain transfer agents, cross-linking agents, antistatic agents, flow aids, and condensing agents may be included in the process. When hydrogen is used as a chain transfer agent in the process, it is used in amounts varying between about 0.001 to about moles of hydrogen per mole ofolefin monomer. Also, as desired for temperature control of the system, any materials inert to the catalyst composition and reactants can also be present in the system.

Organometallic compounds may be employed as scavengers in the polymerization process WO 03/102037 PCT/US03/16266 to scavenge for poisons and increase the catalyst activity. Often the same compounds useful as cocatalysts are also useful as scavengers. Examples of useful external catalysts are metal alkyls, preferably aluminum alkyls, most preferably triisobutylaluminum. Use of such scavengers is well known in the art.

Polymerization preferably is conducted in a fluidized bed polymerization reactor. In accordance with the process, discrete portions of the catalyst are continuously or semi-continuously fed to the reactor in catalytically effective amounts together with cocatalyst and the monomer or monomers to be polymerized while the polymer product is continuously or semi-continuously removed. Suitable fluidized bed reactors are in US-A's 4,302,565, 4,302,566, 4,303,771, and elsewhere.

It is preferred sometimes that such fluidized beds are operated using a recycle stream of unreacted monomer from the fluidized bed reactor, at least a portion of which is condensed to remove heat from the recycle stream. Alternatively, a condensing agent may be included as well.

Operation of a fluidized bed reactor in condensing mode generally is known in the art and described in, for example, US-A's 4,543,399 and 4,588,790. The use of condensing mode has been found to lower the amount of xylene solubles in isotactic polypropylene and improve catalyst performance when using the catalysts of the present invention.

Polymerization temperatures from about 0 to about 200 °C at atmospheric, subatmospheric, or superatmospheric pressures may be employed. Subatmospheric or superatmospheric pressures and temperatures in the range from 40°C to 110°C are used. Preferably, pressures in the range of 1 to 1000 psi (7 kPa to 7 MPa), preferably 50 to 400 psi (350 kPa to 2.8 MPa), most preferably 100 to 300 psi (700 kPa to 2 MPa), and temperatures in the range of 30 to 130°C, preferably 65 to 110°C are employed. Stirred or fluidized bed gas phase reaction systems are particularly useful.

Generally, a conventional gas phase, fluidized bed process is conducted by passing a stream containing one or more monomers continuously through a fluidized bed reactor under reaction conditions and in the presence of catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended condition. A stream containing unreacted monomer is withdrawn from the reactor continuously, compressed, cooled, optionally fully or partially condensed, and recycled to the reactor. Product is withdrawn from the reactor and make-up monomer is added to the recycle stream. As desired for temperature control of the system, any gas, preferably a condensable gas, that is inert to the catalyst composition and reactants may also be present in the gas stream. In addition, a fluidization aid such as carbon black, silica, clay, or talc may be used, as disclosed in US-A-4,994,534.

Polymerization may be carried out in a single reactor or in two or more reactors in series or parallel. The precise procedures and conditions of the polymerization are broadly conventional but WO 03/102037 PCT/US03/16266 the olefin polymerization process, by virtue of the use therein of the polymerization catalyst formed from the solid precursor, provides polyolefin product having a relatively high bulk density in quantities that reflect the relatively high productivity of the olefin polymerization catalyst. In addition, the polymeric products produced in the present invention have a reduced level of fines.

The olefin polymer produced using the spray dried, filled catalyst composition has excellent morphology. It is believed this is because little fragmentation of the catalyst composition particles occurs prior to the onset of polymerization. However, when polymerization begins the catalyst composition particles readily decompose into smaller catalyst particles and continue polymerization in an extremely active manner. Thus the growing polymer particles continue polymerization under highly uniform polymerization conditions without experiencing catalyst fading or decay as in a normal polymerization. This results in polymer particles having a broad molecular weight distribution and uniform morphology. In the event greater uniformity of polymer product is desired, a post reactor blending or extrusion procedure can be employed if desired.

It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention and are not to be construed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term "overnight", if used, refers to a time of approximately 16-18 hours, "room temperature", if used, refers to a temperature of about 20-25 and "mixed alkanes" refers to a mixture of hydrogenated propylene oligomers, mostly C 6

C

12 isoalkanes, available commercially under the trademark Isopar ETM from Exxon Chemicals, Inc.

Examples The following defined terms will be used in the examples.

Glossary Density in g/ml was determined in accordance with ASTM 1505, based on ASTM D-1928, procedure C, for plaque preparation. A plaque was made and conditioned for one hour at 100 °C to approach equilibrium crystallinity, measurement for density was then made in a density gradient column.

MMAO is triisobutylaluminum modified methalumoxane (Type 3A, available from Akzo Corporation).

MI is the melt index reported as grams per 10 minutes, determined in accordance with ASTM D-1238 condition E, 190°C, 2.1 Kg weight.

FI is the flow index (I21), reported as grams per 10 minutes, determined in accordance with ASTM D-1238 condition F, 190 21 Kg weight.

WO 03/102037 PCT/US03/16266 MFR or melt flow ratio, is the ratio of flow index to melt index. It is related to the molecular weight distribution of the polymer.

Activity is given in g polymer/mmol Ti/hour/100 psi ethylene (690 kPa ethylene).

Preparation of solid Group 4 metal- magnesium halide complex component A precursor composition comprising titanium, magnesium, halide and alkoxide moieties was prepared by combining the following components in the indicated molar quantities and precipitating a solid product: 3.00 Mg(OEt) 0.10 TiC14 0.30 (TiC1 3 -1/3AC1 3 0.57 Ti(OEt) 4 0.20 MgBr 2 2.44 EtOH 1.02 BuOH.

A solution of MgBr 2 was prepared by adding bromine (0.81 g, 5.06 mmol) to magnesium diethoxide (0.74 g, 8.19 mmol) in a diluent mixture comprising ethanol (3.4 ml), butanol (2.3 ml), and chlorobenzene (1.4 ml). In a separate glass bottle under nitrogen, TiCl 3 .1/3A1C13 (1.52 g, 7.6 mmol), was mixed with magnesium diethoxide (8.43g, 73.7 mmol) and titanium tetrachloride (0.45g, 2.37 mmol), in 40 ml of chlorobenzene. While stirring, titanium tetraethoxide (3.42 g of a 95 percent hexane solution, 14.2 mmol) was added followed by the addition of another 50 ml of chlorobenzene. The bottle was placed in an oil bath and heated to 100 The previously prepared MgBr 2 mixture was quickly added and the bottle sealed by attaching the cap.

After stirring for 2.5 hours at 440 rpm the cap was removed and a gentle stream of nitrogen was passed through the resulting slurry until the volume decreased by about 10 percent. The warm slurry was then filtered under nitrogen atmosphere. The solids were washed once with chlorobenzene, then twice with hexane, and dried under flowing nitrogen. The precursor product (11.7 g) was recovered in the form of green colored granules having a number average particle diameter of 18 gm.

Approximately 2.30 g of the precursor was slurried in 10 ml of hexane. Ethylaluminum dichloride (EADC, 16 ml of a 25 percent solution in toluene) was then added to the slurry over a period of about 3 minutes. The initially tan colored slurry turned to grayish brown. After stirring for 30 minutes, in an oil bath heated to 60 the slurry was filtered. The solids were washed once with toluene/hexane mixture (50/50 by volume) then twice with hexane and dried under flowing nitrogen to yield 2.23 g of a brown powder.

WO 03/102037 PCT/US03/16266 Preparation of spray-dried catalyst Example 1 In a glove box, a glass bottle is charged with five grams of the Group 4 metal- magnesium complex component prepared as described above, 150 ml of hexane and 6.8 ml of a 2.3 M heptane solution of MMAO (15.6 mmol) to serve as a binder. After stirring the resulting slurry for about two hours, approximately 1 gram of bis(n-butylcyclopentadienyl)zirconium dichloride is added to the slurry, and the mixture was stirred for another one hour. Dichlorodimethylsilane- modified fumed silica (1.0 g, Cabosil T M TS-610 available from Cabot Corporation) is added and the resulting mixture stirred for about 30 minutes. The mixture is then passed through a spray drying apparatus (Buchi Model 190 Mini Spray Dryer). The product (4.0 g) in the form of a dark tan, free flowing powder comprising 2.95 percent Zr, 6.69 percent Al, 5.02 percent Ti, and Mg/Ti+Zr ratio of 3.06 is recovered. The molar ratio of MMAO:Ti of the recovered product is 2:1. D 50 particle size of the recovered, spray dried product is 34 tm. Upon examination, the particles are found to be solid, heterogeneous aggregates containing identifiable silica particles with a mixture of the remaining components, Group 4 metal- magnesium solid complex, metallocene and MMAO, interspersed in the interstices between silica particles.

Example 2: In a glove box, a glass bottle is charged with five grams of the Group 4 metal- magnesium complex component prepared as described above, 103.3 ml of hexane and 34.2 ml of a 2.3 M heptane solution of MMAO (78.7 mmol). After stirring the resulting slurry for about two hours, approximately 1 gram of bis(n-butylcyclopentadienyl)zirconium-dichloride is added to the slurry, and the resulting mixture stirred for another hour. Dichlorodimethylsilane modified fumed silica (1.0 g, CabosilT TS-610 available from Cabot Corporation) is added and the resulting mixture stirred for about 30 minutes. The mixture is then passed through a spray drying apparatus (Buchi Model 190 Mini Spray Dryer). The product (4.0 g) in the form of a dark tan, free flowing powder comprising 3.29 percent Zr, 7.71 percent Al, 5.32 percent Ti, and Mg/Ti+Zr ratio of 2.95 is recovered. The molar ratio of MMAO:Ti of the recovered product is 2:1. D 50 particle size of the recovered, spray dried product is 36 pm. The particles are solid, heterogeneous aggregates containing identifiable silica particles with a mixture of the remaining components, Group 4 metalmagnesium solid complex, metallocene and MMAO, interspersed in the interstices between silica particles.

WO 03/102037 PCT/US03/16266 Example 3: In a glove box, a glass bottle was charged with five grams of the Group 4 metal- magnesium component prepared as described above, 98.5 ml of hexane and MMAO (6.8 ml of a 2.3 M heptane solution, 15.6 mmol). After stirring the resulting slurry for about two hours, bis(nbutylcyclopentadienyl)zirconiumdichloride (1.0 g) was added to the slurry, and the mixture stirred for another hour. Dichlorodimethylsilane modified fumed silica (0.5 g, CabosilTM TS-610 available from Cabot Corporation) was added and the resulting mixture stirred for about 30 minutes. The mixture was then passed through a spray drying apparatus (Buchi Model 190 Mini Spray Dryer).

The product (3.5 g) in the form of a dark tan, free flowing powder comprising 2.34 percent Zr, 14.9 percent Al, 3.99 percent Ti, and Mg/Ti+Zr ratio of 3.07 is recovered. The molar ratio of MMAO:Ti of the recovered product is 10:1. D 50 particle size of the recovered, spray dried product is 39 rm.

The particles are solid, heterogeneous aggregates containing identifiable silica particles with a mixture of the remaining components, Group 4 metal- magnesium solid complex, metallocene and MMAO, interspersed in the interstices between silica particles.

Example 4 A 5 L, nitrogen purged, glass reactor is charged with 1000 ml of previously dried hexane followed by 685 g of a solid, Group 4 metal- magnesium halide complex prepared substantially as above described. Next, 830 g of a 7 percent heptane solution of MMAO is added and the reaction mixture agitated for 1 hour. Bis(n-butylcyclopentadienyl)-zirconiumdichloride (136 g) dissolved in 1000 ml of toluene is charged to the reactor and the mixture mixed for an additional 1 hour.

Dichlorodimethylsilane modified fumed silica (780 g, CabosilTM TS-610 available from Cabot Corporation) is added and the resulting mixture stirred for about 30 minutes. The mixture is then spray-dried using a rotary atomizer. Yield is 1.1 kg of solids. Analysis (percent): Zr: 2.57, Si: 19.4, Al: 4.77, Ti: 3.02, and Mg/Ti+Zr ratio is 2.95. The molar ratio of MMAO:Ti of the recovered product is 2:1. D 50 particle size of the recovered, spray dried product is 34 pm. The particles are solid, heterogeneous aggregates containing identifiable silica particles with a mixture of the remaining components, Group 4 metal- magnesium solid complex, metallocene and MMAO, interspersed in the interstices between silica particles. A scanning tunneling electron micrograph of the resulting product is attached hereto as Figure 1. The form of the resulting spray dried catalyst composition is seen to be a heterogeneous agglomerate involving a loose association of silica particles (white) with regions of Group 4 metal- magnesium complex/ metallocene and MMAO that appear dark due to a higher concentration of heavier atomic weight atoms.

WO 03/102037 PCT/US03/16266 Slurry Polymerization A 1 liter stirred autoclave reactor is charged with 485 ml hexane, 15 ml 1-hexene, MMVAO cocatalyst, and sufficient catalyst (in the form of a slurry in mineral oil) to give a charge of about 1 pmole [Ti+Zr]. Hydrogen (700 ml) is added at a pressure differential of 25 psi (170 kPa) and the temperature raised to 70 Ethylene is fed to maintain the desired reactor pressure, and the temperature during polymerization is controlled below 85 After 30 minutes, ethylene feed is stopped, the reactor cooled and vented, and granular polyethylene recovered. Results are given in Table 1.

Table 1 Run Catalyst Temp (oC) MMAO:Ti* Activity FI MFR 1 Ex. 1 100 1000 79,843 387 146 2 Ex. 2 120 60,098 151 82 3 Ex. 3 120 71,848 4 Ex. 4 120 53,256 170 106 mole ratio added MMAO cocatalyst Gas Phase Polymerization The spray dried catalyst prepared according to Example 4 is evaluated in a fluidized bed, gas phase reactor. The catalyst is preactivated prior to introduction into the reactor by contacting it with a MMAO cocatalyst in heptane solution to provide the desired Al:Ti molar ratio. Sufficient hydrogen is added to provide a molar ratio (H 2

/C

2

H

4 of 0.007. Sufficient 1-hexene is provided to give a molar ratio (Cr6Hz/C 2

H

4 of 0.011. Recirculated partially condensed reactor contents are used to control reactor temperature. Results are shown in Table 2.

Table 2 Run C 2

H

4 Temp MMAO:Ti* Activity FI MI density Ti** 1.0 94 1812 79,843 7.63 0.22 0.948 0.39 6 1.4 80 1590 60,098 6.21 0.11 0.943 0.36 7 1.4 105 1048 71,848 8.93 0.35 0.949 0.36 mole ratio added MMAO cocatalyst residual Ti in polymer

Claims (7)

1. A solid, particulated, heterogeneous, spray-dried, catalyst composition for use in combination with a cocatalyst for the polymerization of addition polymerizable monomers comprising: a) a Group 4 metallocene compound; b) a solid Group 4 metal-magnesium halide complex comprising moieties of at least magnesium, a Group 4 transition metal, and a halide; c) finely divided, inert filler, and d) an optional binder capable of joining components a) and b) and optionally c) into a particulated, heterogeneous, agglomerate without adversely affecting the catalytic properties thereof.

2. The catalyst composition as claimed in claim 1, wherein the Group 4 metal- magnesium halide complex comprises both +3 and +4 oxidation state Ti cations, Mg+2, A1 3 alkoxide and/or aryloxide moieties, halide moieties, and little or no internal electron donor.

3. The catalyst composition as claimed in claim 2, wherein the Group 4 metal metallocene is a zirconocene.

4. The catalyst composition as claimed in claim 1, wherein the metallocene is bis(n- butylcyclopentadienyl)zirconium dichloride.

The catalyst composition as claimed in claim 1, wherein the binder is an alumoxane.

6. The catalyst composition as claimed in claim 5 wherein the binder is methalumoxane.

7. A process for preparing a solid, particulated, heterogeneous, spray-dried, catalyst composition for use in combination with a cocatalyst for the polymerization of addition polymerizable monomers comprising forming a mixture comprising: a) a Group 4 metallocene compound; b) a solid Group 4 metal-magnesium halide complex comprising moieties of at least magnesium, a Group 4 transition metal, and a halide; c) finely divided, inert filler, and d) an optional binder capable of joining components a) and b) and/or c) into a particulated, heterogeneous, agglomerate without adversely affecting the catalytic properties thereof; and e) an organic, volitile, liquid diluent; and spray drying the mixture to remove diluent and leave the product in the form of solid particles.