US-A-5, 308, 811 discloses olefin polymerization catalysts comprising a product obtained by contacting a metallocene metal complex, at least one member selected from the group consisting of clay, clay minerals, ion exchanging layered compounds, diatomaceous earth, silicates and zeolites ; and an organic aluminum compound.

US-A-5, 830, 820 discloses an olefin polymerization catalyst comprising : (A) a clay modified with a compound capable of introducing a cation into layer interspaces in the clay mineral ; (B) a metallocene compound ; and (C) an organoaluminum compound.

US-A-5, 906, 955 discloses olefin polymerization catalysts comprising a Group IV metal complex and a modified clay obtained by treating clay or clay mineral with a compound containing a Group 15 or 16 element.

US-A-5, 928, 982 discloses olefin polymerization catalysts comprising : (A) a metallocene compound ; (B) a dehydrated an ion exchanging layered compound other than a silicate or an inorganic silicate prepared by treating an ion-exchanging layer compound other than a silicate or a starting silicate with a salt, acid or combination thereof ; and (C) an organoaluminum compound.

US-A-5, 973, 084 discloses olefin polymerization catalysts comprising a metallocene metal complex and at least one of an ion-exchanging layered compound other than a silicate and an inorganic silicate obtained by salt-treatment and/or acid treatment and having a water content of not higher than 3 percent by weight.

EP-A-658, 576 discloses the formation of modified clay containing supported catalysts containing a metallocene, wherein an ionic compound, especially a Bronsted acid salt, such as dimethylanilinium chloride, is included in the clay.

Those in industry continue to look for alternate treated clays which will enjoy utility as supports for Group 3-13, preferably Group 3-10, metal complexes used in olefin polymerization reactions, and as thickening or thixotropic agents for paints or greases,

viscosity modifiers for oiis and lubricants, ion exchange media, carners for pigments, nanofillers for thermoplastic polymers, and supports for hydrogenation catalysts.

Accordingly, the subject invention provides a treated clay composition useful in the preparation of a supported catalyst, said composition comprising the reaction product of : (a) clay or a clay derivative, and (b) an organometallic-or organometalloid-reagent of the formula : Rn-X, wherein each R is independently selected from the group consisting of hydride, halide, R', OR', NR'2, wherein each R'independently is a Cl-C30 substituted or unsubstituted aliphatic, cycloaliphatic, and aromatic hydrocarbyl group, and optionally two or more R'groups are bonded together to form a ring or fused ring structure, with the proviso that in at least one occurrence, R is R', or two R groups together are the fused derivative of two R'groups ; X is a Group 1 to 12 metal or a Group 13 metalloid ; and n is an integer corresponding to the valence of X.

The subject invention further provides a supported catalyst composition comprising : (1) a treated clay composition comprising the reaction product of (a) clay or a clay derivative, and (b) an organometallic-or organometalloid-reagent of the formula : Rn-X, wherein each R is independently selected from the group consisting of hydride, halide, R', OR', NR'2, wherein each R'independently is a C,-C3o substituted or unsubstituted aliphatic, cycloaliphatic, and aromatic hydrocarbyl group, and optionally two or more R'groups are bonded together to form a ring or fused ring structure, with the proviso that in at least one occurrence, R is R', or two R groups together are the fused derivative of two R'groups ; X is a Group 1 to 12 metal or a Group 13 metalloid ; and n is an integer corresponding to the valence of X, preferably 1, 2 or 3 ; and (2) a Group 3-13 metal complex comprising a n-bonded-or Lewis base donor- ligand group.

The subject invention further provides a process comprising polymerizing one or more olefin monomers with a catalyst composition comprising : (1) a treated clay composition comprising the reaction product of (a) clay or a clay derivative, and (b) an organometallic-or organometalfoid-reagent of the formula : Rn-X, wherein each R is independently selected from the group consisting of hydride, halide, R', OR', NR'2, wherein each R'independently is a C,-C3o substituted or unsubstituted aliphatic, cycloaliphatic, and aromatic hydrocarbyl group, and optionally two or more R'groups are bonded together to form a ring or fused

ring structure, with the proviso that in at least one occurrence, R is R', or two R groups together are the fused derivative of two R'groups ; X is a Group 1 to 12 metal or a Group 13 metalloid ; and n is an integer corresponding to the valence of X, preferably 1, 2 or 3 ; and (2) a Group 3-13 metal complex comprising a 1-bonded-or Lewis base donor- ligand group.

The subject invention further provides a process for preparing the treated clay, the steps of the process comprising contacting clay or a clay derivative with an organometallic- or organometalloid-reagent of the formula : Rn-X wherein each R is independently selected from the group consisting of hydride, halide, R', OR', NR'2, wherein each R'independently is a C1-C30 substituted or unsubstituted aliphatic, cycloaliphatic, and aromatic hydrocarbyl group, and optionally two or more R'groups are bonded together to form a ring or fused ring structure, with the proviso that in at least one occurrence, R is R', or two R groups together are the fused derivative of two R'groups ; X is a Group 1 to 12 metal or a Group 13 metalloid ; and n is an integer corresponding to the valence of X, preferably 1, 2 or 3.

Finally, the invention provides a process for preparing supported catalyst, the steps of the process comprising contacting clay or a clay derivative with an organometallic-or organometalloid-reagent of the formula : Rn-X wherein each R is independently selected from the group consisting of hydride, halide, R', OR', NR'2, wherein each R'independently is a d-Cso substituted or unsubstituted aliphatic, cycloaliphatic, and aromatic hydrocarbyl group, and optionally two or more R'groups are bonded together to form a ring or fused ring structure, with the proviso that in at least one occurrence, R is R', or two R groups together are the fused derivative of two R'groups ; X is a Group 1 to 12 metal or a Group 13 metalloid ; and n is an integer corresponding to the valence of X, preferably 1, 2 or 3, and contacting the foregoing treated clay with a Group 3-13 metal complex comprising a n-bonded-or Lewis base donor-ligand group.

All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1999.

Also any reference to the 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. As used herein the term"comprising"is not intended to exclude any additional component, additive or step. For purposes of United States patent practice, the contents of any patent,

patent application or publication referenced herein are hereby incorporated by reference in their entirety, especially with respect to the disclosure of synthetic techniques and general knowledge in the art.

Although most conveniently prepared from natural or artificial clays, it is understood that the present treated clay composition may be prepared from the individual aluminum silicate and magnesium silicate compounds or mixtures of silicate compounds or by any suitable technique. If prepared from a clay, the type of clay used in the preparation of the treated clay composition may be any of the five recognized classes, classified by the quantity of negative charge in the silicate layers of the clay. These are : 1) biophilite, kaolinite, dickalite or talc clays, 2) smectite clays, 3) vermiculite clays 4) mica, and 5) brittle mica.

Preferred clays are those that possess good cation transfer properties. The above clay materials exist in nature, and also can be synthesized, generally in higher purity than the native material. Any of the naturally occurring or synthetic clay materials may be used in forming the treated clay compositions of the present invention. Preferred clay materials are smectite clays, including montmorillonite, bidelite, saponite and hectorite or fluoromagnesium silicate. A most preferred clay is montmorillonite clay. Mixtures of the foregoing clays as well as mixtures thereof with inorganic silicates, such as sodium silicate, silica, or similar material may also be used.

By reacting the clay or clay derivative with the organometallic compound, it is believed that residual hydroxyl or other polar functionality of the clay is substantially reduced or removed by capping or reacting such groups with the organometallic compound. Preferably, a stoichiometric excess of organometal-or organometalloid compound compared to residual hydroxyl or other polar groups on the surface of the clay is employed. The resulting reaction product is believed to be the corresponding metal or metalloid derivative bonded to the clay or clay derivative through a moiety comprising the remnant of the hydroxyl (oxygen) or other polar functionality. A hydrocarbon or similar addition by-product is also formed in the reaction and is removed by degassing or similar process. The quantity of residual hydroxyl or other polar group on the surface of the clay may be determined by any suitable technique, preferably by titration with an alkylaluminum compound, especially trimethylaluminum or triethylaluminum. Desirably, the residual surface hydroxyl or other reactive functionality content of the clay or clay derivative,

subsequent to contact with the organometallic compound, is reduced to a level of less than 1 weight percent, preferably less than 0. 1 weight percent of the treated clay composition.

The clay or treated clay may be ion exchanged to replace at least a portion of native alkali metal cations or alkaline earth metal cations, especially sodium or magnesium cations, with a cation selected from the group consisting of H+, conjugate acids of Lewis bases, reducible Lewis acid cations, and reducible metal cations. Examples of conjugate acids of Lewis bases include ammonium, phosphonium, sulfonium, and oxonium cations, containing at least one proton. Preferred conjugate acids of Lewis bases are protonated ammonium cations, especially, NH4'or NR3H+, wherein R is as previously defined.

Examples of reducible Lewis acid cations include quaternary ammonium cations, ferrocenium, carbonium and silylium cations. Examples of reducible metal cations include Ag', Pb 2 and Fe 3. Any suitable anion, especially halide, nitrate, sulfate, tetrakis (perfluoroaryl) borate, or phosphate anions. may be used as a counter anion to the foregoing cations in the exchange process. Preferably the foregoing ion exchange is conducted on the clay prior to reaction with the organometallic-or organometalloid- compound.

Optionally, the alternating aluminum silicate and magnesium silicate layers of the ciaJ may be expanded from the spacing found in the natural clay so as to reduce the bulk density thereof to 1. 0 g/cm3 or less, preferably from 0. 5 to 0. 0001 g/cm3, most preferably from 0. 1 to 0. 001 g/cm3. Such expanded materials are referred to herein as a"clay derivative". Examples include substances including a propping agent within the silicate layers as well as those substances that are permanently expanded by a physical or chemical process, referred to as"aerogels".

Clay derivatives containing propping agents are known compositions. Propping agents are organic or inorganic materials added to a clay, especially an artificial clay, optionally in combination with a binder, during preparation to expand the normal interatomic distance between the silicate layers and remain in the matrix of the resulting clay derivative. Suitable propping agents include silicon dioxide and inorganic silicate materials. The size and porosity of the clay derivative may be controlled by the amount of the propping agent and optional binder, rate of agitation, temperature, use of a coagulant, and other known techniques.

By the term"aerogel"is meant a solid/gas mixture lacking in three dimensional ordered macro-structure. Preferably, the aerogel retains at least a partial lamella structure. That is, in portions of the composition alternating layers of aluminum silicate and magnesium silicate may be found, however the gross morphology of the material is not lamella or the lamella regions of the material are randomly arranged with respect to

one another. Moreover, the interlayer spacing of at least some of the residual lamella is expanded to from 2 to 100, 000 times, preferably 10 to 100, 000 times greater than the spacing of the unexpanded clay material. Preferably, expansion of the clay lamellae will occur prior to contacting with the organometallic-or organometalloid-compound and optional calcining.

Aerogels may be formed according to one technique, by preparing an aqueous dispersion of the clay or treated clay and subsequently drying the same in a manner to preserve a delaminated or partially delaminated, expanded structure, most preferably by freeze drying the same. Any other technique that allows the operator to prepare a similar stable, delaminated or partially delaminated. expanded structure, may be utilized as well.

Preferred support materials for use herein are prepared from aluminum- magnesium silicate-or fluorinated magnesium silicate-materials, especially aerogels prepared therefrom. Such substances provide superior catalyst activity in an olefin polymerization due to the increased distance between the silicate layers thereof compared to other supports, thereby increasing the available surface area of the material for catalyst attachment. In addition, the aerogel materials are desirably ultimately impregnated with Bronsted acid salts containing an organic ligand group, especially protonated ammonium salts, preferably tri (hydrocarbyl ; ammonium salts, most preferably, N, N-dialkylanilinium salts, which may play a role in causing the aerogel to retain its expanded form. Moreover, such aerogels are highly oleophilic and exhibit a remarkable ability to absorb or imbibe hydrocarbons, up to levels of 50 times the weight of the aereogel itself, or higher. This property may also benefit access to catalytic active sites contained within the aerogel by hydrocarbon reagents including monomers.

In the practice of the invention, the clay or clay derivative may be calcined, and desirably is calcined, either prior to or subsequent to treatment with the organometallic compound, preferably prior to such treatment. Calcining can be accomplished by heating the clay or clay derivative, optionally in the presence of an inert gaseous medium, especially nitrogen or argon, for a period of time, preferably from 10 minutes to 48 hours, in order to dehydrate the clay. Suitable calcination temperatures are from 200 to 800°C, preferably from 200 to 400°C, most preferably 200 to 300°C. Desirably the water content of the calcined clay or clay derivative is less than 0. 5 percent by weight, more preferably less than 0. 1 percent by weight.

Treatment of the clay or clay derivative with the organometallic-or organometalloid compound is performed by mixing the clay or clay derivative and the organometallic-or organometalloid-reagent optionally in an organic liquid, preferably an aliphatic or cycloaliphatic hydrocarbon, having from 5 to 12 carbons, or a mixture of such

hydrocarbons. The reaction is ideally conducted at a temperature from 0 to 100°C, preferably from 20 to 70°C for a time from 1 minute to 5 days, preferably from 30 minutes to 24 hours. After contacting the solid reaction product may be washed with an organic liquid, degassed and dried, optionally at reduced pressures. Preferred organometallic or organometalloid compounds are those wherein X is Mg, Zn or boron, most preferably Zn, and R. each occurrence, is C,-C2o alkyl, most preferably C,-C, o alkyi.

In a further embodiment of the invention, the catalyst composition may additionally include an inert inorganic or organic solid substance, such as silica, alumina, boron carbide, aluminosilicates, and polymers. Such polymeric substances may be formed in one or more pre-polymerizations of the supported catalysts of the invention or alternatively, by addition of a previously formed polymer thereto. Desirably, the inert solid substance is uniformly sized in order to assist in polymer particle formation or fluidization of a reactor contents during use in an olefin gas-phase polymerization process.

With respect to supported catalysts according to the present invention, the Group 3- 13 metal complex comprising a-c-bonded ligand or Lewis base donor ligand is desirably added to the support material after all of the foregoing forming and treating processes in order to form the finished supported polymerization catalyst. The metal complex may be added by deposition from an organic solution, such as by spraying, dripping, coating or otherwise contacting a solution of the metal complex with the support, and thereafter removing excess solvent. Suitable Group 3-13 metal complexes are those capable of being activated to polymerize ethylenically unsaturated compounds in combination with the present treated clay or clay derivative supports, desirably in the absence of additional catalyst compounds.

Examples of suitable metal complexes or compounds for use herein include Group 10 diimine Lewis base containing compounds corresponding to the formula : wherein M** is Ni (II) or Pd (II) ; X'is independently halo, hydrocarbyl, or hydrocarbyloxy ; R* is an aryl group, especially 2, 6-diisopropylphenyl or aniline group ; and CT-CT is 1, 2-ethanediyl, 2, 3-butanediyl, or form a fused ring system wherein the two T groups together are a 1, 8-naphthanediyl group.

Similar compounds to the foregoing are also disclosed by M. Brookhart, et al., in J.

Am. Chem. Soc., 118, 267-268 (1996) and J. Am. Chem. Soc., 117, 6414-6415 (1995).

Additional complexes or compounds include derivatives of Group 3, 4, or Lanthanide metal complexes comprising a 7 :-bonded ligand which are in the +2, +3, or +4 formal oxidation state. Preferred are those containing from 1 to 3 n-bonded anionic or neutral ligand groups, which may be cyclic or non-cyclic delocalized n-bonded anionic ligand groups. Exemplary of such n-bonded groups are conjugated or nonconjugated, cyclic or non-cyclic diene and dienyl groups, allyl groups, boratabenzene groups, phosphole, and arene groups. By the term"Z-bonded"is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized 7c-bond.

Each atom in the delocalized ul-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted heteroatoms wherein the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements, and such hydrocarbyl-substituted heteroatom radicals further substituted with a Group 15 or 16 hetero atom containing moiety. 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. Included within the term"hydrocarbyl"are Cl-20 straight, branched and cyclic alkyl radicals, C6 20 aromatic radicals, C7 20 alkyl-substituted aromatic radicals, and C7 20 aryl-substituted alkyl radicais. Suitable hydrocarbyl- substituted heteroatom radicals include mono-, di-and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples include N, N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, methyldi (t-butyl) silyl, triphenylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amino, phosphino, alkoxy, or alkylthio moieties or divalent derivatives thereof, e. g. amide, phosphide, alkyleneoxy or alkylenethio groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group, n-bonded group, or hydrocarbyl-substituted heteroatom.

Examples of suitable anionic, delocalized 7r-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and boratabenzene groups, as well as Cr-tO hydrocarbyl-substituted or C1, 0 hydrocarbyl-substituted siiyl substituted derivatives thereof. Preferred anionic defocalized n-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyctopentadienyl, indenyl, 2, 3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,

tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl, 3-pyrrolidinoinden-1-yl, 3, 4- (cyclopenta (0phenanth ren-1-yl), and tetrahydroindenyl.

The boratabenzenes are anionic ligands which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al. in Orqanometallics. 14, 1, 471-480 (1995). Preferred boratabenzenes correspond to the formula :

wherein R"is selected from the group consisting of hydrogen, hydrocarbyl, silyl, or germyl, said R"having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of such delocalized n-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 grour. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula :

wherein R"is as previously defined.

Phosphinimine/cyclopentadienyl complexes are disclosed in EP-A-890581 and correspond to the formula [(R**) 3-P=N] bM (Cp) (L1) 3-b, wherein : R** is a monovalent ligand, illustrated by hydrogen, halogen, or hydrocarbyl, or two R** groups together form a divalent ligand, M is a Group 4 metal, Cp is an anionic, detocatized, n-bonded group, preferably cyclopentadienyl, L1 is a monovalent ligand group, illustrated by hydrogen, halogen or hydrocarbyl, and bis1 or2.

A further suitable class of transition metal complexes for use herein correspond to the formula :

K'kM*Z'MLIXP, or a dimer thereof, wherein : K'is an anionic group containing delocalized z-electrons through which K'is bound to M, said K'group containing up to 50 atoms not counting hydrogen atoms, optionally two K'groups may be joined together forming a bridged structure, and further optionally one K' may be bound to Z' ; M* is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state ; Z'is an optional, divalent substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M ; L is an optional neutral ligand having up to 20 non-hydrogen atoms ; X independently at 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 bound to M by means of delocalized x-electrons (whereupon M is in the +2 oxidation state), or further optionally one or more X and one or more L 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 ; k is 0, 1 or 2 ; m is 0 or 1 ; I is a number from 0 to 3 ; p is an integer from 0 to 3 ; and the sum, k+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 bound to M via delocalized n-electrons, in which case the sum k+m is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K'groups. The latter complexes include those containing a bridging group linking the two K'groups.

Preferred bridging groups are those corresponding to the formula (ER'2) x 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 30 carbon or silicon atoms, and x is an integer from 1 to 8. Preferably, R' independently at each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K'groups are compounds corresponding to the formula :

wherein : M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state ; R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 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 bound by means of delocalized n-electrons to M, whereupon M is in the +2 formal oxidation state, and R', E and x are as previously defined.

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 Cs symmetry or possesses a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized =-bonded ligand groups, 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. Orqanomet. Chem., 232, 233-47, (1982).

Exemplary bridged ligands containing two n-bonded groups are : ethylenebis- (indenyl) ; dimethylbis (cyclopentadienyl) silane,

dimethylbis (tetramethylcyclopentadienyl) silane. dimethylbis (2-ethylcyclopentadien-1- yl) silane, dimethylbis (2-t-butylcyclopentadien-1-yl) silane, 2, 2- bis (tetramethylcyclopentadienyl) propane, dimethylbis (inden-1-yl) silane, dimethylbis (tetrahydroinden-1-yl) silane, dimethylbis (fluoren-1-yl) silane, <BR> <BR> <BR> <BR> dimethylbis (tetrahydrofluoren-1-yl) silane, dimethylbis (2-methyl-4-phenylinden-1-yl)-silane,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> dimethylbis (2-methylinden-1-yl) silane, dimethyl (cyclopentadienyl) (fluoren-1-yl) silane,<BR> <BR> <BR> <BR> <BR> <BR> <BR> <BR> dimethyl (cyclopentadienyl) (octahydrofluoren-1-yl) silane, dimethyl (cyclopentadienyl) (tetrahydrofluoren-1-yl) silane, (1, 1, 2, 2-tetramethy)-1, 2- bis (cyclopentadienyl) disilane, (1, 2-bis (cyclopentadienyl) ethane, and dimethyl (cyclopentadienyl)-1-(fluoren-1-yl) methane.

Preferred X"groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, or two X"groups together form a divalent derivative of a conjugated diene or else together they form a neutral, n-bonded, conjugated diene. Most preferred X"groups are C1-20 hydrocarbyl groups.

A further class of metal complexes utilized in the present invention corresponds to the preceding formula K'kMZ'mLnXp, or a dimer thereof, wherein 7'is a divalent substituent of up to 50 non-hydrogen atoms that together with K'forms a metallocycle with M.

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

Another preferred class of Group 4 metal complexes used according to the present invention corresponds to the formula : wherein : M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state ;

R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, each X is independently a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof ; Y is-O-,-S-,-NR'-,-PR'- ; and Z is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR'=CR', CR'2SiR'2, or GeR'2, wherein R'is as previously defined, preferably hydrocarbyl.

Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include : <BR> <BR> <BR> cyclopentadienyltitaniumtrimethyl,<BR> <BR> <BR> <BR> <BR> cyclopentadienyltitaniumtriethyl, cyclopentadienyltitaniumtriisopropyl, cyclopentadienyltitaniumtriphenyl, cyclopentadienyltitaniumtribenzyl, cyclopentadienyltitanium-2, 4-dimethylpentadienyl, cyclopentadienyltitanium-2, 4-dimethylpentadienyltriethylphosphine, cyclopentadienyltitanium-2, 4-dimethylpentadienyltrimethylphosphine, cyclopentadienyltitaniumdimethylmethoxide, cyclopentadienyltitaniumdimethylchloride, pentamethylcyclopentadienyltitaniumtrimethyl, indenyltitaniumtrimethyl, indenyltitaniumtriethyl, indenyltitaniumtripropyl, indenyltitaniumtriphenyl, tetrahydroindenyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumtriisopropyl, pentamethylcyclopentadienyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumdimethylmethoxide, pentamethylcyclopentadienyltitaniumdimethylchloride, bis (q5-2, 4-dimethylpentadienyl) titanium, bis (n5-2, 4-dimethylpentadienyl) titaniumtrimethylphosphine, bis (n5-2, 4-dimethylpentadienyl) titaniumtriethylphosphine, octahydrofluorenyltitaniumtrimethyl, tetrahydroindenyltitaniumtrimethyl,

tetrahydrofluorenyltitaniumtrimethyl, (tert-butylamido) (1, 1-dimethyl-2, 3, 4, 9, 10-#-1,4, 5, 6, 7, 8- hexahydronaphthalenyl) dimethylsilanetitaniumdimethyl, (tert-butylamido) (1, 1, 2, 3-tetramethyl-2, 3, 4, 9, 10-r)-1. 4. 5, 6, 7, 8- <BR> <BR> <BR> <BR> hexahydronaphthalenyl) dimethylsilanetitaniumdimethyl,<BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) dimethylsilanetitanium dibenzyl,<BR> <BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethylsi lanetitanium dimethyl,<BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)-1,2-ethan ediyltitanium dimethyl,<BR> <BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido)(tetramethyl-#5-indenyl)dimethylsilanetitan ium dimethyl, (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethylsi lane titanium (III) 2- (dimethylamino) benzyl ; <BR> <BR> <BR> (tert-butylamido) (tetramethyl-, 5-cyclopentadienyl) dimethylsilanetitanium (III) allyl,<BR> <BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethylsi lanetitanium (III) 2, 4-dimethylpentadienyl, (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethylsi lanetitanium (II) 1, 4-diphenyl-1, 3-butadiene, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) dimethylsilanetitaniu, n (I I) 1, 3-pentadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1, 4-diphenyl-1, 3- butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 2, 4-hexadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1, 3- butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) isoprene, <BR> <BR> <BR> <BR> (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) 1, 3-butadiene,<BR> <BR> <BR> <BR> <BR> <BR> (tert-butylamido) (2, 3-dimethylindenyl) dimethylsilanetitanium (IV) 2, 3-dimethyl-1, 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-dimethylindenyl)dimethylsilanetitanium (IV) 1, 3-butadiene, (tert-butylamido) (2, 3-dimethylindenyl)dimethylsilanetitanium (II) 1, 3-pentadiene, (tert-butylamido) (2, 3-dimethylindenyl) dimethylsilanetitanium (II) 1, 4-diphenyl- 1, 3-butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1, 3-pentadiene,

(tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dimethyl, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dibenzyl, (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1, 4-diphenyl-1, 3-butadiene, (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1, 3-pentadiene, (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 2, 4-hexadiene, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) dimethyl-silanetitanium (IV) 1, 3-butadiene, (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethylsi lanetitanium (IV) 2, 3-dimethyl-1, 3-butadiene, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) dimethylsilanetitanium (IV) isoprene, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl) dimethyl-silanetitanium (I I) 1, 4-dibenzyl-1, 3-butadiene, (tert-butylamido) (tetramethyl-#5-cyclopentadienyl)dimethylsilanetitanium (II) 2, 4-hexadiene, (tert-butylamido)(tetramethyl-#5-cyclopentadienyl)dimethyl silanetitanium (II) 3-methyl-1, 3-pentadiene, (tert-butylamido) (2, 4-dimethylpentadien-3-yl) dimethylsilanetitaniumdimethyl, (tert-butylamido) (6, 6-dimethylcyclohexadienyl) dimethylsilanetitaniumdimethyl, (tert-butylamido) (1, 1-dimethyl-2, 3, 4, 9, 10-#-1, 4, 5, 6, 7, 8-hexahydronaphthalen-4- yl) dimethylsilanetitaniumdimethyl, (tert-butylamido) (1, 1, 2, 3-tetramethyl-2, 3, 4, 9, 10-#-1, 4, 5, 6, 7, 8-hexahydronaphthalen-4- yl) dimethylsilanetitaniumdimethyl (tert-butylamido) (tetramethyl-n5-cyclopentadienyl methylphenylsilanetitanium (IV) dimethyl, (tert-butylamido) (tetramethyl-n5-cyclopentadienyl methylphenylsilanetitanium (I I) 1, 4-diphenyl-1, 3-butadiene, 1-(tert-butylamido)-2-(tetramethyl-#5-cyclopentadienyl)ethan ediyltitanium (IV) dimethyl, and 1-(tert-butylamido)-2-(tetramethyl-#5-cyclopentadienyl)ethan ediyl- titanium (II) 1, 4- diphenyl-1, 3-butadiene.

Complexes containing two K'groups including bridged complexes suitable for use in the present invention include : bis (cyclopentadienyl) zirconiumdimethyl, bis (cyclopentadienyl) zirconium dibenzyl,

bis (cyclopentadienyl) zirconium methyl benzyl, bis (cyclopentadienyl) zirconium methyl phenyl, bis (cyclopentadienyl) zirconiumdiphenyl, bis (cyclopentadienyl) titanium-allyi, bis (cyclopentadienyl) zirconiummethyimethoxide, bis (cyclopentadienyl) zirconiummethylchloride, 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 (pentamethylcyclopentadienyl) zirconiummethylchloride, bis (methylethylcyclopentadienyl) zir_oniumdimethyl, bis (butylcyclopentadienyl) zirconiumdibenzyl, bis (t-butylcyclopentadienyl) zirconiumdimethyl, bis (ethyltetramethylcyclopentadienyl) zirconiumdimethyl, bis (methylpropylcyclopentadienyl) zirconiumdibenzyl, bis (trimethylsilylcyclopentadienyl) zirconiumdibenzyl, dimethylsilyl-bis (cyclopentadienyl) zirconiumdimethyl, dimethylsilyl-bis (tetramethylcyclopentadienyl) titanium (III) allyl <BR> <BR> dimethylsilyl-bis (t-butylcyclopentadienyl) zirconiumdichloride,<BR> <BR> dimethylsilyl-bis (n-butylcyclopentadienyl) zirconiumdichloride, (methylene-bis (tetramethylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl, (methylene-bis (n-butylcyclopentadienyl) titanium (IIl) 2- (dimethylamino) benzyl, dimethylsilyl-bis (indenyl) zirconiumbenzylchloride, <BR> <BR> dimethylsilyl-bis (2-methylindenyl) zirconiumdimethyl,<BR> <BR> 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, dimethylsilyl-bis (fluorenyl) zirconiummethylchloride,

dimethylsilyl-bis (tetrahydrofluorenyl) zirconium bis (trimethylsilyl), (isopropylidene) (cyclopentadienyl) (fluorenyl) zirconiumdibenzyi, and dimethylsilyl (tetramethylcyclopentadienyl) (fluorenyl) zirconium dimethyl ; and ethylenebis- (indenyl) zirconium (II) (1, 4-diphenylbutadiene.

Other complexes, especially those containing other Group 4 metals, will, of course, be apparent to those skilled in the art.

The complexes are combined with the treated clay composition by any suitable technique. Ideally they are deposited from solution in an aliphatic, cycloaliphatic or aromatic liquid, by contacting the treated clay composition with a solution of the metal complex and removing the solvent. The treated clay composition may be immersed in the metal complex solution, or the solution may be coated, or sprayed onto the surface of the treated clay composition. Preferably, the liquid is thereafter removed or substantially removed.

When used as catalyst supports, the treated clay compositions of the invention beneficially do not require the use of metallocene catalyst activators, such as alumoxanes or inert non-coordinating anions. Indeed, in a preferred embodiment, the catalyst composition of the invention will comprise the treated clay composition and a Group 3-10 metal complex, in the substantial absence of a supplemental composition rendering the metal complex catalytically active. Such activators tend to add cost and/or lead to polymers having less preferred attributes, such as higher ash contents. However the use of such activators is not necessarily proscribed and may be utilized by the skilled artisan without departing from the scope of the present invention.

The catalysts may be used to polymerize ethylenically and/or acetylenically unsaturated monomers having from 2 to 100, 000 carbon atoms either alone or in combination. Preferred monomers include the C2 20 a-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1- pentene, 1-octene, 1-decene, long chain macromolecular a-olefins, and mixtures thereof.

Other preferred monomers include styrene, C1 4 alkyl substituted styrene, tetrafluoro- ethylene, vinylbenzocyclobutane, ethylidenenorbornene, 1, 4-hexadiene, 1, 7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, and mixtures thereof with ethylene.

Long chain macromolecular a-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions. Under suitable processing conditions such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer. Most preferably the present supported catalysts are used in the polymerization of propylene to prepare polypropylene having a

high degree of isotacticity. Preferred isotactic polypropylene polymers produced using the present supported catalysts have an isotacticity as measured by 13C NMR spectroscopy of at least 80 percent, preferably at least 90 percent, and most preferably at least 95 percent.

In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, such as temperatures from 0-250°C and pressures from atmospheric to 1000 atmospheres (0. 1 to 100 MPa). Slurry or gas phase process conditions are most desired. The support is preferably employed in an amount to provide a weight ratio of Group 3-13 metal complex (based on metal) : support from 1 : 100. 000 to 1 : 5, more preferably from 1 : 50, 000 to 1 : 10, and most preferably from 1 : 10, 000 to 1 : 200. Suitable gas phase reactions may utilize condensation of the monomer or monomers employed in the reaction, or of an inert diluent to remove heat from the reactor.

In most polymerization reactions the molar ratio of catalyst : polymerizable compounds employed is from 1 0-l2 : 1 to 10-' : 1, more preferably from 1 0-t2 : 1 to 10-5 : 1.

Suitable diluents for polymerization via a slurry process are noncoordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof ; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof ; perfluorinated hydrocarbons such as perfluorinated C410 alkanes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, and xylene. Suitable diluents also include liquid olefins which may act as monomers or comonomers including ethylene. propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene 4-methyl-1-pentene, 1, 4-hexadiene, 1, 7- octadiene, 1-octene, 1-decene, styrene, divinylbenzene, ethylidenenorbornene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), 4-vinylcyclohexene, and vinylcyclohexane. Mixtures of the foregoing are also suitable.

The catalysts may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.

The present catalyst compositions are advantageously employed in a process for preparing homopolymers of propylene, random or block copolymers of propylene and an olefin selected from the group consisting of ethylene, C4 10 olefins, and C4-1 0 dienes, and random terpolymers of propylene and olefins selected from the group consisting of ethylene and C4 10 olefins. The C4 10 olefins include the linear and branched olefins

such as. for example, 1-buten, isobutylene. 1-pentene. 3-methyl-1-butene, 1-hexene, 3, 4- dimethyl-1-butene, 1-heptene, and 3-methyl-1-hexene. Examples of C4 0 dienes include 1. 3-butadiene, 1. 4-pentadiene. isoprene, 1. 5-hexadiene, and 2, 3-dimethyl-1, 3-hexadiene.

Preferred polypropylene products have a molecular weight (Mw) of at least 10, 000, more preferably at least 50. 000, and most preferably at least 100, 000. and a molecular weight distribution. Mw/Mn of less than 6. 0, more preferably less than 4. 0, and most preferably less than 2. 5.

The polymerization is generally conducted under continuous or semicontinuous slurry polymerization conditions in hydrocarbon diluents such as propylene, propane, butene, buten-2, isobutane, hexane, heptane, and mixtures of the foregoing, generally at temperatures from 50 to 100 °C, and pressures from atmospheric to 1 MPa. The polymerization may be conducted in one or more continuous stirred tank tubular reactors or fluidized bed. gas phase reactors. or both. connected in series or parallel. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art.

The supported catalyst may also be prepolymerized prior to use as previously disclosed.

In a continuous reaction system, the reaction mixture is typically maintained at conditions at which the polymer is produced as a slurry of powder in the react'on mixture.

Use of highly active and highly stereospecific catalyst systems in propylene polymerization substantially eliminates the need to remove catalyst components or atactic polymer from the polymer product. The mixture of reaction components is fed continuously or at frequent intervals into the reactor system and is continuously monitored so as to ensure an efficient reaction and the desired product. For example, it is well known that supported coordination catalysts and catalyst systems of the type described above are highly sensitive, in varying degrees, to catalyst poisons such as water, oxygen, carbon oxides, acetylenic compounds and sulfur compounds. Introduction of such compounds may result in reactor upset and production of off-grade product. Typically, computer control systems are used to maintain process variables within acceptble limits, often by measuring polymer variables such as viscosity, density and tacticity, or catalyst productivity.

In the process, reactants and diluents, which may be a mixture of propylene, hydrogen, nitrogen, unreacted comonomers and inert hydrocarbons, are continuously recycled through the reactor, optionally with scavenging to remove impurities and condensation to remove the heat of polymerization. Catalyst and cocatalysts, fresh monomer or comonomer (s) and selectivity control agents, branching agents or chain transfer agents, if desired, are likewise continuously fed to the reactor. The polymer product is continuously or semi-continuously removed and volatile components removed and recycled. Suitable processes for preparing polypropylene polymers are known in the

art and illustrated by those taught in US-A-4. 767. 735. US-A-4. 975. 403. and US-A-5, 084, 513, among others.

Utilizing the catalysts of the present invention, copolymers having high comonomer incorporation and correspondingly low density, yet having a low melt index, may be readily prepared. Additionally, high molecular weight polymers are readily attained by use of the present catalysts, even at elevated reactor temperatures. This result is highly desirable because the molecular weight of a-olefin copolymers can be readily reduced by the use of hydrogen or similar chain transfer agent, however increasing the molecular weight of a- olefin copolymers is usually only attainable by reducing the polymerization temperature of the reactor. Disadvantageously, operation of a polymerization reactor at reduced temperatures significantly increases the cost of operation since heat must be removed from the reactor to maintain the reduced reaction temperature, while at the same time heat must be added to the reactor effluent to vaporize the solvent. In addition. productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration. Utilizing the present catalysts, a-olefin homopolymers and copolymers having densities from 0. 85 g/cm3 to 0. 96 gicm3, and melt flow rates from 0. 001 to 1000 dg/min. preferably 0. 01 to 150 g/10 minutes, are readily attained in a high temperature process. One skilled in the art will recognize that the targeted melt index will depend on the end use contemplated. In this regard, for instance, when it is desired to employ the polymer in a blown film application, appropriated melt indices will range from 0. 01 to 3 g/10 minutes.

The catalysts of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/a-olefin copolymers having high levels of long chain branching. The use of the catalysts of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch. The use of the present catalysts system advantageously allows for the economical production of ethylene/a-olefin copolymers having processability similar to high pressure, free radical produced low density polyethylene.

The present supported catalysts may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/a-olefin mixtures with low levels of a"H"branch inducing diene, such as norbornadiene, 1, 7-octadiene. or 1, 9-decadiene. The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical

production of polymers having excellent physical properties and processability. Preferably such polymers comprise ethylene, a C320 a-olefin and a"H"-branching comonomer.

The present supported catalysts are also well suited for the preparation of EP and EPDM copolymers in high yield and productivity. The process employed is preferably a slurry process such as that disclosed in US-A-5, 229, 478.

In general terms, it is desirable to produce such EP and EPDM elastomers under conditions of increased reactivity of the diene monomer component. The reason for this was explained in the above identified'478 patent in the following manner, which still remains true despite the advances attained in such reference. A major factor affecting production costs and hence the utility of an EPDM is the diene monomer cost. The diene is a more expensive monomer material than ethylene or propylene. Further, the reactivity of diene monomers with previously known metallocene catalysts is lower than that of ethylene and propylene. Consequently, to achieve the requisite degree of diene incorporation to produce an EPDM with an acceptably fast cure rate, it has been necessary to use a diene monomer concentration which, expressed as a percentage of the total concentration of monomers present, is in substantial excess compared to the percentage of diene desired to be incorporated into the final EPDM product. Since substantial amounts of unreacted diene monomer must be recovered from the polymerization reactor effluent for recycle, the cost of production is increased unnecessarily.

Further adding to the cost of producing an EPDM is the fact that, generally, the exposure of an olefin polymerization catalyst to a diene, especially the high concentrations of diene monomer required to produce the requisite level of diene incorporation in the final EPDM product, often reduces the rate or activity at which the catalyst will cause polymerization of ethylene and propylene monomers to proceed. Correspondingly, lower throughputs and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other a-olefin copolymer elastomer.

The present catalyst system advantageously allows for increased diene reactivity thereby preparing EPDM polymers in high yield and productivity. Additionally, the supported catalysts of the present invention achieve the economical production of EPDM polymers with diene contents of up to 20 weight percent or higher, which polymers possess highly desirable fast cure rates.

The non-conjugated diene monomer can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Examples of suitable non- conjugated dienes are straight chain acyclic dienes such as 1, 4-hexadiene and 1, 6- octadiene : branched chain acyclic dienes such as 5-methyl-1, 4-hexadiene ; 3, 7-dimethyl- 1, 6-octadiene ; 3, 7-dimethyl-1, 7-octadiene and mixed isomers of dihydromyricene and

dihydroocinene : single ring aiicyclic dienes such as 1. 3-cyciopentadiene ; 1, 4- cyclohexadiene ; 1, 5-cyclooctadiene and 1. 5-cyclododecadiene : and multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene ; bicyclo- (2. 2, 1)-hepta-2. 5-diene ; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB) ; 5-propenyl-2- norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl)-2-norbornene, 5- cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.

Of the dienes typically used to prepare EPDMs. the particularly preferred dienes are 1, 4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyciopentadiene (DCPD). The especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1, 4-hexadiene (HD).

The preferred EPDM elastomers may contain 20 up to 90 weight percent ethylene, more preferably 30 to 85 weight percent ethylene. most preferably 35 to 80 weight percent ethylene.

The alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably C3-, 6 alpha-olefins. Illustrative non-limiting examples of such alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene. 1-decene, and 1- dodecene. The alp ha-olefin is generally incorporated into the EPDM polymer at 10 to 80 weight percent, more preferably at 20 to 65 weight percent. The non-conjugated dienes are generally incorporated into the EPDM at 0. 5 to 20 weight percent ; more, preferably at 1 to 15 weight percent, and most preferably at 3 to 12 weight percent. If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified above.

At all times, the individual ingredients as well as the catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen.

Ethylene is generally added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the a-olefin and diene monomers. The ethylene content of the polymer is determined by the ratio of ethylene differential pressure to the total reactor pressure. Generally the polymerization process is carried out with a differential pressure of ethylene of from 10 to 1000 psi (70 to 7000 kPa), most preferably from 40 to 400 psi (30 to 300 kPa). The polymerization is generally conducted at a temperature of from 25 to 200°C, preferably from 75 to 170°C, and most preferably from greater than 95 to 140°C.

The polymerization may be carried out as a batchwise or a continuous polymerization process A continuous process is preferred, in which event supported catalyst, ethylene. a-olefin, and optionally diluent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom.

The present supported catalysts may also be employed to advantage in the gas phase copolymerization of olefins. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher a-olefins such as, for example, 1-butene, 1- hexene, 4-methyl-1-pentene are well known. In such processes, cooling will preferably be effected by introducing a volatile liquid to the bed to provide an evaporative cooling effect.

The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid (or can be condensed to provide such a liquid) this can be suitably be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be employed in this manner are olefins containing three to eight, preferably three to six carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed.

The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP 89691 ; US-A-4, 543, 399 ; WO 94/25495 and US-A-5, 352, 749. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO 94/28032.

The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such catalyst can be prepolymerized as described above, if desired.

The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers on the fluidized particles of supported catalyst within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin. Such

processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.

The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone.

Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidization grid, by a flow of fluidization gas.

The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.

A preferred method of cooling of the bed, involves the use of a co. idensed liquid which vaporizes in the reactor thereby removing heat therefrom. Such a condensing agent generally is rrecondensed and recycled along with unreacted monomers. The monomer (s) and any other liquids or gases which it is desired to charge to the reactor, such as, for example a diluent gas or hydrogen chain transfer agent, are desirably thoroughly dried and purified prior to use. Suitably, such materials may be contacted with alumina or zeolite beds or otherwise purified prior to use.

The gas phase processes suitable for the practice of this invention are preferably continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.

Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50°C, preferably from 60°C to 110°C, more preferably from 70°C to 110°C.

Typically the molar ratio of comonomer to monomer used in the polymerization depends upon the desired density for the composition being produced and is 0. 5 or less. Desirably, when producing materials with a density range of from 0. 91 to 0. 93 the comonomer to monomer ratio is less than 0. 2, preferably less than 0. 05, even more preferably less than

0. 02, and may even be less than 0. 01. Further typically, the ratio of hydrogen to monomer is less than 0. 5, preferably less than 0. 2, more preferably less than 0. 05, even more preferably less than 0. 02 and may even be less than 0. 01.

The above-described ranges of process variables are appropriate for the gas phase process of this invention and may be suitable for other processes adaptable to the practice of this invention. A number of patents and patent applications describe gas phase processes which are adaptable for use in the process of this invention, particularly, US-A-4, 588, 790 ; US-A-4, 543, 399 ; US-A-5, 352, 749 ; US-A-5, 436, 304 ; US-A-5, 405, 922 ; US-A-5, 462, 999 ; US-A-5, 461, 123 ; US-A-5, 453, 471 ; US-A-5, 032, 562 ; US-A-5, 028, 670 ; US-A-5, 473, 028 ; US-A-5, 106, 804 ; US-A-5, 541, 270 and EP applications 659, 773 ; 692, 500 ; and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032 ; WO 95/13305 ; WO 94/26793 ; and WO 95/07942.

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 20-25 oC, and"mixed alkanes"refers to a mixture of hydrogenated propylene oligomers, mostly C6-C12 isoaikanes, available commercially under the trademark Isopar E from Exxon Chemicals Inc.

Example 1 : K-20 montmorillonite (an ion exchanged clay in acid form available from Sud- Chemie) was sieved and 1 gram of a fraction having an average particle size between 15 and 35 pm was heated at 250°C for 4 days and was then suspended in 20 ml hexane and 1. 33 g of a 20. 8 percent solution of butylethylmagnesium in mixed alkanes was added.

The slurry was agitated for 2 h. The support was filtered, washed with toluene and re- slurred in 15 mi hexane. To this slurry, 0. 2 mi of a 0. 2 M solution of [tetramethylcyclopentadienyl-(dimethylsilyl) (t-butylamido)] titanium (II) piperylene in mixed alkanes were added. After 15 min the solid was filtered and washed with hexane. The solid was dried under dynamic vacuum and was used as such in a polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 3 bar (0. 83 MPa) ethylene and heated to 70°C. 1-Hexene was introduced to a level of 6000 ppm as measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. In a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were

subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed as a liquid to the reactor to maintain the above concentration. Temperature was regulated by dual heating and cooling baths. After 90 minutes the reactor was depressurized. and the salt and polymer were removed via a dump valve. The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 25. 8 g of ethylene/hexene copolymer corresponding to an activity of 25. 4 g/ghrBar (254 g/g-hr-MPa).

Example 2 : K-20 montmorillonite was sieved and 1 gram of a fraction having an average particle size between 15 and 35 um was heated at 250°C for 4 days, suspended in 10 ml hexane and 2. 66 g of a 20. 8 percent solution of butylethylmagnesium in mixed alkanes was added. The slurry was agitated for 1. 5 h. Then the solid was filtered, washed with toluene and re-slurried in 15 ml hexane. To this slurry 2. 1 ml of a 0. 019 M solution of ethylenebis (indenyl) zirconium (II) (1, 4-diphenylbutadiene) in mixed alkanes were added.

After 1 3/4 h the solid was filtered and washed with hexane. The solid was dried under dynamic vacuum and was used as such in the polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 5 bar (0. 85 MPa) ethylene and heated to 70 °C. 1-Hexene was introduced to a level of 6000 ppm as measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. In a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed to the reactor to maintain the above concentration. The reaction temperature was regulated by dual heating and cooling baths. After 90 minutes the reactor was depressurized, and the salt and polymer were removed via a dump valve.

The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 37. 1 g of ethylene/hexene copolymer corresponding to an activity of 36. 8 g/ghrBar (368 g/g-hr-MPa).

Example 3 : K-20 montmorillonite was sieved and 1 gram of a fraction having an average particle size between 15 and 35 um was heated at 250°C for 4 days, suspended in 10 ml hexane and 2 ml of a 1. 0 M triethylboron solution in hexane was added. The slurry was agitated for 1. 5 h. Then the solid was filtered, washed with toluene and re-slurried in 10 ml

hexane. To this slurry, 0. 2ml of a 0. 2 M solution of [tetramethylcyclopenta- dienyl (dimethylsilyl) (t-butylamido)] titanium (II) piperyiene in mixed alkanes were added.

After 2. 5 h the solid was filtered and washed with hexane. The solid was dried under dynamic vacuum and was used as such in a polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 6 bar (0. 86 MPa) ethylene and heated to 70°C. 1-Hexene was introduced to a level of 6000 ppm measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. In a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed to the reactor to maintain the above concentration.

Temperature was regulated by dual heating and cooling baths. After 16 minutes the reactor was depressurized, and the salt and polymer were removed via a dump valve. The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 3. 8 g of ethylene/hexene copolymer corresponding to an activity of 19. 5 g/ghrBar (195 g/g'hr-MPa).

Example 4 : K-20 montmorillonite was sieved and 1 gram of a fraction having an average particle size between 15 and 35 zm was heated at 250°C for 4 days, suspended in 10 ml hexane and 2 ml of a 1. 0 M solution of triethylboron in hexane were added. The slurry was agitated for 1. 5 h. Then the solid was filtered, washed with toluene and re-slurried in 15 ml hexane. To this slurry 2. 1 ml of a 0. 019 M solution of ethylenebis- (indenyl) zirconium (li) (1, 4-diphenylbutadiene in mixed alkanes were added. After 2. 5 h the solid was filtered and washed with hexane. The silica was dried under dynamic vacuum and was used as such in the polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 3 bar (0. 83 MPa) ethylene and heated to 70°C. 1-Hexene was introduced to a level of 6000 ppm as measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. In a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed to the reactor to maintain the above concentration.

Temperature was regulated by dual heating and cooling baths. After 16 minutes the

reactor was depressurized, and the salt and polymer were removed via a dump valve. The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 4. 5 g of ethylene/hexene copolymer corresponding to an activity of 24. 1 g/ghrBar (241 g/g-hr-MPa).

Example 5 : K-20 montmorillonite was sieved and 1 gram of a fraction having an average particle size between 15 and 35 sim was heated at 250°C for 4 days, suspended in 10 mi hexane and 2 ml of a 1. 0 M diethylzinc solution in hexane were added. The slurry was agitated for 2 h. Then the solid was filtered, washed with hexane and reslurried in 10 ml hexane. To this slurry 0. 21 ml of a 0. 019 M solution of [tetramethylcyclopenta- dienyl (dimethylsilyl) (n-t-butylamido)] titanium (II) piperyiene in mixed alkanes was added.

After 0. 5 h the solid was filtered and washed with hexane. The silica was dried under dynamic vacuum and was used as such in the polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 5 bar (0. 85 MPa) ethylene and heated to 70°C. 1-Hexene was introduced to a level of 6000 ppm as measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. In a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed to the reactor to maintain the above concentration.

Temperature was regulated by dual heating and cooling baths. After 90 minutes the reactor was depressurized, and the salt and polymer were removed via a dump valve. The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 20. 2 g of ethylene/hexene copolymer corresponding to an activity of 20. 1 g/ghrBar (201 g/g hr MPa).

Example 6 : K-20 montmorillonite was sieved and 1 gram of a fraction having an average particle size between 15 and 35 ßm was heated at 250°C for 4 days, suspended in 10 ml hexane and 2 ml of a 1. 0 M diethylzinc solution in hexane was added. The slurry was agitated for 2 h. Then the solid was filtered, washed with hexane and re-slurried in 10 ml hexane. To this slurry 2. 1 ml of a 0. 019 M solution of ethylenebis- (indenyl) zirconium (II) (1, 4-diphenylbutadiene in mixed alkanes were added. After 0. 5 h the solid was filtered and

washed with hexane. The silica was dried under dynamic vacuum and was used as such in the polymerization.

A 2. 5-L stirred, fixed bed autoclave was charged with 300 g dry NaCI, and stirring was begun at 300 rpm. The reactor was pressurized to 8. 7 bar (0. 87 MPa) ethylene and heated to 70°C. 1-Hexene was introduced to a level of 6000 ppm as measured by mass 56 on a mass spectrometer. A scavenger, 0. 5 g of triethylaluminum (TEA) treated silica, was introduced to the reactor. in a separate vessel, 0. 075 g of the above catalyst was mixed with an additional 0. 5 g scavenger. The combined catalyst and scavenger were subsequently injected into the reactor. Ethylene pressure was maintained and fed on demand, and hexene was fed to the reactor to maintain the above concentration.

Temperature was regulated by dual heating and cooling baths. After 30 minutes the reactor was depressurized, and the salt and polymer were removed via a dump valve. The polymer was washed with copious amounts of distilled water to remove the salt, then dried at 50°C.

Yield was 3. 5 g of ethylene/hexene copolymer corresponding to an activity of 10. 6 g/ghrBar (106 g/g hr MPa).