CA2087181C - Group ivb, vb and vib metal hydrocarbyloxides, with alumoxane for olefin polymerization - Google Patents

Abstract

The invention is a catalyst system including a Group IVB, VB or VIB transition m etal hydrocarbyloxide component and an alumoxane component which may be employed in liquid, slurry or bulk phase reacto rs to polymerize ethylene and .alpha.-olefins to produce a high molecular weight, narrow molecular weight distribution homo- and co-polymer.

Description

GROUP IVB, VB AttD VIB METAL
HYDROCARBYLOXIDES, WITH A~UMOXANE
FOR OLEFIN POLYHERIZATION
SPECIFICATION
F~FTn OF Tu~ I~VENTION
This invention relates to a catalyst and to a process using such catalyst for preparing polyolefins by liguid, solution, slurry, high pressure fluid, bulk or gas phase polymerization of the requisite monomers.
The catalyst comprises a Group IVB, VB, or VIB
transition metal hydrocarbyloxide compound which, when cocatalyzed with an alumoxane, provides an active catalyst system.
10 BACX~ND OF TH~ ~Nv~:lON
As is well known to those skilled in the art, various procecsQF and catalysts exist for the homopolymerization or copolymerization of ~-olefins.
For example, procecs-~ are Xnown for polymerizing ethylene or propylene, either alone or in the presence of small quantities of other monomers, to produce plastics. These plastics are typically used in such applications as blow and injection molding, extrusion coating, film and sheeting, pipe, ~ire and cable.
It is known that catalysts of a type generally described as Ziegler catalysts are useful for the polymerization of olefins under moderate conditions of temperature and pressure. It is also well known that the properties of polymer resin product obtained by ,s polymerizing olefins in the presence of Ziegler-type WO92/Ol~K PCT/US91/~92~

catalysts vary greatly as a function of the monomers of choice, catalyst components, catalyst modifiers and a variety of other conditions which affect the catalytic polymerization process.
Important among properties of polymer resins is the average molecular weight and nolecular weight distribution of the polymer. Hig~ molecular weights generally signify polymers having high strength properties. The melt index value (nMIn) of a polymer is a measure of its average molecular weight. However two different polyethylene resins can have the same MI
value and be significantly different in the distribution of the number of molecules of various molecular weights that make up the average molecular weight of the resin. Even ~ho~ different resins may have the same Ml value, one resin mig~t have very different quantities of higb molecular weiqht and low molecular weight fractions and thus exhibit very different processing characteristics and properties.
Thus, the molecular weight distribution (~MWDn) provides important additional information about the procesf-hility and mechanical properties of a polymer. The MWD may be determined by gel permeation chromatography measurements. Alternatively, another measure of the breadth of the MWD is Melt Index Ratio ( "MIR" ) .
Among Ziegler-type catalysts, ~ o~ed vanadiuc catalysts are known for a ~en~ency to produce polyethylene resins having a broad MWD. By reason of the reain's broad MWD a significant portion of the resin material may exist as polyethylenQ polymer chains h~ving a low degree of polymerization, i.e. ethylene oligomers. As an example, European patent publication 099 660 teaches that unless certain precautions are taken, such ethvlene oligomers are formed ~he W~92/OI~K 2 0 8 7 1 8 1 PCT/US91/04929 presence in the polyethylene resin of a significant proportion of low molecular weight oils or ethylene oligomers in the C10-C~z range poses certain disadvantages to the use of such resin for blow molding applications. The ethylene oligomers have relatively low boiling points, and at elevated temperatures during processing of the polyethylene resin to form useful articles, such as blow molding of household or industrial containers, in which the resin is heated to about ~00-F the ethylene oligomers in the resin vaporize, and, upon ex~osu~e to ambient air, condense into airborne droplets, ma~ing smoke. ~he smoke is considered ob~ectionable by prc_essors and impairs acceptability of broad MWD polyethylene resin products.
Further, such low molecular weight oils can have other adverse effects. For example, since such materials have a waxy nature, they can exude into mold vent holes causinq plugqing of the hole and thus poor operation.
A~ong catalyst systems useful for thermoplastic polyolefin production are those utilizing a catalyst component in combination with an alumoxane cocatalyst.
For example, U.S. 4,536,484 to Lacombe et al teaches a variation of the trad$tional Ziegler-Natta catalyst wherein the aluoinum alkyl cocatalyst is replaced with the reaction p~G~ of an alumoxane and a ~agnesium composition. The ~agnesiu~ co~po~ition is of the foroula Y~Mg~ wherein Y is an alkyl or alkoxy group having from 1 to 12 carbon atoms, X is a halogen, m is greater than or equal to 1 and a+b = 2m. The reaction between the magne~ium composition and alunoxane is carried out in an inert liquid medium. The resulting organo-magnesium-aluminum product is then ~ub~ected to chlorination and treatment with a transition metal compound wherein the transition ~etal i~ titaniu~, zirconium, vanadium, or chroniu~. Preferred W092/01~K PCT/US91/W92r transitional metal compo~n~s include Ti(OR)~Cl~ and Zr(OR)~Cl(,~ wherein R is a C~-C~ alkyl radical and p is from 1 to 4. The catalyst may be ~Y~G~ ~ed on an inorganic or organic support and ronsQsuently may be used in gas or slurry phase reactors. The catalyst is said to be useful for the polymerization of C2-C1, Q~
olefins, conjugated and non-conjugated dienes. The polymers produced using t~e Lacombe catalysts have melt flow ratios (HFR) in excess of about 30, indicating a broad molec~lar weight distribution.
The Chemical Abstract (105:173246z) of JP 61-141708 of Ube Industries relates to a solid catalyst system said to be useful for the production of a low halogen content polyethylene. One component of the catalyst system is a composition containing magnesium, a halide and a transition metal while the other component is an alumoxane. The first component is prepared by contacting a magnesium compound such as a magnesium halide, a hy~ OAY magnesium halide, a ~ 20 dialkoxy magnesium composition, etc. with a halogen containing compound such as aluminum, tin or silicon halides, alkoxysilane halides, etc. The product of this reaction is then treated with a transition metal composition preferably a titanium composition, such as TiX,(OR),_ wherein X is a halogen, R is Cl-C~ alkyl and m i~ 1 to 4; or P.TiX~_ wherein P is C~-C~ alkyl; or vanadium halide or vanadium oxyhalide compounds.
The Chemical Abstract (107:96316~) of JP 62-072631 to Hitsui relates to a catalyst system for the production of dimers or oligomers of Q-olefins. The catalyst systen includes a transition metal component, a phocphorous ester/soluble magnesium component and, optionally, an alumoxane. The transition metal component nay include bis-butoxytitaniun dichloride, ~92/OI~K 2 0 8 7 1 8 1 PCT/US91/~929 tTi(OBu)2Cl2] tetrakis-butoxytitanium tTi(oBu)~]~ or tetrakis-2 ethylhexoxytitanium [Ti(0-2-ethylhexyl),].
Chemical Abstract (108:222271b) also lists Idemitsu Kosan's JP 63-003008 which relates to the s production of polyolefins which are said to be of "high purity~ and "high molecular weight.~ Idemitsu's process uses a catalyst system including oxygen-containing titanium com~ouJ-~s and the reaction product of water and organic aluminum compounds (apparently alumoxane compositions). The titanium com~o~"d_ include those of the formulae: Ti(OR)~X,~, Ti(o~).(oR~ Ti(OR)~(OCOR),~ or RO(Ti(OR)2o)~-R
wherein R and R' are Cl-C20 alkyl groups, X is a halogen, n is greater than O but less than or equal to 4, m and k are less than 4 but greater than 0, and p is greater than or egual to 2 but less than or equal to 20.
The Che~ical Abstract (99:105887s) of Polish patent P~ 116,247 discloses a supported transitional metal complex-alumoxane catalyst syste~ for the production of polyethylene having a molecular weight of about 82,000 and a bulk density of 480 g/d~3. The transitional metal complex of the catalyst system is of the formula: Ti(OR)~Cl3~ wherein n equals 0-3 and R is phenyl, C2-C10 alkyl, chlorinated phenyl or c~lorinated C2-C10 alkyl.
Chemical Abstract (108:151044s) on an article by Oliva et al. in Makromol. Che~.. Ra~d Commun., 9(2), pp. 51-5 (1988) relates to the production of polypropylene in the ~re-ence of soluble transition metal com~o~n~s and alumoxane as the catalyst system.
The disclosure indicates that the solution process may employ tetrakis-butoxyt~tan~um rTi(OBu),], tetrakis-phenylzirconium t2r(Ph),~ or tetrakis phenyltitanium WO92/Ol~K PCT/US91/W9?-2o87l8l tTi(Ph),~ in combination with mQthylalumoxane as an effective catalyst system for propylene polymerization.
European Patent Application 241,560 describes a catalyst system the transition metal component of which is a hydrocarbyloxide compound. In that embodiment of the catalyst system comprising a tetrakis-hydrocarbyloxide transition metal compound (exemplified by propoxy and butoxy species of titanium and zirconium) or a bis-hydrocarbyloxide transition metal dihalide (exemplified by bis-rheno~y titanium dichloride) cocatalyzed by an alumoxane, the catalyst system is shown to polymerize propylene to an amorphous polypropylene of high ~olecular weight. In a s~:~.d embodiment of the catalyst system, a transition metal halide is first reacted with an organic compound having at least two hydroxy groups to form a product compound wherein the two hydroxy ~Lou~S of the organic com~ou--d are bonded to one transition metal atom. The product transition metal compo~n~ may be ~iewed as a bihydrocarbyloxide derivative wherein the hydrocarbyloxide ligands are interbridged one with another. Cocatalyzing this interbridged bihydrocarbyloxide transition Detal compound with an alumoxane provides a catalyst system which polymerizes propylene to a crystalline polymer the isotactic stereoregularity of which depends upon the type of bihydroxy organic compound used to produce the transition metal deri~ative. Similarly, Niyatake et al., ~Akromol. Chem.. Rapi~ c -~.., 10, pp. 349-352 (1989) describes the reaction of 2,2'-thiobis(6-~-butyl-~ methylphenol) to for~ titanium and zirconium derivatives having a bidentate ligand which, when cocatalyzed with methyalumoxane, provides a catalyst system which is active for ethylene and propylene Polymerization.

~92/01~K 2 0 ~ 7 1 8 1 PCT/US91/~929 From the above, it is clear that efforts have been directed toward the development of olefin polymerization wherein a transition metal complex is employed in combination with an alumoxane. Some of 5- these transition metal complexes have included transition metals complexed with hydrocarbyloxide groups wherein the hydrocarbyl ligand is an alkyl or an aryl ligand. Those refe~. -f- which do indicate the MWD of the polymer p~G~UC~ of the prior catalyst systems show a broad MWD of greater than about 30 MFR.
It would be desirable to develop a catalyst syste~
highly active for olefin polymerization which comprises a transition metal/alumoxane complex which allows the production of a polymer having both high molecular weight and a narrow MWD.

SUMM~RY OF T~ Ihv~r..lON
The invention is a catalyst syste~ comprising, a Group IVB, VB or VIB transition metal hydrocarbyloxide component and an alumoxane component, ~hich may be employed in liquid, solution, slurry, high pressure fluid, bulk or gas phase reactors to polymerize olefins, diolefins, acetylenic~lly unsaturated monomerC~ ethylene or C3 to Cw Q-olefins alone or in combination with one or ~ore C~ to C20a-olefins or other unsaturated monomers to produce high moler~ r weight, narrow moleru1ar weight distribution homopolymers and copolymers.
Transition metal hyd~o~arbyloxide compounds useful in preparing catalyst systens of this invention are Le~ Pstnted by the formulae:
M(OR~
~Rl) (ORl) ~--2XI~
or (~lO)M(ORl)(ORl) ,Y ~

WO92/Ol~K PCT/US91/~92~
2o87l8l wherein M is a Group IVB, VB or VIB transition metal;
each X is in~pen~ently halogen, or a hydrocarbyl, alkoxy or an amide group having from one to 30 carbon atoms; Rl is a hydrocarbyl radical of the formula ~1~R' ~7 ~ RS

or q ~~ 2~

~ ~R' "R'5 wherein "t~ is an integer nu~ber of 0 to 10 and each of 2S the R2 to Rl~ substituents are independently hyd~Gye--, halogen, a hy~lG~arbyl group such as a straight or br~nc~e~ chain alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a halogenated hydrocarbyl group, an alkoxy group, an amine group, or at least two of the substituents R2 to R~ or R~ to Rl~ may be a single hyd.o~arbylene radical which forms a fused polycyclic ring sy~te~ or a polynuclear aromatic system; ~n~ is a number at least equal to ~ and is equal to the valence of the transition metal M; and ~y~ i8 a number equal to 3s or greater than 2 and less than or equal to "n", ~y~ n ~)92/0l006 2 0 8 7 1 8 1 PCr/USgl/04929 is a number equal to or greater than 3 and less than or equal to ~n", and "y"n is a number equal to or greater than 4 and less than or equal to "nn. R7 and R~ may independently be the same as the cyclic group containing R2 to R~ or R~ to Rl~ when t = 1. Rs ic preferably a bulky ligand selected to provide steric hinderance which should prevent the dimerization or association of two or more of the transition metal hydrocarbyloxides. It is therefore preferably that be selected from those large oxy ligands such as substituted phenoxy ligands or substituted cyclohexoxy ligands. Substituted phenoxy ligands such as 2,6-disubstituted and 2,4,6-trisubstituted phenoxy ligands are preferred.
lS The alumoxane component of the catalyst system may be represented by the formulae:
(R'-Al-0). and R'(Rn-Al-0).-AlR'''' or mixtures thereof, wherein R', R~, R''' and R'"' are independently a univalent anion ligand such as a C~-C~
alkyl group or halide and ~m" is an integer from 1 to about 50, and ~m~ is preferably from about 13 to about 25.
Catalyst systems of the invention may be prepared by placing the transition metal hydrocarbyloxide compound and the alumoxane in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of one or more olefin monomer(s).
A typical polymerization process of the in~ention such as for the polymerization or copolymerization of olefin~ comprises the steps of contactinq ethylene or C~ to C20 ~-olefins alone, or with other unsaturated monomers including C,-C20 Q-olefins, W~ ~ PCT/US9l/~92 C,-C20 diolefins, and/or acetylenically unsaturated monomer6 either alone or in co~b~nation with ot~er olefins and/or other unsaturated monomers, with a catalyst comprising, in a suitable polymerization diluent, the hydrocarbyloxide compound illustrated above and a methylalumoxane in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1 or more; and reacting such monomer in the presence of such catalyst system at a temperature of from about -lOO-C to about 300-C for a ti~e of from about 1 s~co..d to about 10 hours to produce a polyolefin having a ~eigbt average molecular weight of from about 500 or les~ to about 2,000,000 or more, typically from about 1,000 to about 1,000,000 and a molecular weight distribution of from about 1.5 to about 15Ø
D~CRIPTION OF THF P~F~RED ~R~DI~F~TS
The catalyst cystem of thi~ invention comprise~ a hydrocarbyloxide compound of a Group IVB, VB or VIB
transition metal of the Periodic Table of Element~ (CRC
Handbook of C~emistrY and P~ysics. 68th ed. 1987-86) in combination with an alumoxane cocatalyst. Catalyst system~ of this invention may b~ used ~n liqu~d, solution, slurry, ~$gh pres~ure fluid, bulk or ga~
phase reactor~ to produce homo- and co- polyolefins of high weight average molecular weight (MW) and narrow molecular weight distribution (~WD). lf desired, a catalyst system of thi~ in~ention ~ay b~ used together w$th another cataly~t syste~ of con~entional compos$tion to form a mixed cataly~t 6ystem to produce polymer product~ of a broadened or b$modal NW~.
tal~st Com~nents The tran~$tion metal hyd~o~arbyloxide component used in prepar~ng cataly~t system~ of this invention are represented by the formulae:

~092/01~K 2 ~ 8 7 1 8 1 PCT/U591/~929 M(OR~
)(0R~ 2Xo~ or (~lo) M(ORl) (ORl) ,. ,Y_ ~.
wherein M is a Group IVB, VB or VIB transition metal;
s each X is independently halogen, or a hydrocarbyl, alkoxy or an amide group ha~ing from one to 30 carbon atoms; R1 is a hydrocarbyl radical of the formula:

0 R~

~7 R5 ~ ~lS -wherein ~t~ i~ an integer number of O to lO and each of the R2 to R1~ substituent~ are independently hydroqen, halogen, a hydLo~arbyl group such as a straight or branc~-~ chain alkyl group, an aryl group, an alkylaryl group, an arylaLkyl group, a halogenated hydrocarbyl group, an alkoxy group, an amine group or at least two of the substituents R~ to R~ or R~ to R1~ may be a ~ingle hyd~o~rbylene radical which for- a fused polycyclic ring system or a polynuclear arooatic syste~, "n~ is a number at least equal to 4 and is equal to the valence of the transition metal M; ~ is a nu~ber equal to or WO92/01~K PCT/US91/W92~

greater than 2 and less than or equal to ~n", ~y~ n is a number equal to or greater than 3 and les than or equal to "n~, and ~y"~ is a number equal to or greater than 4 and less than or equal to ~nn. Preferably Rl is a hydroarbyl radical wherein ~t~ is 0 to 4, and when "t~
is 1, R7 and R~ may independently be the same as the cyclic group containing RZ to R~ or R~ to R~. More preferably, Rl is of the formula:

lS ~R~

wherein R~ and R~ are a~ defined before and at least R
and R' are hy~ocarbyl or hy~,o~arbyloxy substituents.
Transitlon ~etal l.ydkG~arbyloxide compo~AC which, when cocatalyzed with an alu~oxane, act as single-sited catalysts for olefin polymerization and hence produce narrow MWD polyolefin~ which are preferred.
Accordingly, the preferred transition metal hydrocarbyloxide components are those of the Group IVB, VB and VIB transition metal~ (M) which are least susceptible to reduction and wherein the Rl hydrocarbyl radical has sufficient bulk as to prevent dimerization or ~s~oeiation of two or ~ore of the transition metal hy~Lo ~rblyoxides due to steric h ~n~rance. $he preferred transition metal~ are those of ~GU~ IVB and ! VB. Preferably the R1 },y~o~arbyl radical is an aromatic radlcal wherein at least the R2 and R~

~ 92/OI~K 2 ~ 8 7 1 8 1 PCT/US91/~929 substituents are hydrocarbyl or hydrocarbyloxide radical~ having from 1 to 20 carbon atoms.
Particularly useful for preparing catalyst syste~s which produce high molecular weight narrow MWD
polyolefins are those transition metal hydrocarbyloxide compounds where the hydrocarbyl radical Rl is 2,6-disubstituted and 2,4,6-trisubstituted with alkyl, aryl, alkylaryl, arylalkyl or alkoxy substituents.
Illustrative compounds are the:
(A) tetrakis-2,6-disubstituted phenoxy Group IVB
transition metal compounds [M(ORl)~; H is Group IV~ metal; R3, R', R5 are hydrogen wherein the substituents ~R2 and R~] are each, independently, methyl, ethyl, isopropyl, tert-butyl, phenyl or the like, as for example:
(1) tetrakis-2,6-di-tert-butylphenoxy zirconium;
(2) tetrakis-2-methyl-6-tert-butylphenoxy hafniu~;

(3) tetrakis-2,6-diphenylphenoxy titanium:
(8) tetrakis-2,4,6-trisubstituted phenoxy ~GU~
IVB transition metal com~Q~ tHtORl),; M is a Group IVB metal; R~ and R~ are hydrogen]
wherein the substituents ~R2, R' and R~] are each, ;ndepen~ently, methyl, ethyl, isopropyl, tert-butyl, phenyl or the like and the R' substituent may be an alkoxy or another univalent anionic ligand, as for example;
(1) tetrakis-2,4,6-trimethylphenoxy hafnium;
(2) tetrakis-2,6-di-tert-butyl-4-met~oxy-phenoxy zirconium:
(C) tris-2,6-disubstituted phenoxy Group IVB
,s transition metal sonpounds ~M(ORl) 3X; M ~s a W092/Ol~K PCT/US91/~9 Z08~ 18 1 - 14 -Group IVB metal; R3, R', R5 are hydrogen; X is halogen or a psuedo halogen group such as a hydrocarbyloxide or amide] wherein the substituents [R2 and R~] are each, independently, methyl, ethyl, iso~.o~yl, tert-butyl, phenyl or the like, as for example;
(1) tris-2,6-di-tert-butylphenoxy zirconium chloride;
(2) tris-2,6-di-tert-butylphenoxy hafnium methoxide;
(D) Tris-2,4,6-trisubstituted phenoxy Group IVB
transition metal compounds ~M(OR'),X; M is a Group IVB metal; R3 and Rs are hydrogen; X is lS a halogen or a pseudo halogen group such as a hydrocarbyloxide or amide~ wberein the substituents tR2, R' and R'] are each independently, methyl, ethyl, isoyLG~yl, tert-butyl, phenyl or the like and the R' substituent may be an alkoxy or other univalent anionic ligand, as for example;
(1) tris-2,6-di-tert-butylphenoYy-4-methoxy zirconiuc chloride;
(2) tris-2,6-di-tert-butylphenoxy-4-N,N'-dimethyamino hafniu~ chloride:
(E) tris-2,6-disubstituted phenoxy }l~dL~ ~arbyl Group IVB transition metal coml-o~ s [M(ORl) 3X; M is a Group rVB metal; R3, R' and R5 are hydrogen; X is a hyd~o-arbyl radicall wherein the substituents ~R2 and R~] are each independently methyl, ethyl, iso~,G~l, tert-butyl, phenyl or tbe like, as for example;
(1) tris-2,6-di-tert-butylphenoxy methyl zirconium;

WO92/01~K 2 0 8 71 81 PCT/US91/W929 (2) tris-2,6-di-tert-butylphenoxy methyl hafnium:
(F) tris-2,4,6-trisubstituted phPno~y Group IVB
transition metal compo~nA~ [M(OR1)3X; M is a Group IVB metal; R3 and R5 are hydrogen; X is a hydrocarbyl radical wherein the substituent ~o~ R2, R', R~l are each independently methyl, ethyl, isopropyl, tert-butyl, phenyl, or the like and the R' substituent may be an alkoxy or other univalent anionic ligand, as for example:
(l) tris-2,6-di-tert-butyl-4-methoxy-phenoxy methyl zirconium;
(2) tris-2,6-di-tert-butyl-4-methylphenoxy methyl zirconium:
(G) bis-2,6-disubstituted phenoxy GLOU~ IVB
transition metal compo~nAs [M(OR1)2X2; M is a Group IVB metal; R~, R' and R~ are hydrogen; X
is halogen, h~llG~arbyl, hydrocarbyloxide or amide~ wherein the ~ubstituents tR2 and R~
are independently methyl, ethyl, isopropyl, tert-butyl, phenyl, or t-he li~e, as for examplc;
(l) bis-2,6-di-tert-butyl-4-nethylphenoxy 2S zirconium dichloride;
(2) bis-2,6-di-tert-butyl-4-~ethylphenoxy-tert-butoxy titanium chloride:
(H) bis-2,4,6-trisubstituted F~enoxy Group IVB
transition metal comFo~nA~ [M(ORl)2X2; M is a Group IVB metal; R~ and R~ are hydrogen; X is halogen, hyl~c-arbyl, hyl~G~arbyloxide or amide~ wherein the ~ubstituent- lR2, R', R~
are each, independently, ~ethyl, ethyl, is~r~yl, tert-butyl, phenyl, or the like, an~ the R' sl~kst.ituent ~ay be an al!~oxy o, WO92/01~K - PCT/US91/0492 ~ 0 8~ 18 1 - 16 -any other univalent anionic ligand for exanple:
(1) bis-2,6-di-tert-butyl-4-methylphenoxy zirconium dichloride;
(2) bi~-2,6-di-tert-butyl-4-methylphenoxy-tert-butoxy tltanium chloride.
(I) pentakis-phenoxy Group VB transition metal com~ , for example:
(1) pentakis-phenoxy tantalum;
(2) pentakis-~heno~y niobium:
(J) pentakis-2,6-disubstituted r~enoxy Group VB
transition metal compounds [M(ORl)~; M is a Group VB metal; R3, R' and R5 are hydrogen]
wherein the ~ubstituents tR2 and R~ are each, independently, hydrogen, methyl, ethyl, propyl, or the like, for example;
(1) pentakis-2,6-dimethylphenoxy tantalum;
(2) pentakis-2,6-dimethylphenoxy niobium:
(~) pentakis-2,4,6-trisubstituted phenoxy Group IVB tran~ition ~etal compon~AC (M(ORl)~; M is a Group V~ metal; RJ and R~ are hydrogen]
wherein the ~ubstitute~ -tR2, R' and R~] are each, independently, hydrogen, methyl, ethyl, propyl, or the l~ke and the R' substituent may be an alkoxy or other univalent anionic ligand, for exa~ple;
(1) pentakis-2,4,6-trimethyl phenoxy tantalum;
(2) pentakis-2,4,6-trimethyl phenoxy niobium:
(~) tetraki~-2,6-di~ub~tituted phenoYy Group VB
metal co~po~A~ tH(ORl)~X; M is a Group VB
metal; R~, R' and R~ are hyd~Gg~..; X is halogen, hy~ocarbyl, hy~o~arbyloxide or amid~] wherein the substitu2nts ~R2 and R']

WO92/Ol~K 2 0 8 7 1 8 1 PCT/US91/04929 are each independently nethyl, ethyl, propyl, or thc like, for example;
(1) tetraki~-2,6-dimethylpbenoxy ~ethyl tantalum;
(2) tetrakis-2,6-dimethylphenoxy methyl niobium;
(3) tetrakis-2,6-dimethyl phenoxy tantalum chloride;

(4) tetrakis-2,6-dimethyl phenoxy niobium chloride:
(M) tetra~is-2,4,6-trisubstituted phenoxy Group IVB transition metal com~ou,.ds ~H(ORl),X; M
ia a Group VB metal; R3 and Rs are hydrogen;
X is a halogen, hydrocarbyl, hydrocarbyloxide or amide] wherein the substitutes [R2, R~ and R~] are each independently methyl,ethyl, propyl, or the like and the R~ sub~tituent may be an alkoxy or other univalent anionic ligand, for example;
(1) tetrakis-2,~,6-trimethyl phenoxy tantalum chloride;
(2) tetrakis-2,4,6-trimethyl phenoxy niobiun chloride;
(N) tris-2,6-~is~hstituted Group VB metal compo~dc tH(ORl)3X2; M is a Group VB metal;
R~, R~ and R5 are hy~.G~en; X is halogen, hydLooarbyl, hydlocarbyloxide or amide]
wherein each substituent tR2 and R'] is, in~ep~n~ently, methyl, ethyl, isopropyl, tert-butyl, phenyl or the like, for exa~ple;
(1) tris-2-methyl-6-tert-butylphenoxy tantalu~ dichloride;
(2) trls-2-~ethyl-6-tert-butylphenoxy niobium dichloride;

WO92/Ol~K PCT/US91/~9 2 0 87 18 ~ - 18 -(3) triQ-2,6-dimethylp~enoYy dlbenzyl tantalum:
(o) tris-2,4,6-trisubstituted Group VB metal compo~n~ tM(ORl)~X2; ~ is a Group VB metal;
R~ and Rs are hydrogen; X i5 halogen, hydrocarbyl, hydrocarbyloxide or amide]
wherein each substituent [R2, R' and R~] i~
independently, methyl, ethyl, isG~o~yl, tert-butyl, phenyl or the like and the R' substituent may be alkoxy or any other univalent anionic ligand, for example;
(1) tris-2,6-diphenyl-4 methylphenoxy tantalum dichloride;
(2) tris-2,4-dimethyl-4-tert-butylphenoxy tantalum dichloride:
(p) bis-2,6-~is-lhstituted ~?no~y Group VB
transition metal compounds lM(ORl)2%3; H is a Group VB metal; X is halogen, hydrocarbyl, hyd.o~arbyloxide or amide; R~, R' and R5 are hydrogen] where the cubstituents t~2 and R']
are, ~n~epenAently, methyl, ethyl, iso~G~yl, tert-butyl, phenyl or the like, for example;
(1) bis-2,6-di-tert-butylph~nQYy trimethyl niobium;
(2) bis-2,6-dimethyl~enoxy tribenzyl tantalum;
(3) bis-2,6-diphenylrhenQxy tantalun trichloride;
(~) bi~-2,4-di-tert-butylphenoxy tris-trimethylsilyl methyl tantalun:
(Q) bis-2,~,6-trisub~tituted phenoxy Group VB
transition Detal co~po~n~ [~(ORl)2X~; h ls a Group VB metal; X is halogen, hyl-o~rbyl, hydrocarbyloxide, or anid-; Rl and R~ are hydrogenl wherein the s~lbsti'uents ~2, R', WO92~01~K 2 0 8 7181 PCT/US91/W929 R~ are nethyl, ethyl, isopropyl, tert-butyl, phenyl or the like and the R~ substituent may be an alkoxy or other univalent anionic ligand, for example;
S (1) bis-2,4,6-tri-tert-butylphenoxy tantalu~
trichloride;
(2) bis-2,6-diphenyl-4-methylphenoxy tantalum trichloride:
(R) mono- or di- cyclometalated transition metal hyd~Gcarbyloxide compounds [~(OR1)~ wherein one or nore of the R~ or R~ substituents become bonded to the transition metal (M) for example compounds represented by the formulas:

C--h~O R )y:~
k f~s~R~-h~ a3 W092/01~K PCT/US91/W9?~
2o87l8l or s R~

C M
~' \ ~ O

p~S ~R~
k ~3 wherein R~' is an R~ ~ubstituent where one carbon has beco~e bonded to the transition ~etal witb retention of-the carbons valency of four by loss of an attached ligand, most likely being a proton;
illustrative examples include:
(1) Ph2Ta(0-2-tBu-6-C(CH3)2CH2C~H3)-(0-2,6-t~u2C~

(2) PhTa(0-2-tBu-6-C~CH3)2CH2C~H3) 2 (S) alkylidene derivatives of transition metal hyd.ocarbyloxide com~ou.-ds ~H(OR1)~X~1 wherein at least a quantity of the n-y value for X is supplied by an alkylidene radical--i.e., 2 ~5 values of X fulfilled by an alkyliden~

WO92/01~K 2 0 8 7181 PCT/US91/~929 radical], for example ComFo~nAs represented by the formulas:
(1) Ta(OR1)2(- CHSi(CH~)~)(CH2Si(CH3)~), R1 - 2,6-tBu2C~H3;
(2) Ta(OR1)2(- CH(C~H5))(CH2(C~H~)), R1 ~ 2,6-tR~l2C~H~: and (T) polynuclear aromatic deri~atives of transition metal hydrocarbyloxide compo~n~c ~M(OR')~ wherein at least two of the substituents R2 to R~ of at least one radical are a single hydrocarbylene radical]~
for example:
(1) tetrakisnaphthoxy zirconiu~;
(2) trisnaphthoxy hafnium chloride;
(3) bisnaphthoxy zirconium dichloride;
(4) tetrakisanthroxy zirconium;
(S) tetrakiQbirh~noYy zirconium;
(6) trisnapthoxy tantalu~ dichloride;
(7) bisnapthoxy zirconium dichloride;
and (8) bisnapthoxy molybdenum tetrachloride.~
Some of the transition metal comyo~.~s ~ay be prepared by the reaction ~ res described in: (l) L.R. Chamberlain, et al. Tnorg. ÇhÇ~- Vol. 23, p. 2575 (1984); (2) S. L. ~atesky, et ~l.; Inorq. ÇhÇ~-, Vol.
24, p. 995 (1985); (3) A. W. Duff, et al.; ~. Çhç~.
Soc. ~lton Trans., p. 489 (1986).
The alumoxane component of the catalyst complex is an oligomeric aluminum co~pound which ~ay be represented by the general formula (R'-Al-O)., which is a cyclic co~o~.d, or R" (R" '-Al-O-).-AlR " "2, ~hich is a linear compound, or i~ a mixture of the cyclic and linear ~pecies. In the general alumoxane formula each of R', R", R'''~ and ~" " are ~ C1-C3 alkyl ra~ical, W092/Ol~K PCT/US91/0492~

2o87l8l for example, methyl, ethyl, ~Gyyl, butyl or pentyl and one or more of R', R~, R'" or R'"' ~ay b- a halide, and "m~ is an integer fro~ 1 to about 50. Nost preferably, R', Rn, R"' and R' "' are methyl and ~m"
is at least 4. Alumoxanes can be prepared by various procedures known in the art. For example, an alu~inum alkyl may be treated with water in the for~ of a ~oist inert organic solvent, or it may be contacted with a hydrated salt, such as hydrated copper sulfate lo suspended in an lnert organlc sol~ent, to yield an alumoxane. Generally, however prepared, the reaction of an aluminum alkyl with a limited amount of water yields a mixture of the linear and cyclic ~pecies of the alumoxane.
Suitable alumoxanes which are preferred for use in preparing catalyst systems of this invention arc prepared by the hydrolysi~ of an trialkylaluminu~, ~uch as trimethylalu~inum, triethylaluoinu~, tripropylaluminu~, and triisobutylaluminu~; or a dialkylaluminum halide ~uch a~ dimet~ylaluminu~
chloride, diisobutylaluminum chloride, diethylaluminum chloride and t~e like. The most preferred alu~oxanes for preparing catalyst ~y~tems of this invention are those prepared from trimethylalu~inum. Particularly preferred are methylalumoxan6~ (MA0) havlng an a~erage degree of oligomerization of frou about 4 to about 25 (nmn = 4 to 25), with the most pref~rred methylalumoxane~ being of a de~-Pe of oligomerization ranging from about 13 to about 25 ("m~ ~ 13 to 25).
~a~lyst Sy~te~
The catalyst employed in the method of the invention compri~e~ a syste~ for~ed upon ad~ixture of a Group IVB, VB or VIB tran~ition ~etal hy~ooarbyloxide with an alumoxane. The catalyst ~yste~ ~ay b~ prepared 3s by addition of the regui~ite Group IVB, VB or VIB

Wo92/OI~K 2 0 8 7 1 8 1 PCT/US91/~929 transition metal hydrocarbyloxid- and alumoxane to an inert solvent or diluent ln which polymerization can be carried out by solution, slurry or bulk phase polymerization y~ ures s ~be cataly~t system may be con~eniently prepared by placinq the selected transltion metal hyd,G~arbyloxid- compound and the selected alumoxane, in any order of addition, in an alkane or aromatic hyd.G~arbon solvent--prererably one which is al~o ~uitable for ~ervice as a polynerization diluent Where the hydrocarbon ~olvent utilized i~ also suitable for use as a polyuerization diluent, the catalyst systen may be prepared in ~itu in the poly~erization reactor by direct addition of the transition metal and alumoxane components to the polymerizat$on diluent Alternatively, the catalyst syste~ ~ay be separately prepared outside of the r-actor, in ror entrated form, and added to tbe polymerization diluent in a reactor Or, if desired, the components of the cataly~t system nay be prepared as ~eparate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as i~ ~uitabl- for a cont~n~us liguid polymerization reaction p~c~ Alkane and aromatic hydrocarbon~ suitable as solvents for formation of the catalyst syste~ and al80 as a polymerization diluent are exemplifled by, but are not ne~ ~rily li~ited to, straight and branr~e~ chain hyd.Gca~L~ a such as isobutane, butan-, pentane, hexane heptane, octane and the like, cyclic and alicyclic h~l~G~arbons ~uch as cycloh~xAne, cycloheptan-, nQthylcyclr~eYan-, methylcyclopentan- and the lik , and aro~atic and alkyl-~ub~tituted aromatlc conpQ~lnAQ 8UC~ a~ benzene, toluene, xylenQ and th- like Suitable ~olvQnts al~o include liquid olefins which may act a8 uonomers or WO92/Ol~K PCT/US91/~92~

2o87l8l comonomers including ethylene, propylene, l-butene, 1-hexene and the llke.
In accordance with this invention optimum results are generally obtained wherein the transition metal hydrocarbyloxide com~o~-r,l is present in the polymerization diluent in a concentration of from about 0.0001 to about 1.0 millimoles/liter of diluent and the alumoxane component is present in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1. Sufficient solvent should be employed so as to provide adeguate heat transfer away from the catalyst component~ during reaction and to permit good mixing.
The catalyst system ingredients -- that is, the transition metal hydrocarbyloxide compound, the alumoxane, and polymerization diluent can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from -10- to 300-C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst systeu, the reaction is maintained within a temperature of from about 25- to lOO-C, most preferably about 25-C.
At all times, the individual catalyst system com~Gt.ents, as well as the catalyst ey~tem once formed, are protected from oxygen and moisture. Therefore, the reactions are performed in an oxygen and moisture free atmosphere and, where the catalyst system is recovered separately lt is recovered in an oxygen and moisture free atmoeF~ere, Preferably, therefore, the reactions are performed in the pre~? e of an inert dry gas such as, for example, helium or nitrogen.

WO92/OI~K 2 0 8 7 1 8 1 PCT/US91/~929 Polymerizat~on Process In a preferred embodiment of the p~G-e~- of this invention the catalyst syste~ is utilized in the liquid, solution, slurry, bulk, hiqh pressure fluid or gas phase polymerization of an olefin monomer. These prores~es may be employed singularly or in series. The liquid phase process comprises tbe steps of contacting an olefin monomer with the catalyst syste~ in a suitable poly~erization diluent and reacting said monomer in the presence of said catalyst system for a time and at a temperature and pressure sufficient to produce a polyolefin of high molecular weight.
The monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an ~-olefin having 3 to 20 carbon atoms for the production of an ethylene-~-olefin copolymer. Homopoly~ers of higher ~-olefin such as propylene, and copolymers thereof with ethylene and/or C, or higher ~-olefins and diolefins can also be prepared. Conditions most preferred for the homo- or co-polymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from about 0.019 psia to about 50,000 psia and the reaction temperature is main~in~ at from about -lOO-C
to about 300-C. The aluminum to transition metal molar ratio is preferably from about 1:1 to about 18,000:1.
A more preferable range would be 1:1 to 1000:1. The reaction time is preferably from about 1 minute to about 1 hour.
In accordance with one of the proce--e~ of this invention, a polyolefin is pro~c~ by solution polymerization utilizing ethylene, an ~-olefln ~onomer having 3 to 20 carbon atoms or mixture of such monomers in a polymerization diluent to produce a homo-polyolefin or a copol~mer of ethylene and an ~-olefin~

WO92/Ol~K PCT/US91/~92~

Ethylene is added to the reaction Yessel in an amount sufficlent to produce the desired ethylene content in the polyolefin product. The differential pressure of ethylene, in excess of the vapor pressure of the ~-olefin monomer, reguired to p.G~u~e a given ethylene content depends on the particular transition metal hydrocarbyloxide used. Generally the polymerization proces~ is carried out at an ethylene differential pressure of from about 10 to about 1000 psi, most preferably from about 40 to about 600 psi; and the polymerization diluent is mainta~ned at a temperature of fron about -50 to about 250-C; preferably fro~ about -lo to about 220-C. Under the condition~ a~ indicated above, the ethylene and/or ~-olefin monomers polymerize to a polyolefin.
Wlthout limiting in any way the scope of the invention, one means for carrying out the ~ 5c of the present invention is as follow~: in a ~tirred-tank reactor liquid l-butene monomer i~ .G~ced. The catalyst system is introduced vi~ nozzles in either tbe vapor or liquid phase. Feed ethylene gas i8 iJ--L Gd~ced either into the vapor phase of the reactor, or sparged into the liquid phase as i~ well known in the art. The reactor contains a l~quid phase composed ~ubstantially of liquid 1-butene together with dis~olved ethylene gas, and a ~apor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled via reflux of vaporizing ~-olefin monomer (autorefrigeration), as well as by cooling coils, ~ackets et~. The poly~eriz~tion rate is ~G-.~Lolled by the concentration of cataly~t. The ethylene content of the polymer product is determined by the ratio of ethylene to l-butene in the reactor, which i~
cGn~lolled by manipulating the relative feed rates of these components to the reactor.

- 27 - ao~ ~ 8 ~' EXAMPLES
In the Examples which illustrate the practice of the invention the analytical techniques described below were employed for the analysis of the resulting polyolefin products. Molecular weight determinations for polyolefin products were made by gel permeation chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix~ KMX-6 on-line light scattering photometer. The system was used at 135~C with 1,2,4-trichlorobenzene as the mobile phase. Shodex~ (Showa Denko America, Inc.) polystyrene gel columns 802, 803, 804 and 805 were used.
This technique is discussed in "Liquid Chromatography of Polymers and Related Materials III", J. Cazes editor, Marcel Dekker, 1981, p. 207. No corrections for column spreading were employed; however, data on generally accepted standards, e.g. National Bureau of Standards Polyethylene 1484 and anionically produced hydrogenated polyisoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections on Mw/Mn (= MWD) were less than 0.05 units.
Mw/Mn was calculated from elution times. The numerical analyses were performed using the commercially available Beckman/CIS customized LALLS software in conjunction with the standard Gel Permeation package, run on a HP 1000 computer.
The following examples are intended to illustrate process and product properties of specific embodiments of the invention and are not intended to limit the scope of the invention.

~, ~

.

- 28 - 2 ~ ~ 7 ~

All procedures were performed under an inert atmosphere of helium or nitrogen. Solvent choices were often optional, for example, in most cases either pentane or 30-60 petroleum ether could be interchanged. The lithiate alkoxides were prepared from the corresponding alcohols and either n-BuLi or MeLi. ZrCl4, HfCl4 and TiCl5 were purchased from Aldrich Chemical Co., Strem or Cerac. Most alcohols were purchased from Aldrich. Methylalumoxane was supplied by either Sherring or Ethyl Corp.
Examples A-F of Group IVB and VB~ransition Metal Hydrocarbyloxide Com~onents Example A
Compound A
ZrCl4 (1.0 g, 0.0043 mol) was suspended in ~30 ml of ether. Lithium 2,6-di-t-butylphenoxide, LioR (2.73 g, 0.0129 mol) R = 2,6-t-Bu2C6H3 was slowly added and the mixture was allowed to stir for several hours. The reaction solvent was then removed via vacuum, and toluene was added to the mixture. The mixture was then filtered through Celite~ to remove the LiCl. The toluene was removed via vacuum and ~10 ml petroleum ether was added. The flask was cooled to -40~C for about one hour to maximize precipitation. The white product was filtered off and washed with two small aliquots of petroleum ether. The filtrate was reduced in volume to precipitate out additional product. This too was filtered off, washed and added to the previous fraction. The yield of Zr(OR)3Cl, R = 2,6-t-Bu2C6H3, was 81~ (2.59 g, 0.0035 mol).

Example B
Compound B
HfCl4 (1.5 g, 0.0047 mol) was suspended in ~50 ml of ether. Lithium 2,6-di-t-butylphenoxide, LiOR (3.03 W092/Ol~K 2 0 8 7 1 8 1 PCT/US91/~929 g, 0.0143 mol) R ~ 2,6-~-B~C~3 was ~lowly added to the mixture and allowed to stir for gever_l hours. ~he ether was then removed viA vacuum, toluene was added to solubilize the product and precipitate out the LiCl.
The mixture was filtered through Celite, and the toluene was reduced in volume and petroleum ether was added to precipitate out the product. The white solid was filtered off and washed with a small portion of petroleum ether. Hf(OR)~Cl, R ~ 2,6-7-BuzC~H3, was isolated in a 67% yield (2.61 g, 0.0031 mol).

FYample C
Compound C:
TaCl~ (1.0 g, 0.0028 mol) was suspended in -50 ml of toluene. Lithiu~ 2,6-di-t-butylphenoxide, LioR
(1.19 g, 0.0056 mol) R ~ 2,6-t-R~C~ was slowly added and the mixture vas allowed to stir for several hours.
The mixture was filtered through Celite to remove the LiCl. The toluene was e~aporated off and petroleuD
ether was added to precipitate out the product. The orange solid was filtered off and washed with petroleum ether. The filtrate was reduced in volume in order to precipitate out additional product. mi. too vas filtered off giving Ta(OR)~Cl~, R - 2,6-t-~u2C~H~, in a total yield of 51% (1.0 g, 0.0014 mol).

FYAmple D
Compo~n~ D:
Lithium 4-methyl-2,6-di-~-butylr~Pnoxide, LiOR
(2.185 g, 0.010 mol) R ~ 4-Me-2,6-~-Bu2C~H3 was suspended in -100 ~1 of benzene. ZrCl, (0.75 g, 0.0032 mol) was slowly added and the mixture wa~ allowed to stir for ~e~eral hour6. The ~iCl wa~ then removed from the mixture by filtration through Celite. ~he solvent 3S was then removed via vacuum transfer. Pentane Y~S

WO92/01~K PCT/US91/~929 ~08~181 added to redissolve the ~aterial and the resulting solution was placed in a refrigerator at -40-C which induced precipitation within one hour. The white solid was filtered off and washed with cold pentane.
S Repetition of the recrystallization p~Oced~ using the filtrate yielded a total o~ 0.73 g Zr(OR)2Cl~, R ~ 4-Me-2,6-t-Bu2C~H3 (29% yield).

EXamDle F.
ComDound ~:
Lithiu~ 4-methyl-2,6-di-~-butylphenoxide, LiOR
(1.29 g, 0.0057 mol) R - 4-Me-2,6-t-Bu2C~H2 was suspended in -100 ml of toluene. TaCl~ (1.0 g, 0.0028 mol) was slowly added and the ~ixture wa~ allowed to stir for several hours. The mixture was filtered through Celite to remove the LiCl. The solid was removed via vacuum to recover an orange solid which was washed with pentane. The product, Ta(OR)2Cl~, R ~
4-Me-2,6-~-Ru~C5H2, was recovered in a 72t yield (1.45 g, 0,0020 mol).

FYample F
Compo~lnd F:
Lithium 2,6-di-~-butyl-4-methoxy rhDno~e, LiOR
(2.4 g, 0.0099 mol) R ~ 2,6-t-Bu-4-OMe-CH was suspended in -100 ml of toluene. 2rCl, (0.75 g, 0.0032 mole) was slowly added and the mixture was allowed to stir for several hours. The mixture was filtered through Celite to remove the LiCl. me toluene was evaporated off giving a pale yellow solid which was washed vith small portion~ of solvent. Zr~OR)3Cl, R ~ 2,6-t-Bu-~-OMe-C~H2, was recovered in a ~3% yield (1.15 g, 0.0014 mole).

WO92/Ol~K 2 0 8 7 1 8 1 PCT/US91~W929 E~mPles 1-14 of Poly~er~zAtion ~xam~le 1 PolYmer~zat1on Co~ n~ A:
$he poly~erization was performed in a l-liter autoclave reactor equipped with a paddle stirrer, and external water ~acket for tenperature control, a regulated supply of dry nitrogen, ethylene, propylene, l-butene and hexane, and a septum inlet for introduction of other ~olvents, transition netal compound and alumoxane ~olutions. The reactor was dried and degassed thoroughly prior to use. A typical polymerization consisted of injecting 400 ml of toluene, 5.0 ~1 of 1.0 M MA0 (methylalumoxane), and 0.416 mg of compound A ~0.~ ml of a 10.~ ~g in 10 ml of toluene solution) into the reactor. The reactor was then heated toj80-C1and the ethylene (60 psi) was i..-.c~uced into the system. The duration of the polymerization reaction was limited to 30 ~inutes. The reaction was terminated by rapidly cooling and venting the ~yste~. The ~ol~ent was then evaporated by a stream of nitrogen and 1.3 q of polyethylene was ~eco~e~e~ (MW ~ 359,200, MWD ~ 2.036).

Exa~ple 2 Polymer~zation - Co~ou..~ A:
Using the ~ame reactor design and general ~oce-3~e as in Example 1, the same polymerization run was repeated except using a compound A solution that had been aged for one day. All other reaction conditions remained the same. Polyethylene was ~c~v2~1 (1.4 g) (MW - 373,600, MWD - 1.966).

WO92/OI~K PCT/US91/~929 20~7181 ~ yAm~le 3 PolymP-izat~on - Co~und A:
Using the same reactor design and general p,ocelu.e as in Example 1, the same polymerization run s was repeated except using a compound A solution that had been aged for one week. All other reaction conditions remained the same. Polyethylene was recovered (1.4 g) (MW = 393,300, MWD = 2.105).

E~mple 4 Polymerization - Compound ~:
Using the same reactor de~ign and general prG~edu.e as in Example 1, the same polymerization run was made with the exception of using 0.464 mg of comlo~ B (0.4 ml of a 11.6 mg in 10 ml of toluene solution) instead of Compound A. All other react~on conditions remained the same. Polyethylene was recovered (1.2 g) (MW ~ 360,100, MWD - 1.886) FYAmple 5 Polymerizat~on - ComDound C:
Uslng the same reactor design and general yLo~e~ as in Example 1, the same polymerization run was made with the exception of using 0.39 mg of comlo~.l C (0.~ ml of a 9.75 mg in 10 ml of toluene solution) instead of compound A. All other reaction conditions rema~ned the same. Polyethylene was ~COve~ (1.3 g) (MW - 381,700, MWD = 1.963).

FY~ple 6 poly~r~zat~on - Com~ n~ D:
Using the same reactor design and general pL~ ure a~ in Exa~ple 1, the same polymerization run was made with the exception of using 0.44 mg of 3s compound D (0.4 ml of a 11.0 mg in 10 ml of toluene WO92/01~K 2 0 ~ 7181 PCT/US91/~929 solutlon ) instead of compound A. All other reactlon conditlons remained the sa~e. Polyethylene was recovered (1.4 g) (Mw - 536,500, MWD - 1.996).

Fyample 7 Polymerization - ComDound ~:
Using the same reaetor design and general y~Gcel~re as in Example 1, the same polymerization run was made with the exeeption of using 0.404 mg of Catalyst E (0.4 ml of a 10.1 mg in 10 ml of toluene solution) instead of compound A. All other reaetion eonditions remained the same. Polyethylene was reeovered (1.5 g) (HW ~ 352,700, MWD - 1.978).

FYAmDle 8 Polymerization - Co~po~d F:
Using the same reaetor design and general proeedure a~ in Example 1, the same polymerization run was made with the exeeption of using 0.464 mg of eom~ound F (0.4 ml of a 11.6 mg in 10 ml of toluene solution) instead of compound A. All other reaetion eonditions remained the same. Polyethylene was reeovered (1.4 g) (MW ~ 304,500, MWD ~ 1.916).

FYamDle 9 poly~eri7ation - Co~poun~ A:
U~ing the ~ame reaetor design and general ~e_-~ure as in Example 1, 300 ml of toluene, 200 ml of propylene, 3.0 ml of l.S M HA0, and 0.20 mg of eoml-o~ A (0.2 ml of a 10.0 mg in 10 ~1 of toluene solution) were i--L~ into the reaetor. The reaetor was heated to 60-C, ethylene wa~ int~G~ (40 psi), and the reaetion was allowed to run for 30 minutes, followed by rapld eooling and venting of the 3s system. After evaporation of the solvent, 8.5 g of an WO92/Ol~K PCT/US91/~92~
2o87l8l ethylene-propylene copolymer were ~ecovered having a molecular weight of 32,600 and a nolecul~r weight distribution of 2.285 and containing 30.3 mole %
propylene as determined by ~C NMR.

~ YA~ple 1 o Polymeri~ation - Compound A:
Using the same reactor design and general procedure already described, 400 ~l of toluene, 1.0 ml of 1.0 M MA0, and 0.4 ml of a preactivated compound A
solution (10.4 mg of compound A dissolved in 9.5 ml of toluene and 0.5 ml of 1.0 M MA0) were added to the reactor. The reactor was heated to 80-C, the ethylene was introduced (60 psi), and the reaction wa~ allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 0.4 g of polyethylene was recovered (MW - 393,400, MWD = 1.966).

E~Dle l~
PolYmerizatlon - ComDound A:
Using the same reactor design and general p~G~r-l~.e already described, 400 ml of toluene, 0.5 ml of 1.0 M MA0, and 0.4 ml of ~ preacti~ated compound A
solution (10.4 mg compound A dis~olYed in 9.5 ~l of toluene and 0.5 ml of 1.0 M MA0) were added to the reactor. The reactor was heated to 80-C, the ethylene was i..~-cduced (60 psi), and the reaction wa~ allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 0.2 g of polyethylene was recovered (~W - 372,400, MWD z 2.~52).

WO92/Ol~K 2 0 8 7 1 8 1 PCT/US91/~929 ~ Y~mple 12 Polvm~riz~tion - Co~ n~ C:
Usinq the same reactor design and general procedure already described, 400 ml of toluene, 1.0 ml s of 1.0 M MAO, and 0.4 ml of a preactivated compound C
solution (9.75 mg of compound C dissolved in 9.5 ml of toluene and 0.5 ml of 1.0 MA0) were added to the reactor. The reactor was heated to 80-C, the ethylene was followed by rapidly cooling and venting tbe system.
~0 A~ter evaporation of the solvent, O.4 g of polyethylene was leco~ered (MW - 399,700, MWD= 2.093).

~ Ya~ple 13 Polymerization - Compound C:
Using the same reactor design and general procedure already described, 400 ~1 of toluene, 0.5 ml of 1.0 M MA0, and 0.4 ml of a preactivated compound C
solution (9.75 mg of compound C dissolved in 9.5 ml of toluene and 0.5 ~1 of 1.0 M NAO) were added to the reactor. The reactor was heated to 80-C, the ethylene YaS introduced (60 p5i), and the reaction wa~ allowed to run for 30 minutes, followed by rapidly cooling and venting the sy~tem. After evaporation of the solvent, 0.1 g o~ polyethylene was .ecu~ered (MW - 428,700, MWD ~ 2.218).

E~ele Polymeriz~tion - Co~po~n~ A
Using the same reactor design and general ~lo~ed~e already described in Example 1, the same polymerization run wa~ repeated except for increasing the ethylene pressure to 400 psi. All other reaction conditions remained the ~ame. Polyethylene was recovered (10.3 g) (MW ~ 433,000, MWD ~ 2.073) WO92/OI~K PCT/US91/04929 ~YamDle 1 S
The polymerization was performed in a st~rred 100 ml stainless steel autoclave which was equipped to perform polymerizations at pres~ures up to 40,000 psi s and temperatures up to 3000C. The autoclave was purged with nitrogen and heated to 1600C. Solutions of com~ou-.d A and alumoxane were prepared in separate vials. A stock solution was prepared by dissolving 13 mg of com~o~ A in 25 ml of toluene. The compound A
solut$on was prepared by diluting 0.5 ml of the stock solution with 5.0 ml of toluene. The alumoxane solution consisted of 2.5 ml of a 1.0 M MAO solution added to 5.0 ml of toluene. The compound A solution was added to the alu~oxane solution; then 0.43 ~1 of the mixture was transferred under nitrogen pressure to a constant volume injection tube. The autoclave was pressurized with ethylene to 1701 bar and was stirred at 1500 rpm. The mixed solutions were injected into the autoclave with eYcess pressure, at which time a temperature rise of 22-C was observed. The temperature and pressure were ,ecG,ded for 120-seconAc, after which the contents of the autoclave were vented rapidly into a receiving vessel. The autoclave was wa~h~ three times with xylene to recover any additional polymer remaining within. These wa~ngs were combined with the polymer released when the autoclave was vented to yield 2.45 g of polyethylene (MW = 177,500, MWD =
2.657).

30FYample 16 The polymerization was performed in the high pressure autoclave system described in Example 15. The comonomer, l-hexene (75 ml), which had previously been dried over basic alumina wa~ added to the reactor under 35ethylene pressure. A stock solution of compound A was 20871~1 W092/01~K PCT/US91/~929 prepared by dissolving 1~.3 mg of compound A in 30.6 ml of toluene. The test ~olution was prepared by ad~n~
2.5 ml of the compound A stock solution to 10 ml of a 10% MAO solution. The test solution (0.43ml) w_s s transferred by nitrogen pressure into a constant volume injection tube. The autoclave wa~ pres~urizQd with ethylene to 1725 bar and was stirred at 1800 rpm. The test solution was in~ected into the autoclave vith excess pressure, at which time a temperature rise of 130C was observed. The temperature and p~P~~re were recorded continuously for 120 ~ ~n~, at which time the contents of the autoclave were rapidly vented into a receiving vessel. The reactor was wA~h~ with xylene to ~ecover any polymer remaining within. These washings were combined with the polymer released when the reactor was vented. Precipitation of the poly~er from the mixture by addition of acetone yielded 1.9 g of polymer (MW - 52,400, MWD ~ 2.592, 7.~ SC8/lOOOC).

FYA~le 17 U~ing the same reactor design and general re as in Example 1, 300 ~1 of toluene, 100 ~1 of l-butene, 7.0 ~1 of 1.0 M HAO and 4.16 Dg of compound A
(4.0 ~1 of a 10.4 mg in 10 ~1 of toluen- solution) were 2S intro~ce~ into the reactor. The reactor was heated to 80-C, ethylene was introduced (400 psi), and the reaction was allowed to run for 10 minutes, followed by rapid cooling and venting of the sy~te~. After evaporation of the solvent, 33.7 g of an ethylene-butene copolymer was recovered having a ~ole~l~r weight of 348,100 and mole~lAr weight distribution of 2.244 and cont~ining 8.0 mole ~ of butene ~s deter~ined by IR spectro~copy.

W092/Ol~K PCT/US91/~929 E~ e 18 Using the same reactor de~ign and gsnsral p~o~e~ e as in Exampls 1, 300 ~1 of toluene, 100 ml of propylene, 7.0 ml of 1.0 H MA0 and 4.16 mg of compound s A (4.0 ~1 of a 10.4 ~g in 10 ~1 of toluene solution) were introduced into the reactor. me reactor was heated to 800C, ethylene wa~ Gdu_~ (100 psi), and the reaction was allowed to run for 10 minutes, followed by rapid cooling and venting of the system.
After evaporation of the solvent, 31.0 g of an ethylene ~.G~ylene copolymer was .e_overed ha~ing a molec~lar weight of 128,700 and nole~lar weight distribution of 2.789 and containing 3.3 mole % of propylsns as determined by IR spectroscopy.
e 1 9 Using the same reactor design and general procel~e as in Example 1, 300 nl of toluene, lOOml of l-hexens, 7.0 ~1 of 1.0 ~ MA0 and ~.16 mg of comyou--d A
(4.0 ml of a 10.4 mg in 10 ml of toluens solution) were intro~c~ into the reactor. The reactor was heated to 800C, ethylene was i~ (100 psi), and the reaction was allowed to run for 10 ~inutes, followed by rapid cooling and venting of the syste~. After evaporation of the solvent, 1~.2 g of an ethylene-hexene copolymer was ~e_overed having a mole~lAr weight of 130,000 and molecular ~eight distribution of 2.097 and containing 3.71 mole ~ hexene as determined by NMR sp._~ opy.
The invention has been described with reference to its preferred embodiments. Tho~e skilled in the art may appreciate changes or modification~ which do not depart from the scope and spirit of the invention described above or claimed hereafter.

Claims (16)

1. A catalyst system, effective for the production of polyolefins comprising:
(a) a transition metal hydrocarbyloxide compound represented by the formula:
M(OR1)yXn-y, or wherein M is a Group IVB, VB or VIB transition metal; each X is independently a halogen, or a hydrocarbyl, alkoxy or amide group having from one to 30 carbon atoms;
R1 is a bulky radical of the formula:

or wherein t is 0 or an integer number of 1 to 10 and each of the R2 to R19 substituents is independently hydrogen, a halogen, a hydrocarbyl radical selected from the groupconsisting of straight or branched chain alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a halogenated hydrocarbyl group, an alkoxy group, an amine group, with the proviso that at least R2 and R6 cannot be hydrogen, or at least one of R9 to R19 cannot be hydrogen, or at least two of the substituents R2 to R6 or R9 to R19 may be a single hydrocarbylene radical which forms a fused polycyclic ring system or polynuclear aromatic system, and R7 and R8 may independently be a cyclic group selected from:

or n is a number at least equal to 4 and is equal to the valence of the transition metal M; y is a number equal to or greater than 2 and less than or equal to n, y' is a number equal to or greater than 3 and less than or equal to n, and y" is a number equal to or greater than 4 and less than or equal to n, and (b) an alumoxane.

2. The catalyst system of claim 1, wherein the alumoxane is methylalumoxane.

3. The catalyst system of claim 1 or 2, wherein the alumoxane to transition metal mole ratio is from 1:1 to 1000:1.

4. The catalyst system of any one of claims 1 to 3, wherein M is zirconium, hafnium, niobium or tantalum.

5. The catalyst system of any one of claims 1 to 4, wherein y is 2.

6. The catalyst system of any one of claims 1 to 4, wherein y is 3.

7. The catalyst system of any one of claims 1 to 4, wherein y is 4.

8. The catalyst system of any one of claims 1 to 4, wherein y is 5 and M is a Group VB or VIB transition metal.

9. The catalyst system of any one of claims 1 to 8, additionally comprising a polymerization diluent.

10. The catalyst system of claim 9, wherein the transition metal hydrocarbyloxide is present in said polymerization diluent in an amount from 0.001 to 1.0 millimoles per liter.

11. The catalyst system of claim 9 or 10, wherein the polymerization diluent is an alkane or aromatic hydrocarbon.

12. A process for producing a polyolefin which comprises polymerizing one or more olefinic monomers in the presence of a catalyst system according to any one of claims 1 to 11.

13. The process according to claim 12, which comprises polymerizing ethylene alone or in combination with one or more higher alpha-olefins containing from 3 to 20 carbon atoms, or propylene alone or in combination with ethylene and/or one or more higher alpha-olefins containing from 4 to 20 carbon atoms.

14. The process according to claim 12 or 13 which comprises a high pressure polymerization process.

15. The process according to claims 12 or 13, which comprises a low pressure polymerization process selected from liquid, solution, slurry, bulk and gas phase processes.

16. The process according to any one of claims 12 to 15, wherein the catalyst system is formed in situ by combining catalyst components (a) and (b) in a reactor for the polymerization.