TECHNICAL BACKGROUND Polymers of olefins are important items of commerce, and these polymers are used in a myriad of ways, from low molecular weight polyolefins being used as a lubricant and in waxes, to higher molecular weight grades being used for fiber, films, molding resins, elastomers, etc.

Olefins may be polymerized by a variety of transition metal containing catalysts, for example metallocene and Ziegler-Natta type catalysts. More recently, late transi- tion metal containing polymerization catalysts have also been discovered, and among them are nickel and other transi- tion metal containing catalysts in which the nickel atom is complexed to a neutral or monoanionic ligand, see for in- stance US5714556, US5880241, US6060569, W09842664, W09842665 and W09830609, all of which are incorporated by reference herein for all purposes as if fully set forth. None of these references describes the complexes disclosed herein.

Since polyolefins are important commercial materials, new catalysts for their manufacture are constantly being sought.

SUMMARY OF THE INVENTION One aspect of the present invention concerns a first process for the polymerization of olefins, comprising the step of contacting, at a temperature of about-100°C to

about +200°C, one or more monomers selected from the group consisting of ethylene and an olefin of the formula H2C=CH (CH2) nG (XVII), with an active catalyst comprising a Group 3 to Group 10 transition metal complex of an anion of the formula (I) wherein : R1 is hydrocarbyl or substituted hydrocarbyl, and R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and pro- vided that R1 and R2 taken together may be ortho-arylene or substituted ortho-arylene ; R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that when R1 and R2 taken to- gether are ortho-arylene or substituted ortho-arylene, R3 may form a fused ring system therewith ; Q is nitrogen, oxygen, phosphorous or sulfur ; R4 and R5 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that R4 and R5 taken to- gether may form a ring, and further provided that when Q is oxygen or sulfur R5 is not present ; Z is a bridging group of the formula (II) or (III) R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3 and R6 together may form a ring ;

R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 together may form an aromatic ring or R6 and R7 taken together may form a ring ; R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl ; R9 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R4 and R9 taken together may be part of a dou- ble bond to an imino nitrogen atom, or R8 and R9 taken to- gether may form a ring, or R4, R5, R8 and R9 taken together may form an aromatic ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R4, R5, R6, R, R8, and R9 taken together may form a fused aromatic ring system ; R, Rll, R and R'are each independently hydrogen, hy- drocarbyl or substituted hydrocarbyl or R10, Rll, R12 and R13 taken together are ortho-arylene ; R14 is hydrogen, hydrocarbyl or substituted hydrocarbyl ; R4 and R15 together are part of a double bond to an imino nitrogen atom ; n is an integer of 1 or more ; G is hydrogen,-CO2Rl6 or-C (O) NR162 ; and each R16 is independently hydrogen, hydrocarbyl or sub- stituted hydrocarbyl.

Another aspect of the present invention conerns a sec- ond process for the polymerization of olefins, comprising the step of contacting, at a temperature of about-100°C to about +200°C, one or more monomers selected from the group consisting of ethylene and H2C=CH (CH2) nG (XVII), with a com- pound of the formula (IV)

wherein : R1 is hydrocarbyl or substituted hydrocarbyl, and R2 is hydrogen, hydrocarbyl or substituted hydrocarbyl, and pro- vided that R1 and R2 taken together may be ortho-arylene or substituted ortho-arylene ; R3 is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that when R1 and R2 taken to- gether are ortho-arylene or substituted ortho-arylene, R3 may form a fused ring system therewith ; R4 and R5 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl, provided that R4 and R5 taken to- gether may form a ring, and further provided that when Q is oxygen or sulfur Rs is not present ; Q is nitrogen, oxygen, phosphorous or sulfur ; Z is a bridging group of the formula (II) or (III) R6 is hydrogen, hydrocarbyl or substituted hydrocarbyl, or R3 and R6 together may form a ring ; R7 is hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that R3, R6 and R7 together may form an aromatic ring, or R6 and R7 taken together may form a ring ; R8 is hydrogen, hydrocarbyl or substituted hydrocarbyl ;

R9 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or R4 and R9 taken together may be part of a double bond to an imino nitrogen atom, or R8 and R9 taken together may form a ring, or R4, R5, R8 and R9 taken together may form an aromatic ring, or R4 and R9 taken together may form a ring, or R4, R8 and R9 taken together may form a ring, or R4, R5, R6, R', R8 and R9 taken together may form a fused aromatic ring system ; R, Rll, R and R'3 are each independently hydrogen, hy- drocarbyl or substituted hydrocarbyl, or R10, Rll, R 12 and R13 taken together are ortho-arylene ; R14 is hydrogen, hydrocarbyl or substituted hydrocarbyl ; R4 and R15 together are part of a double bond to an imino nitrogen atom ; n is an integer of 1 or more ; G is hydrogen,-CO2R16, or-C (O) NR 162 each R16 is independently hydrogen, hydrocarbyl, or sub- stituted hydrocarbyl ; M is a Group 3 to Group 10 transition metal ; m is an integer equal to the valence of M minus 1 ; and each L1 is independently a monodentate monoanionic li- gand and at least for one of L1 an ethylene molecule may in- sert between L1 and M, and L2 is a monodentate neutral ligand which may be displaced by ethylene or an empty coordination site, or an L1 and L2 taken together are a monoanionic poly- dentate ligand and at least for one of these polydentate ligands ethylene may insert between said monoanionic poly- dentate ligand and M.

In the above-mentioned processes, (IV) and/or the tran- sition metal complex of (I) may in and of themselves be ac- tive catalysts, or may be"activated"by contact with a co- catalyst/activator.

The present invention also concerns a compound of the formula (V)

h i R1 R2 R3 R4 R5, Q, Z (and all R groups asso- ciated with Z), M and m are as defined above for (IV), p is 0 or 1 ; and each L3 is independently a monodentate monoanionic li- gand, and L4 is a monodentate neutral ligand or an empty co- ordination site, or an L3 and L4 taken together are a mono- anionic bidentate ligand.

Further aspects of the present invention include, for example, the anion of the formula (I) as defined above, as well as a Group 3 to Group 10 transition metal complex of such anion.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Herein, certain terms are used. Some of them are : A"hydrocarbyl group"is a univalent group containing only carbon and hydrogen. As examples of hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls.

If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.

By"substituted hydrocarbyl"herein is meant a hydro- carbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected (e. g., an in- ert functional group, see below). The substituent groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. If not otherwise stated, it is preferred

that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of"substi- tuted"are chains or rings containing one or more heteroa- toms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the het- eroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl.

By" (inert) functional group"herein is meant a group other than hydrocarbyl or substituted hydrocarbyl that is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process de- scribed herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as-OR22 wherein R22 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a metal atom the functional group should not coordinate to the metal atom more strongly than the groups in those compounds are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group.

By a"catalyst activator"is meant a compound that re- acts with a transition metal compound to form an activated catalyst species. A preferred catalyst activator is an"al- kyl aluminum compound", that is, a compound which has at least one alkyl group bound to an aluminum atom. Other groups such as alkoxide, hydride, and halogen may also be bound to aluminum atoms in the compound.

By"neutral Lewis base"is meant a compound, which is not an ion, that can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides and organic ni- triles.

By"neutral Lewis acid"is meant a compound, which is not an ion, that can act as a Lewis acid. Examples of such compounds include boranes, alkylaluminum compounds, aluminum halides and antimony [V] halides.

By"cationic Lewis acid"is meant a cation that can act as a Lewis acid. Examples of such cations are sodium and silver cations.

By an"empty coordination site"is meant a potential coordination site on a metal atom that does not have a li- gand bound to it. Thus if an ethylene molecule is in the proximity of the empty coordination site, the ethylene mole- cule may coordinate to the metal atom.

By a"ligand into which an ethylene molecule may insert"between the ligand and a metal atom is meant a ligand coordinated to the metal atom into which an ethylene molecule (or a coordinated ethylene molecule) may insert to start or continue a polymerization. For instance, this may take the form of the reaction (wherein L is a ligand) : By a"ligand which may be displaced by ethylene"is meant a ligand coordinated to a transition metal, which when exposed to ethylene is displaced as the ligand by the ethyl- ene.

By a"monoanionic ligand"is meant a ligand with one negative charge.

By a"neutral ligand"is meant a ligand that is not charged.

"Alkyl group"and"substituted alkyl group"have their usual meaning (see above for substituted under substituted hydrocarbyl). Unless otherwise stated, alkyl groups and

substituted alkyl groups preferably have 1 to about 30 car- bon atoms.

By"aryl"is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring.

An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups.

By"substituted aryl"is meant a monovalent aromatic group substituted as set forth in the above definition of "substituted hydrocarbyl". Similar to an aryl, a substi- tuted aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups ; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a het- eroatom (such as nitrogen) of the heteroaromatic ring in- stead of a carbon.

By a"n-allyl group"is meant a monoanionic ligand with 1 Sp3 and two adjacent sp2 carbon atoms bound to a metal cen- ter in a delocalized zu fashion. The three carbon atoms may be substituted with other hydrocarbyl groups or functional groups.

By"ortho-arylene" (or"o-arylene") is meant a divalent aryl group in which the free valencies are on adjacent car- bon atoms. The o-arylene ring may be part of a fused and/or heterocyclic ring system and/or contain substituents such as hydrocarbyl groups or functional groups.

The polymerizations herein are carried out by a transi- tion metal complex of anion (I). Many of the groups in (I) may have various forms, that is they may be"simple"groups such as hydrogen or alkyl, or they may participate in multi- ple bonds such as an imino bond to nitrogen or a carbon atom in an aromatic ring and/or they may be part of ring or ring systems. Some of these groups may optionally for instance be part of two different rings. Clearly simple valence

rules are not broken in these anions and compounds, for ex- ample carbon will have a valence of 4. Thus if a particular group is part of one ring, it cannot be part of another ring or group that would violate these simple valence rules.

In order to illustrate this, and since (I) and its con- jugate acid and transition metal complexes may have various individual structures, some conjugate acids of these anions are shown below, with some salient features pointed out.

In (VI), R1 and R2 taken together are o-arylene ; Z is a bridging group of the formula (II) ; and R4, R5, R8 and R9 taken together form an aromatic ring. In addition, each of Ria Rl9 R20, R21, R22, R23 R24 and R25 is independently, hydro- gen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of Rl8, R19, R20 and R21 vicinal to one another may form a ring, any two of R22, R23, R and R25 vicinal to one another may form a ring, and R3 and R21 taken together may form a ring.

In (VII), R1 and R2 taken together are o-arylene ; Z is a bridging group of the formula (II) ; R3 is hydrogen ; and R4, R5, R6, R, R8 and R9 form a fused aromatic ring system.

In (VIII), R1 and R2 taken together are o-arylene ; Z is a bridging group of the formula (II) ; R3 and R6 taken to- gether form a ring ; R7 and R8 are hydrogen ; R4 and R9 taken together form part of an imino bond to nitrogen ; and Rs is 2, 6-diisopropylphenyl.

In (IX), R1 and R2 taken together are o-arylene ; Z is a group of the formula (II) ; R3 is hydrogen ; R5, R6 and R7 are hydrogen, and R4 and R9 taken together form a ring.

In (X), R1 and R2 taken together are o-arylene ; Z is a group of the formula (II) ; R3, R6 and R'together form an aromatic ring ; R4 and R9 taken together form part of an imino bond to nitrogen ; R8 is hydrogen ; and R5 is 2, 6- diisopropylphenyl.

In (XI), Rl is trifluoromethyl ; Z is a group of the for- mula (II) ; R, R6, and R7 are hydrogen ; R3 is methyl ; and R4, R5, R8 and R9 taken together form an aromatic ring.

In (XII), R1 and R2 taken together are o-arylene ; R3 is hydrogen ; Z is a group of the formula (III) ; R10, Roll, R12 and R13 taken together are o-arylene ; R14 is methyl ; R4 and R15 to- gether are part of a double bond to an imino nitrogen atom ; and R5 is 2, 6-diisopropylphenyl.

In (XIII), R1 and R2 taken together are o-arylene ; R3 is hydrogen ; Z is a group of the formula (II) ; R6, R7, R8 and R9 are hydrogen ; and R4 and R5 are methyl.

In (XIV), Rl and R2 taken together are o-arylene ; Z is a group of the formula (II) ; R3, R6, R7 and R8 are hydrogen ; R4 and R9 together are part of a double bond to an imino nitro- gen atom ; and R5 is 2, 6-diisopropylphenyl.

In (XV), Rl and R2 taken together are o-arylene ; Z is a bridging group of the formula (II) ; R3 and R6 taken together form a ring ; R7 is hydrogen ; and R4, R5, R8 and R9 taken to- gether form an aromatic ring.

In (XVIII), R1 and R2 taken together are o-arylene ; Z is a group of the formula (II) ; R3, R6 and R7 are hydrogen ; Q is

sulfur and thus R is not present ; and R4, R8 and R9 together form a ring.

In (XIX), Rl and R2 taken together are o-arylene ; Z is a group of the formula (II) ; R3, R6 and R7 are hydrogen ; Q is oxygen and thus R5 is not present ; and R4, R8 and R9 together form a ring.

In (XX), R1 is trifluoromethyl ; R2 is hydrogen ; R3 is methyl ; Z is a group of the formula (II) ; R6 and R7 are hy- drogen ; Q is oxygen and thus R5 is not present ; and R4, R8 and R9 together form a ring.

In all of compounds (VI) through (XV) and (XVIII) through (XX), groups and/or substituents may be changed where appropriate, for example methyl groups may be changed to other hydrocarbyl groups or hydrogen, hydrogen may be change to hydrocarbyl or functional groups.

A preferred anion (and it conjugate acid and metal com- plexes) is (VI). In (VI) it is preferred that : R18 and R21 are each independently alkyl containing 1 to 4 carbon atoms, halo, nitro or hydrogen ; and/or Rl9 and R20 are hydrogen ;

R3 is hydrogen ; and/or R6 and R7 are hydrogen ; and/or R22 R23 R24 and R25 are hydrogen ; and/or Q is nitrogen.

In preferred specific compounds (VI), R18 and R21 are both ni- tro or t-butyl, and Rl9, R, R, R I R, R, R, R and R are hydrogen; R18, R21, R19, R20, R3, R6, R7, R22, R23, R24 and R25 are all hydrogen ; R'8 is t-butyl and R19, R°, R R I R, R R22 R23 R24 and R25 are hydrogen.

The structure illustrated in (I) is not meant to pre- clude other tautomers, and all such tautomers are included herein. For instance such structures may include The conjugate acids of (I) can be made by a variety of methods, most of which are familiar to the skilled organic synthetic chemist, and which method (s) are chosen will de- pend on the particular structure desired, such as (VI) through (XV). In all instances, if certain substitu- ents/substitution patterns are desired, starting materials with those substituents/substitution patterns may be used.

For example (VI) may be made by reacting an appropriate salicylaldehyde with an appropriate 2-aminomethylpyridine.

(VII) may be made by reacting salicylaldehyde with 8-aminoquinoline. (XIII) can be made by reacting N, N- dimethylethylenediamine with salicylaldehyde. (XIV) can be made by reacting salicylaldehyde with 2- (N-2, 6- diisoprpopylphenylimino) ethylamine. (XI) may be made by re- acting l, l, l-trifluoro-2, 5-pentanedione with 2-

aminomethylpyridine. (XVIII) may be made by reacting sali- cylaldehyde with 2-aminomethylthiophene. (XIX) may be made by reacting salicylaldehyde with 2-aminomethylfuran. (XX) may be made by reacting 1, 1, l-trifluoro-2, 5-pentanedione with 2-aminomethylfuran.

(I), the anion of the above conjugate acids, can be prepared by reaction of the conjugate acid with a strong base, such as an alkali metal hydride, an alkali metal alk- oxide or a lithium disilylamide. It is preferred at this point that the cation to this anion is an alkali metal ca- tion, such as lithium, sodium and potassium. (I) may iso- lated as a salt and then used to form the transition metal compound, or may be formed and used in situ to produce the transition metal compound. The transition metal compound of (I) may be prepared by reacting (I) with an appropriate com- pound of the transition metal. Especially for early transi- tion metals such as Zr and Ti, the transition metal compound may be a halide such as TiCl4 or ZrCl4, in which case the ligands other than (I) attached to the metal will be halide such as chloride. Especially for late transition metal other types of compounds may be used. For example to make nickel complexes one may use : (Ph3P) 2Ni (Ph) (Cl) which gives (IV) in which Ll is Ph, and L2 is Ph3P ; (TMEDA) 2Ni (Ph) (Cl) in the presence of a"trapping li- gand"L2 such as pyridine, which gives (IV) for instance in which Ll is Ph, and L2 is pyridine ; (Ph3P) 2NiCl2 which gives (IV) in which Ll is Cl, and L2 is Ph3P ; and/or [ (allyl) Ni (X)] 2 which gives (IV) in which Ll and L2 taken together are n-allyl.

Methods of synthesis of these types of complexes may also be found in previously incorporated US6060569,

W09830609 and W09842664, and in R. H. Grubbs., et al., Or- ganometallics, vol. 17, p. 3149 (1988). If (V) is not al- ready equivalent to (IV), it may be converted to (IV) before or during the polymerization process by reaction with other appropriate compounds (such as cocatalysts).

In some of the structures written herein, such as (IV) and (V), it is not meant that (I) is a tridentate ligand, although it may be. The structures are written as they are for convenience, and to show that the anionic ligands (I) could be tridentate, but it may be only bidentate or even monodentate. Although it is believed in theory the ligands can be tridentate, Applicants do not wish to be bound by this theory.

As implied above, (I) will normally be associated with a positively charged species, such as a cation. This may be a transition metal cation (as in (IV)), or may be another cation such as an alkali metal cation.

In (IV) useful groups Ll include halide (especially chloride), hydrocarbyl and substituted hydrocarbyl espe- cially phenyl and alkyl and particularly phenyl, methyl, hy- dride and acyl. Useful groups for L2 include phosphine such as triphenylphosphine, nitrile such as acetonitrile, ethers such as ethyl ether, pyridine, and tertiary alkylamines such as TMEDA (N, N, N', N'-tetramethyl-1, 2-ethylenediamine). Al- ternatively Ll and L2 taken together may be a s-allyl or s- benzyl group such as

wherein R is hydrocarbyl, and a-allyl and n-benzyl groups are preferred.

In another variation, L3 and L4 taken together may be a P-diketonate ligand. If this ligand is present in (V), it may be converted to (IV) by use of a suitable alkylating agent such as an alkylaluminum compound, Grignard reagent, or alkyllithium compound.

In (IV) when ethylene may insert between Ll and the transition metal atom, and L2 is an empty coordination site or is a ligand which may be displaced by ethylene, or Ll and L2 taken together are a bidentate monoanionic ligand into which ethylene may be inserted between that ligand and the transition metal atom, (IV) may by itself catalyze the po- lymerization of an olefin. Examples of L1 which form bonds with the transition metal into which ethylene may insert are hydrocarbyl and substituted hydrocarbyl, especially phenyl and alkyl, and particularly methyl, hydride and acyl. Lig- ands L2 which ethylene may displace include phosphine such as triphenylphosphine, nitrile such as acetonitrile, ether such as ethyl ether, pyridine and tertiary alkylamines such as

TMEDA. Ligands in which Ll and L2 taken together are a bidentate monoanionic ligand into which ethylene may insert between that ligand and the transition metal atom include n- allyl-or n-benzyl-type ligands (in this instance, sometimes it may be necessary to add a neutral Lewis acid cocatalyst such as triphenylborane to initiate the polymerization, see for instance previously incorporated W09830609). For a sum- mary of which ligands ethylene may insert into (between the ligand and transition metal atom) see, for instance, J. P.

Collman, et al., Principles and Applications of Organotran- sition Metal Chemistry, University Science Book, Mill Val- ley, CA, 1987, included herein by reference. If for in- stance L1 is not a ligand into which ethylene may insert be- tween it an the transition metal atom, it may be possible to add a cocatalyst which may convert Ll into a ligand which will undergo such an insertion. Thus if Ll is halo such as chloride or bromide, or carboxylate, it may be converted to hydrocarbyl such as alkyl by use of a suitable alkylating agent such as an alkylaluminum compound, a Grignard reagent or an alkyllithium compound. It may be converted to hydride by used of a compound such as sodium borohydride.

In (V) in one preferred form at least one of L3 is a li- gand into which ethylene may insert between L3 and the tran- sition metal atom, and L4, is an empty coordination site or a ligand which may be displaced by ethylene. In another pre- ferred for of (V) each of L3 is a ligand into which ethylene may not insert between that ligand and the transition metal atom, such as halide, especially chloride, and carboxylate.

Generally a cocatalyst (sometimes also called an activator) which is an alkylating or hydriding agent is also present in the olefin polymerization. A preferred cocatalyst is an alkylaluminum compound, examples of which include trialkylaluminum compounds such as

trimethylaluminum, triethylaluminum and tri-i-butylaluminum ; alkyl aluminum halides such as diethylaluminum chloride and ethylaluminum chloride ; and aluminoxanes such as methylaluminoxane. More than one such cocatalyst may be used in combination.

In (IV) and other transition metal complexes preferred metals are Pd, Co, Fe, Cr, V, Ti, Zr and Hf. More preferred are Ti, Zr, Pd and Ni, and Ni is especially preferred. Gen- erally speaking early transition metal complexes such as Ti and Zr produce polymers with the"expected"number and length of branches (see previously incorporated US5880241 for an explanation of"expected"branching). For example homopolyethylene will have essentially no branching (after correcting for end groups), while poly (l-hexene) will have an n-butyl branch every other carbon atom (on average) of the main polymer chain. Polyolefins made with late transi- tion metal complexes such as Ni or Pd will generally have the"wrong"number and branch lengths in the polyolefin.

For example, homopolyethylene will often have branches of methyl and longer.

A preferred olefin is ethylene, and when olefins other than ethylene are polymerized, it is preferred that they be copolymers with ethylene. In other preferred olefins n is 1 to 20, and/or G is hydrogen, and/or G is-CO2Rl6 wherein Rl6 is hydrocarbyl or substituted hydrocarbyl, especially alkyl.

In the polymerization processes herein, the temperature at which the polymerization is carried out is about-100°C to about +200°C, preferably about-60°C to about 150°C, more preferably about-20°C to about 100°C. The pressure of the olefin (if it is a gas) at which the polymerization is car- ried out is not critical, atmospheric pressure to about 275 MPa being a suitable range.

The polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, monomer (s) and/or polymer may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from oc- curring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons and aromatic hydrocarbons.

Specific useful solvents include hexane, toluene, benzene methylene chloride, and 1, 2, 4-trichlorobenzene.

The olefin polymerizations herein may also initially be carried out in the"solid state"by, for instance, support- ing the transition metal compound on a substrate such as silica or alumina, activating it if necessary with one or more cocatalysts and contacting it with the olefin (s). Al- ternatively, the support may first be contacted (reacted) with one or more cocatalysts (if needed) such as an alkyla- luminum compound, and then contacted with an appropriate transition metal compound. The support may also be able to take the place of a Lewis or Bronsted acid, for instance an acidic clay such as montmorillonite, if needed. These"het- erogeneous"catalysts may be used to catalyze polymerization in the gas phase or the liquid phase. By gas phase is meant that a gaseous olefin is transported to contact with the catalyst particle.

In all of the polymerization processes described herein oligomers and polymers of the various olefins are made.

They may range in molecular weight from oligomeric POs (polyolefins), to lower molecular weight oils and waxes, to higher molecular weight POs. One preferred product is a polymer with a degree of polymerization (DP) of about 10 or more, preferably about 40 or more. By"DP"is meant the av- erage number of repeat (monomer) units in a polymer mole- cule.

Depending on their properties, the polymer made by the processes described herein are useful in many ways. For in- stance if they are thermoplastics, they may be used as mold- ing resins, for extrusion, films, etc. If they are elasto- meric, they may be used as elastomers. If they contain functionalized monomers such as acrylate esters, they are useful for other purposes, see for instance previously in- corporated US5880241.

Depending on the process conditions used and the polym- erization catalyst system chosen, polymers, even those made from the same monomer (s) may have varying properties. Some of the properties that may change are molecular weight and molecular weight distribution, crystallinity, melting point and glass transition temperature. Except for molecular weight and molecular weight distribution, branching can af- fect all the other properties mentioned, and branching may be varied (using the same nickel compound) using methods de- scribed in previously incorporated US5880241.

It is known that blends of distinct polymers, that vary for instance in the properties listed above, may have advan- tageous properties compared to"single"polymers. For in- stance it is known that polymers with broad or bimodal mo- lecular weight distributions may be melt processed (be shaped) more easily than narrower molecular weight distribu- tion polymers. Thermoplastics such as crystalline polymers may often be toughened by blending with elastomeric poly- mers.

Therefore, methods of producing polymers that inher- ently produce polymer blends are useful especially if a later separate (and expensive) polymer mixing step can be avoided. However in such polymerizations one should be aware that two different catalysts may interfere with one

another, or interact in such a way as to give a single poly- mer.

In such a process the transition metal containing po- lymerization catalyst disclosed herein can be termed the first active polymerization catalyst. Monomers useful with these catalysts are those described (and also preferred) above. A second active polymerization catalyst (and option- ally one or more others) is used in conjunction with the first active polymerization catalyst. The second active po- lymerization catalyst may be another late transition metal catalyst, for example as described in previously incorpo- rated W09830609, US5880241, US5714556 and US6060569, as well as US5955555, W099/10391, W097/38024, W097/48735, W098/38228, W099/46302 and W099/50318, which are also incor- porated by reference herein for all purposes as if fully set forth.

Other useful types of catalysts may also be used for the second active polymerization catalyst. For instance so- called Ziegler-Natta and/or metallocene-type catalysts may also be used. These types of catalysts are well known in the polyolefin field, see for instance Angew. Chem., Int.

Ed. Engl., vol. 34, p. 1143-1170 (1995), EP-A-0416815 and US5198401 for information about metallocene-type catalysts, and J. Boor Jr., Ziegler-Natta Catalysts and Polymeriza- tions, Academic Press, New York, 1979 for information about Ziegler-Natta-type catalysts, all of which are hereby in- cluded by reference. Many of the useful polymerization con- ditions for all of these types of catalysts and the first active polymerization catalysts coincide, so conditions for the polymerizations with first and second active polymeriza- tion catalysts are easily accessible. Oftentimes the"co- catalyst"or"activator"is needed for metallocene or Zieg- ler-Natta-type polymerizations. In many instances the same

compound, such as an alkylaluminum compound, may be used as an"activator"for some or all of these various polymeriza- tion catalysts.

In one preferred process described herein the first olefin (s) (the monomer (s) polymerized by the first active polymerization catalyst) and second olefin (s) [the mono- mer (s) polymerized by the second active polymerization cata- lyst] are identical, and preferred olefins in such a process are the same as described immediately above. The first and/or second olefins may also be a single olefin or a mix- ture of olefins to make a copolymer. Again it is preferred that they be identical particularly in a process in which polymerization by the first and second active polymerization catalysts make polymer simultaneously.

In some processes herein the first active polymerization catalyst may polymerize a monomer that may not be polymerized by said second active polymerization catalyst, and/or vice versa. In that instance two chemically distinct polymers may be produced. In another scenario two monomers would be present, with one polymerization catalyst producing a copolymer, and the other polymerization catalyst producing a homopolymer, or two copolymers may be produced which vary in the molar proportion or repeat units from the various monomers. Other analogous combinations will be evident to the artisan.

In another variation of this process one of the polym- erization catalysts makes an oligomer of an olefin, prefera- bly ethylene, which oligomer has the formula R7°CH=CH2, wherein R70 is n-alkyl, preferably with an even number of carbon atoms. The other polymerization catalyst in the pro- cess them (co) polymerizes this olefin, either by itself or preferably with at least one other olefin, preferably ethyl- ene, to form a branched polyolefin. Preparation of the oli-

gomer (which is sometimes called an a-olefin) by a second active polymerization-type of catalyst can be found in pre- viously incorporated US5880241 and W099/02472 (included by reference).

Likewise, conditions for such polymerizations, using catalysts of the second active polymerization type, will also be found in the appropriate above mentioned references.

Two chemically different active polymerization catalysts are used in this polymerization process. The first active polymerization catalyst is described in detail above. The second active polymerization catalyst may also meet the limitations of the first active polymerization catalyst, but must be chemically distinct. For instance, it may have a different transition metal present, and/or utilize a different type of ligand and/or the same type of ligand which differs in structure between the first and second active polymerization catalysts. In one preferred process, the ligand type and the metal are the same, but the ligands differ in their substituents.

Included within the definition of two active polymeri- zation catalysts are systems in which a single polymeriza- tion catalyst is added together with another ligand, pref- erably the same type of ligand, which can displace the original ligand coordinated to the metal of the original ac- tive polymerization catalyst, to produce in situ two differ- ent polymerization catalysts.

The molar ratio of the first active polymerization catalyst to the second active polymerization catalyst used will depend on the ratio of polymer from each catalyst de- sired, and the relative rate of polymerization of each cata- lyst under the process conditions. For instance, if one wanted to prepare a"toughened"thermoplastic polyethylene that contained 80% crystalline polyethylene and 20% rubbery

polyethylene, and the rates of polymerization of the two catalysts were equal, then one would use a 4 : 1 molar ratio of the catalyst that gave crystalline polyethylene to the catalyst that gave rubbery polyethylene. More than two ac- tive polymerization catalysts may also be used if the de- sired product is to contain more than two different types of polymer.

The polymers made by the first active polymerization catalyst and the second active polymerization catalyst may be made in sequence, i. e., a polymerization with one (either first or second) of the catalysts followed by a polymeriza- tion with the other catalyst, as by using two polymerization vessels in series. However it is preferred to carry out the polymerization using the first and second active polymeriza- tion catalysts in the same vessel (s), i. e., simultaneously.

This is possible because in most instances the first and second active polymerization catalysts are compatible with each other, and they produce their distinctive polymers in the other catalyst's presence. Any of the processes appli- cable to the individual catalysts may be used in this polym- erization process with 2 or more catalysts, i. e., gas phase, liquid phase, continuous, etc.

The polymers produced by this process may vary in mo- lecular weight and/or molecular weight distribution and/or melting point and/or level of crystallinity, and/or glass transition temperature and/or other factors. The polymers produced are useful as molding and extrusion resins and in films as for packaging. They may have advantages such as improved melt processing, toughness and improved low tem- perature properties.

Catalyst components which include transition metal com- plexes of (I), with or without other materials such as one or more cocatalysts and/or other polymerization catalysts

are also disclosed herein. For example, such a catalyst component could include the transition metal complex sup- ported on a support such as alumina, silica, a polymer, mag- nesium chloride, sodium chloride, etc., with or without other components being present. It may simply be a solution of the transition metal complex, or a slurry of the transi- tion metal complex in a liquid, with or without a support being present.

Hydrogen or other chain transfer agents such as silanes (for example trimethylsilane or triethylsilane) may be used to lower the molecular weight of polyolefin produced in the polymerization process herein. It is preferred that the amount of hydrogen present be about 0. 01 to about 50 mole percent of the olefin present, preferably about 1 to about 20 mole percent. When liquid monomers (olefins) are pres- ent, one may need to experiment briefly to find the relative amounts of liquid monomers and hydrogen (as a gas). If both the hydrogen and monomer (s) are gaseous, their relative con- centrations may be regulated by their partial pressures.

In the Examples, all pressures are gauge pressures.

Branching was determined by 1H NMR, taking the total of the methyl carbon atoms as the number of branches. Branching is uncorrected for end groups. Some of the transition metal complexes may have one or molecules of THF coordinated per molecule of complex. In the examples the group" (A)" is the s-allyl group (XVIII) The following abbreviations are used : AH-heat of fusion MI-melt index (2160 g, at 190°C)

MMAO-modified methylaluminoxane (1. 7 M in hexane) from Akzo Chemicals, Inc.

Mn-number average molecular weight Mw-weight average molecular weight PMAO-IP-Improved processing MMAO (4. 5 M in toluene) from Akzo Chemicals, Inc.

PE-polyethylene RT-room temperature THF-tetrahydrofuran Tm-melting point Example 1 Synthesis of (XVI) A sample of 2. 1809 g (9. 30 mmol) of 3, 5-di-t- butylsalicylaldehyde and 1. 0064 g (9. 3 mmol) of 2- aminomethylpyridine were placed in about 20 mL of methanol in a 100 mL flask and 3 drops of formic acid were added at RT. Since no precipitate formed, the methanol was removed and ether and sodium sulfate were added to the residue. The yellow solution was filtered through CeliteX plug on a frit.

After removal of the solvent, a yellow solid (2. 5508 g, 7. 86 mmol) product was obtained in 85% yield. 1H NMR (CDC13) : 1. 24 (s, 9H, CH3), 1. 34 (s, 9H, CH3), 4. 82 (s, 2H, CH2), 7. 11 (d, 1H, Ar-H), 7. 14 (t, 1H, Py-H), 7. 27 (d, 1H, Py-H), 7. 3 (d, 1H, Ar-H), 7. 63 (t, 1H, Py-H), 8. 48 (s and s, 2H, Py-H and C-H).

Example 2 Synthesis of (XVII) A sample of 4. 445 g (0. 021 mol) of 3, 5-di- nitrosalicylaldehyde and 2. 7194 g (0. 025 mol) of 2- aminomethylpyridine were placed in about 80 mL of methanol in a 250 mL flask and 5 drops of formic acid was added at RT. A yellow precipitate formed immediately. The reaction mixture was stirred overnight and filtered to collect the yellow solid which then was dissolved in THF and dried with sodium sulfate. After removal of the solvent, a yellow solid (5. 3088 g, 0. 018 mol) was obtained in 84% yield. 1H NMR (CD2Cl2) : 4. 94 (s, 2H, CH2), 7. 22 (t, 1H, Py-H), 7. 28 (d, 1H, Py-H), 7. 66 (t, 1H, Py-H), 8. 44 (d, 1H, Ar-H), 8. 52 (d, 1H, Ar-H), 8. 60 (s, 1H, C-H), 8. 78 (d, 1H, Py-H).

Example 3 Synthesis of the Sodium salt of (XVII) In a dry box, 0. 0683 g (2. 85 mmol) of sodium hydride was slowly added to a suspension of (XVII) (0. 7818 g, 2. 587 mmol) in 20 mL of THF. An orange precipitate formed while hydrogen gas was released. The reaction mixture was stirred overnight and filtered to collect the orange solid which then was rinsed with THF and pentane and dried under vacuo.

An orange powder (0. 6401 g, 1. 97 mmol) was obtained in 76% yield.

Example 4 Synthesis of the Sodium salt of (XVI) In a dry box, 0. 0966 g (4. 025 mmol) of sodium hydride was slowly added to a solution of (XVI) (1. 1873 g, 3. 66 mmol) in 50 mL of THF. The reaction mixture was stirred overnight and filtered through a CeliteX plug on a frit.

The solvent was removed and the residue was rinsed with pen- tane and dried under vacuo. A pale yellow solid (1. 1593 g, 3. 35 mmol) was obtained in 91% yield. H NMR (C6D6) : 1. 28 (m, THF-CH2), 1. 28 (s, 9H, CH3), 1. 50 (s, 9H, CH3), 3. 42 (m, THF-CH2), 4. 25 (s, 2H, CH2), 6. 30 (br, 1H, Ar-H), 6. 42 (br, 1H, Py-H), 6. 78 (br, 1H, Py-H), 6. 90 (br, 1H, Ar-H), 7. 46 (br, 1H, Py-H), 7. 68 (br, 1H, Py-H), 7. 92 (br, 1H, C-H).

Example 5 Synthesis of (XVII) Ni (A) _ In a dry box, 0. 0804 g (0. 169 mmol) of s- [H2CC (CO2Me) CH2] Ni (p-Br2) (see World Patent Application 9830609) and the product of Example 3 (0. 1097 g, 0. 338 mmol) were mixed in 20 mL of THF and stirred for one h. The reac- tion mixture was filtered to collect the brown solid which then was rinsed with THF and pentane and dried under vacuo.

An orange powder (0. 1427 g, 0. 31 mmol) was obtained in 92% yield.

Example 6 Synthesis of (XVI) Ni (A) In a dry box, 0. 0995 g (0. 209 mmol) of methyl methac- rylate nickel bromide dimer and the product of Example 4 (0. 1450 g, 0. 418 mmol) were mixed in 20 mL of THF and stirred for one h. The solvent was removed under vacuo. The dark brown residue was dissolved in methylene chloride and the solution was filtered through CeliteX plug on a frit.

After removal of the solvent, the brown solid was rinsed

with pentane and dried under vacuo. Product (0. 1203 g, 0. 25 mmol) was obtained in 60% yield. The 1H NMR was complex.

Example 7 Synthesis of (XVII) TiCl3 In a dry-box, a suspension of 0. 1197 g (0. 3695 mmol) of the product of Example 3 (0. 1097 g, 0. 338 mmol) in 20 mL of a mixture of toluene and THF (1 : 1) was added dropwise to a pre-cooled solution of TiCl4 (THF) 2 (0. 1234 g, 0. 3695 mmol) in 20 mL of toluene at-30°C. The brown reaction mixture was stirred 3 d and filtered to collect the solid, which was then rinsed with THF and pentane and dried under vacuo. A light brown powder (0. 1109 g, 0. 24 mmol) was obtained in 66% yield.

Example 8 Synthesis of (XVI) TiCl3 In a dry-box, a solution containing a sample of 0. 2135 g (0. 616 mmol) of the product of Example 4 in 20 mL of tolu- ene was added dropwise to a pre-cooled solution of TiCl4 (THF) 2 (0. 2058 g, 0. 616 mmol) in 20 mL of toluene at- 30°C. The red reaction mixture was stirred 3 d and filtered through a CeliteX plug on top of a frit. Removed the solvent, rinsed the residue with pentane and dried under vacuo. An orange powder (0. 2624 g, 0. 55 mmol) was obtained in 89% yield. 1H NMR (CD2Cl2) : 1. 41 (s, 9H, CH3), 1. 60 (s, 9H, CH3), 5. 54 (s, 2H, CH2), 7. 48 (d, 1H, Ar-H), 7. 57 (d, 1H, Py-H), 7. 64 (t, 1H, Py-H), 7. 78 (d, 1H, Ar-H), 8. 08 (t, 1H, Py-H), 8. 45 (s, 1H, C-H), 9. 46 (d, 1H, Py-H).

Example 9 Synthesis of (XVI) ZrCl3 In a dry-box, a solution of 0. 1920 g (0. 554 mmol) of the product of Example 4 in 20 mL of toluene was added drop- wise to a pre-cooled solution of ZrCl4 (THF) 2 (0. 2091 g, 0. 554 mmol) in 20 mL of toluene at-30°C. The yellow reaction

mixture was stirred 3 d and filtered through a CeliteX plug on top of a frit. Removed the solvent, rinsed the residue with pentane and dried under vacuo. A yellow powder (0. 2528 g, 0. 485 mmol) was obtained in 88% yield. 1H NMR (CD2C12) : 1. 27 (s, 9H, CH3), 1. 44 (s, 9H, CH3), 1. 73 (br, CH2, THF), 3. 60 (br, CH2, THF), 5. 38 (s, 2H, CH2), 7. 30 (d, 1H, Ar-H), 7. 53 (m, 2H, Py-H), 7. 65 (d, 1H, Ar-H), 8. 02 (t, 1H, Py-H), 8. 40 (s, 1H, C-H), 9. 05 (d, 1H, Py-H).

Example 10 Synthesis of (XVI) CoCl In a drybox, a solution containing a sample of 0. 3103 g (0. 8957 mmol) of the product of Example 4 in 20 mL of THF was added dropwise to a pre-cooled suspension of CoC12 (0. 1163 g, 0. 8957 mmol) in 10 mL of toluene at-30°C. The red brown reaction mixture was stirred overnight. Removed the solvent, extracted the residue with methylene chloride and dried under vacuo. A yellowish green powder (0. 3103 g, 0. 743 mmol) was obtained in 83% yield. 1H NMR (CD2Cl2) : very broad due to paramagnetism.

Example 11 Synthesis of (XVI)-CrCl2 In a dry-box, a solution of 0. 1248 g (0. 36 mmol) of the product of Example 4 in 20 mL of toluene was added dropwise to a pre-cooled solution of CrCl3 (THF) 3 (0. 1350 g, 0. 36 mmol) in 20 mL of toluene and 2 mL of THF at-30°C. The brown re- action mixture was stirred 3 d and filtered through a Ce- lite@ plug on top of a frit. After removing the solvent, the residue was rinsed with pentane and dried under vacuo.

A brown powder (0. 112 g, 0. 25 mmol) was obtained in 70% yield. H NMR (CD2C12) : very broad due to paramagnetism.

Examples 12-22 Polymerization of Ethylene In a drybox, 0. 02 mmol of the transition metal compound (catalyst) was placed in a glass vial and dissolved in 5 mL of 1, 2, 4-trichlorobenzene. The vial was cooled to-30°C in the drybox freezer. PMAO was added to the vial on top of the frozen solution, then the vial was capped, sealed and placed into a shaker tube which was then shaken mechanically under 3. 45 MPa of ethylene in a shaker apparatus outside the dry box for about 18 h. The reaction mixture was slowly poured to a 100 mL of methanol solution of concentrated HC1 (10% volume). The mixture was stirred overnight and fil- tered. The polymer was collected on a frit, washed with acetone and dried in vacuo.

If a cocatalyst was triarylborane, catalyst and cocata- lyst were placed in the reaction vial and cooled at-30°C, then 1, 2, 4-trichlorobenzene was added.

Results of the polymerization are given in Table 1.

Table 1 Ex. Catalyst Cocatalyst PE (g) Produc- MI Mw Tm (°C), Me/1000 ( equiv. ) tivity #H(J/g) CH2 (mol PE/mol Cata- lyst) 12 (XVI)#Ni (A) BPh3 (20) 0 0 13 (XVI)#Ni (A) B(C6F5)3 (20) 3.2882 5757 198 9694 bi- 43.98, --- 83.92 modal 115.41, 4.509 14 (XVI)#Ni (A) MMAO (300) 1.2006 2000 56.4 53499 bi- 119.81, 30.8 108.26 modal 15 (XVII)#Ni (A) BPh3 (20) 0 0 16 (XVII)#Ni (A) B(C6F5)3 (20) 1.076 1779 0.33 181632 127.74, 204.8 19.5 very broad 17 (XVII)#Ni (A) MMAO (300) 2.0038 3489 0.06 279468 bi- 126.26, 166.2 28.25 modal 18 (XVI)#CoCl MMAO (300) 0.2084 358 30160 126.96, 63.81 72.45 19 (XVI)#TiCl3a MMAO (500) 8.4812 2.83 x 0 insoluble 133.98, 188.6 7.97 104 20 (XVII)#TiCl3a MMAO (500) 4.9081 1.66 x 0 insoluble 127.49, 198.3 7.6 104 21 (XVI)#CrCl2 MMAO (500) 0.0558 100 49926 129.71, 226.7 21.22 22 (XVI)#ZrCl3 MMAO (500) 7.489 1.28 x 0 insoluble 135.49, 208.5 0 104 0.01 mmol catalyst.

Examples 23-25 Copolymerization of 1-Hexene and Ethylene In a drybox, 0. 005 mmol of the catalyst was placed in a glass vial and dissolved in 3 mL of 1, 2, 4-trichlorobenzene.

The vial was cooled to-30 C in the drybox freezer. PMAO (500 equiv.) and 2 mL of 1-hexene then were added to the vial on top of the frozen solution, then the vial was capped, sealed and placed into a shaker tube which was then shaken mechanically in a shaker apparatus under 1. 38 MPa ethylene for about 18 h. The reaction mixture was slowly poured to a 100 mL of methanol solution of concentrated HC1 (10% volume). The mixture was stirred overnight and fil- tered. The polymer was collected on a frit, washed with ace- tone and dried in vacuo. The copolymer formed was high in molecular weight because in the melt index test there was no flow. Results of the polymerizations are given in Table 2.

Table 2 Ex Catalyst Copolymer Productivity (kg Tm (°C), Me/ (g) polymer/mol AH (J/g) 1000 CH2 Cat.) 23 (XVII) TiCl3 0 9151 42 9 120 27, 59. 96 54. 89 24 (XVI) #TiCl3 4.1818 951.3 114. 84, 51. 8338. 46 25 (XVI) ZrCl3 3 0236 525 1 129 07, 116. 0 14. 94 Example 26 Polymerization of Ethylene In a drybox, 40 mL of toluene and 0. 93 mL (4. 29 mmol) of PMAO-IP were placed in a 100 mL Schlenk flask and stirred 3 min. Then 0. 0041 g (0. 0086 mmol) of (XVI) TiCl3 was added to the solution. The flask was sealed, removed from the drybox and attached to an ethylene Schlenk line. After pumping off the air and nitrogen and purging with ethylene,

the reaction mixture was stirred 20 min under ethylene (34. 5 kPa) and quenched with 50 mL of a methanol solution of con- centrated HC1 (10% volume). The polymer was collected on a frit, washed with methanol and acetone thoroughly and then, dried in vacuo overnight. A crystalline white polymer (1. 0257 g) was obtained with Mw = 387728, Mw/Mn = 3. 82 ; Me/1000CH2 (1H NMR in TCE-d2) = 0. 0 and Tm = 134. 31, AH = 165. 0 J/g.

Example 27 Copolymerization of 1-Hexene and Ethylene In a drybox, 40 mL of toluene, 0. 9 mL (4. 05 mmol) of PMAO-IP and 5 mL of 1-hexene were placed in a 100 mL Schlenk flask and stirred 3 min. Then 0. 0039 g (0. 0082 mmol) of the (XVI) TiCl3 was added to the solution. The flask was sealed, removed from the drybox and attached to an ethylene Schlenk line. After pumping off the air and nitrogen and purging with ethylene, the reaction mixture was stirred 45 min under ethylene (34. 5 kPa) and quenched with 50 mL of a methanol solution of concentrated HC1 (10% volume). The polymer was collected on a frit, washed with methanol and acetone thor- oughly, and then dried in vacuo overnight. A rubbery white polymer (1. 705 g, 207. 93 kg polymer/mol catalyst) was ob- tained with Mw = 624577, MW/Mn = 3. 02 ; Me/lOOOCHsH NMR in TCE-d2) = 46. 83 and Tm = 76. 95, AH = 33. 35 J/g.