POLYMERIZATION OF ETHYLENE

Abstract: Ethylene is polymerized by novel nickel or iron complexes of selected novel 2,2-bipyridine-6-imines, optionally with the addition of other cocatalysts. The polymers are useful for films and molding resins.

Description: TITLE POLYMERIZATION OF ETHYLENE FIELD OF THE INVENTION Ethylene is polymerized using selected iron or nickel complexes of 2 , 2 ' -bipyridme-6 -imines , optionally m the presence of certain activators such alkylaluminum compounds. Also disclosed herein are novel 2 , 2 ' -bipyridme- 6- imines and their iron and nickel complexes. TECHNICAL BACKGROUND Polyethylene is a very important item of commerce, large quantities of various grades of this polymer being produced annually for a large number of uses, such as packaging films and moldings. There are many different methods for making such polyethylenes, including many used commercially, such as free radical polymerization to make low density polyethylene, and many so-called coordination catalysts such as Ziegler-Natta-type and metallocene-type catalysts. Each of these catalyst systems has its advantages and disadvantages, including cost of the polymerization and the particular structure of the polyethylene produced. Due to the importance of polyethylene, new catalyst systems which are economical and/or produce new types of polyethylenes are constantly being sought . US5866663 describes the polymerization of ethylene and other olefms using nickel and other transition metal complexes of various imines and similar compounds. This publication is incorporated by reference herein for all purposes . US5955555, WO98/30612, 098/38228, O99/02472 and 099/12981 (all incorporated by reference herein for all purposes) describe the use of iron or cobalt complexes of 2 , 6-diacylpyridinebisimines or 2 , 6-pyridinedicarboxaldehydebisimines as catalysts for the polymerization of olefins, mostly of ethylene. These publications describe the preparation of polyethylenes ranging in molecular weight from low molecular weight alpha-olefins and other oligomers to high molecular weight polyethylenes. EP-A-0454231 (also incorporated by reference herein for all purposes) describes the use of various complexes of transition metals with selected ligands such as "bipyridine" to polymerize ethylene or other olefins. In all of the publications cited above, the ligands described herein are not mentioned. SUMMARY OF THE INVENTION This invention concerns, a first process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene and a Ni or Fe complex of a ligand of the formula wherein: R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an imino nitrogen atom has at least two carbon atoms bound to it; and each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R s , R 7 , R 8 and R 9 vicinal to one another, or R 6 and R 7 taken together, may form a ring . Also disclosed herein is a second process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene, a compound of the formula and: (a) a first compound , which is a neutral Lewis acid capable of abstracting X an alkyl group or a hydride group from M to form WX , (WR ) or H , and which is also capable of transferring an alkyl group or a hydride to M, provided that WX is a weakly coordinating anion; or (b) a combination of second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X , a hydride or an alkyl group from M to form a weakly coordinating anion; wherein: M is Fe or Ni ; each X is an anion; n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation state of M; R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an imino nitrogen atom has at least two carbon atoms bound to it; and each of R 3 , R , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 vicinal to one another, or R 6 and R 7 taken together, may form a ring. This invention also concerns a third process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200 °C, ethylene and a compound of the formula wherein : each X is an anion; R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an immo nitrogen atom has at least two carbon atoms bound to it; each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R s , R 7 , R 8 and R 9 vicinal to one another, or R 6 and R 7 taken together, may form a ring; Z 1 is hydride or alkyl or an anionic ligand into which ethylene can insert ; Y is a neutral ligand capable of being displaced by ethylene, or a vacant coordination site; Q is a relatively non-coord ating anion; P is a divalent polyethylene group containing one or more ethylene units; and Z is an end group. Also described herein is a compound of the formula R 8 wherein: R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an immo nitrogen atom has at least two carbon atoms bound to it; and each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R , R 5 , R 6 , R 7 , R 8 and R 9 vicinal to one another or, R 6 and R 7 taken together, may form a ring . Described herein is a compound of the formula wherein : M is Fe or Ni ; each X is an anion; n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation state of M; R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl ,- R 2 is hydrocarbyl or substitited hydrocarbyl, provided that a carbon atom of R 2 bound to an imino nitrogen atom has at least two carbon atoms bound to it; each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 vicinal to one another, or R 6 and R 7 taken together, may form a ring; Z 1 is hydride or alkyl or an anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene, or a vacant coordination site; Q is a relatively non-coordinating anion; P is a divalent polyethylene group containing one or more ethylene units; and Z is an end group. 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. 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 hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included m the meaning of "substituted" are heteroaromatic rings. By "(inert) functional group" herein is meant a group, other than hydrocarbyl or substituted hydrocarbyl, which 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 described herein that the compound m which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and lodo) , ether such as -OR wherein R 18 is hydrocarbyl or substituted hydrocarbyl. In cases which the functional group may be near a nickel or iron atom, the functional group should not coordinate to the metal atom more strongly than groups m (I) which are shown as coordinating to the metal atom m the complexes, that is they should not displace the desired coordinating group. By an "alkyl aluminum compound" is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, hydride and halogen may also be bound to aluminum atoms 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, sul fides, and organic nitπles . 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 "relatively noncoordinatmg anions" (or "weakly coordinating anions" is meant those anions as are generally referred to m the art m this manner, and the coordinating ability of such anions is known and has been discussed m the literature, see for instance W. Beck., et al . , Chem. Rev. , vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev. , vol. 93, p. 927-942 (1993), both of which are hereby included by reference . Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X " , including R 9 3 AlX " , R 9 2 A1C1X " , R 9 A1C1 2 X " , and "R AlOX " , wherein R 9 is alkyl . Other useful noncoordinatmg anions include BAF " {BAF = tetrakis [3 , 5- bis (trifluoromethyl)phenyl]borate} , SbF 6 " , PF 6 " , and BF 4 " , trifluoromethanesulfonate, p-toluenesulfonate, (R f S0 2 ) 2 ~ / an *J (C 6 F 5 ) 4 B\ By an "empty coordination site" is meant a potential coordination site that is not occupied by a ligand. Thus if an ethylene molecule is in the proximity of the empty coordination site, the ethylene molecule may coordinate to the metal atom. By a "ligand that may add to ethylene" is meant a ligand coordinated to a 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) : WO 00/68280 PCT USOO/l 1916 > Herein a compound of the " formula" L - -*- MX n (vi : signifies a ligand L [such as (I)] coordinated to the transition metal group MX n . In this representation whether L is acting as a monodentate, bidentate, tridentate, etc. ligand is unspecified. In (I) and its various Ni and Fe complexes as described herein it is preferred that: R 1 is hydrogen or hydrocarbyl, more preferably hydrogen or alkyl containing 1 to 10 carbon atoms, especially preferably hydrogen or methyl ; and/or R 2 is aryl or substituted aryl , more preferably phenyl or substituted phenyl, especially phenyl substituted in the 2 , or 2 and 6 positions, with alkyl containing 1 to 10 carbon atoms or halogen, and optionally substituted with alkyl containing 1 to 10 carbon atoms in the 4 position; and/or each of R 3 , R 4 , R 5 , R s , R 7 , R 8 and R 9 is hydrogen. In specific preferred compounds (I) and complexes thereof the following groups are present. In all instances each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is hydrogen: R 1 is hydrogen and R 2 is 2 , 6-diisopropylphenyl ; or R 1 is hydrogen and R 2 is 2 , 4 , 6-tri-t-butylphenyl ; or R 1 is hydrogen and R 2 is pentafluorophenyl ; or R 1 is methyl and R 2 is 2 , 6-diisopropylphenyl . (I) may be prepared by the well-known general reaction of a primary amine with a carbonyl compound, in this case a 2 , 2 ' -bipyridme-6-carboxaldehyde or a 6-acyl-2,2'- bipyridme, to make an lmme . Such preparations are illustrated herein m Examples 1-4. In (II) it is preferred that X is chloride, bromide or acetylacetonate (acac) . Useful neutral monodentate ligands Y include etners such as diethyl ether and tetrahydrofuran and mtriles such as acetonitπle . In the second polymerization process described herein an iron or nickel complex (II) is contacted with ethylene and a neutral Lewis acid W capable of abstracting X , hydride or alkyl from (II) to form a weakly coordinating anion, and must alkylate or be capable of adding a hydride ion to the metal atom, or an additional alkylatmg agent or an agent capable of adding a hydride anion to the metal atom must be present. The neutral Lewis acid is originally uncharged (i.e., not ionic) . Suitable neutral Lewis acids include SbF 5 , Ar 3 B (wherein Ar is aryl) and BF 3 . Suitable cationic Lewis acids or Bronsted acids include NaBAF, silver trifluoromethanesulfonate, HBF 4 , or [C 6 H 5 N (CH 3 ) 2 ] + [B(C S F 5 ) 4 ] . In those instances m which (II) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid) does not contain an alkyl or hydride group already bonded to the metal atom, the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal or a separate alkylatmg or hydridmg agent is present, i.e., causes an alkyl group or hydride to become bonded to the metal atom. These alkyl groups, especially methyl, and hydride are groups that may also be Z 1 in (III) and (IV) . It is preferred that the alkyl groups an alkyl aluminum compound contain 1 to 4 carbon atoms each, and more preferred that the alkyl groups are methyl or ethyl . For instance, alkyl aluminum compounds (see next paragraph) may alkylate (II) . However, not all alkyl aluminum compounds may be strong enough Lewis acids to abstract X or an alkyl group from the metal atom. In that case a separate Lewis acid strong enough to do the abstraction must be present. A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R 3 A1 , R 19 A1C1 2 , R 19 2 A1C1, and "R 19 A10" (alkylalummoxanes) , wherein R is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylalummoxane (which is an oligomer with the general formula [MeAlO] n ), (C 2 H 5 ) 2 A1C1, C 2 H 5 AlCl 2 , and [ (CH 3 ) 2 CHCH 2 ] 3 A1. Metal hydrides such as NaBH 4 may be used to bond hydride groups to the metal M. In the third polymerization process described herein a nickel or iron complex of (I) is either added to the polymerization process or formed m situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form a living ended polymer containing such a complex. Examples of such complexes which may be formed initially m situ include (III) and (IV), as defined above, and wherein the "parallel lines" are an ethylene molecule coordinated to the metal . These complexes may be added directly to the process or formed in situ. For instance, (III) may be formed by the reaction of (II) with a neutral Lewis acid such as an alkyl aluminum compound. Another method of forming such a complex situ is adding a suitable iron or nickel compound such nickel [II] acetylacetonate, (I) and an alkyl aluminum compound. Other metal salts in which anions similar to acetylacetonate are present, and which may be removed by reaction with the Lewis or Bronsted acid. For instance metal halides and carboxylates (such as acetates) may be used, particularly if they are slightly soluble in the process medium. It is preferred that these precursor metal salts be at least somewhat soluble in the process medium. After the ethylene polymerization has started, the complex may be in a form such as (V) as defined above wherein P may be a divalent (poly) ethylene group of the formula -(CH 2 CH 2 ) X - wherein x is an integer of 1 or more, and Z is an end group (assuming no branching taking place during polymerization), for example the groups listed for Z 1 above. Those skilled in the art will note that (V) is in essence a polymer containing a so-called living end. It is preferred that M be in +2 oxidation state in (III) , (IV) and (V) . Compounds such as (III) , (IV) and (V) may or may not be stable away from an environment similar to that of the polymerization process, but they may be detected by NMR spectroscopy, particularly one or both of " "Ή and 13 C NMR, and particularly at lower temperatures. Such techniques, especially for polymerization "intermediates" of these types are known, see for instance US5880241, especially Examples 197-203, which is hereby included by reference. (Ill) , (IV) and (V) may also be used in the absence of any "co-catalysts" or "activators" to polymerize ethylene in a third polymerization process. Except for the ingredients in the process, the process conditions for the third process, such as temperature pressure, polymerization medium, etc., may be the same as for the first and second polymerization processes, and preferred conditions for those processes are also preferred for the third polymerization process . In all the polymerization processes herein, the temperature at which the polymerization is carried out is about -100°C to about +200°C, preferably about 0°C to about 150°C, more preferably about 25°C to about 100°C. A convenient ethylene pressure to use m the polymerization is about 300 kPa to about 275 MPa, more preferably about 2 MPa to about 100 MPa. The polymerization processes herein may be run m the presence of various liquids, particularly aprotic organic liquids. The catalyst system, ethylene, and polyethylene may be soluble or insoluble m these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes , selected halogenated hydrocarbons, and aromatic hydrocarbons. Hydrocarbons are the preferred solvent. Specific useful solvents include hexane, toluene, benzene, chloroform, methylene chloride, 1 , 2 , 4 -tπchorobenzene, p-xylene, and cyclohexane. The catalysts herein may be "heterogenized" by coating or otherwise attaching them to solid supports, such as silica or alumina. Where an active catalyst species is formed by reaction with a compound such as an alkylaluminum compound, a support on which the alkylaluminum compound is first coated or otherwise attached is contacted with the nickel compound precursor to form a catalyst system m which the active nickel catalyst is "attached" to the solid support . These supported catalysts may be used m polymerizations m organic liquids, as described m the immediately preceding paragraph. They may also be used m so-called gas phase polymerizations m which the olefm(s) being polymerized are added to the polymerization as gases and no liquid supporting phase is present. It is known that certain transition metal containing polymerization catalysts including those disclosed nere , are especially useful m varying the branching m polyolefms made with them, see for instance previously incorporated US5714556, US5880241, WO98/30610 and WO98/30609. It is also known that blends of distinct polymers, that vary for instance m the properties listed above, may have advantageous properties compared to "single" polymers For instance it is known that polymers with broad or bimodal molecular weight distributions may be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Similarly, thermoplastics such as crystalline polymers may often be toughened by blending with elastomeπc polymers. Therefore, methods of producing polymers which inherently produce polymer blends are useful especially if a later separate (and expensive) polymer mixing step can be avoided. However m 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 polymer. In such a process the catalysts 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 optionally one or more others) is used in conn unction with the first active polymerization catalyst. The second active polymerization catalyst may be another late transition metal catalyst, for example as described m previously incorporated US5714556, UΞ5880241, US5955555, WO98/30610 and 98/30609. 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 m the polyolefm field, see for instance Ange . 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 Polymerizations , Academic Press, New York, 1979 for information about Ziegler-Natta-type catalysts, all of which are hereby included by reference. Many of the useful polymerization conditions for all of these types of catalysts and the first active polymerization catalysts coincide, so conditions for the polymerizations with first and second active polymerization catalysts are easily accessible. Oftentimes the "co-catalyst" or "activator" is needed for metallocene or Ziegler-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 polymerization catalysts. Suitable catalysts for the second polymerization catalyst also include metallocene-type catalysts, as described m US5324800 and EP-A-0129368 ; particularly advantageous are bridged bis-mdenyl metallocenes , for instance as described m US5145819 and EP-A-0485823. Another class of suitable catalysts comprises the well-known constrained geometry catalysts, as described m EP-A-0416815, EP-A-0420436 , WP-A-067140 , EP-A-0643066 and WO91/04257. Also the class of transition metal complexes described m W096/13529 can be used. In one preferred process described herein the first olefm(s) [ethylene polymerized by the first active polymerization catalyst] and second olefm(s) [the monomer (s) polymerized by the second active polymerization catalyst] are identical, and preferred olefins such a process are the same as described immediately aoove . The second olefins may also be a single olef or a mixture of olefins to make a copolymer. Again it is preferred that they be identical particularly a process m 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 m 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 polymerization catalysts makes an oligomer of an olefm, preferably ethylene, which oligomer has the formula R 70 CH=CH 2 , wherein R 70 is n-alkyl, preferably with an even number of carbon atoms. The other polymerization catalyst in the process then (co) polymerizes this olefm, either by itself or preferably with at least one other olefm, preferably ethylene, to form a branched polyethylene. Preparation of the oligomer (which is sometimes called an α-olefm) by a second active polymerization-type of catalyst can be found m previously incorporated US5880241, and WO99/02472 (also incorporated by reference herein for all purposes) . Likewise, conditions for such polymerizations, using catalysts of the second active polymerization type, will also be found m the appropriate above mentioned references. Two chemically different active polymerization catalysts are used m this polymerization process. The first active polymerization catalyst is described m 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 m 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 m their substituents . Included withm the definition of two active polymerization catalysts are systems m which a single polymerization catalyst is added together with another ligand, preferably the same type of ligand, which can displace the original ligand coordinated to the metal of the original active polymerization catalyst, to produce in situ two different 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 desired, and the relative rate of polymerization of each catalyst 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 active polymerization catalysts may also be used if the desired 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 m sequence, i.e., a polymerization with one (either first or second) of the catalysts followed by a polymerization with the other catalyst, as by using two polymerization vessels m series. However it is preferred to carry out the polymerization using the first and second active polymerization catalysts m the same vessel (s) , i.e., simultaneously. This is possible because m most instances the first and second active polymerization catalysts are compatible with each other, and they produce their distinctive polymers m the other catalyst's presence. Any of the processes applicable to the individual catalysts may be used m this polymerization process with 2 or more catalysts, i.e., gas phase, liquid phase, continuous, etc. The polymers produced by this "mixed catalyst" process may vary in molecular weight and/or molecular weight distribution and/or melting point and/or level of crystallmity, and/or glass transition temperature and/or other factors. For copolymers the polymers may differ m ratios of comonomers if the different polymerization catalysts polymerize the monomers present at different relative rates. The polymers produced are useful as molding and extrusion resms and m films as for packaging. They may have advantages such as improved melt processing, toughness and improved low temperature properties. Hydrogen may be used to lower the molecular weight of polyethylene produced m the first or second processes. It is preferred that the amount of hydrogen present be about 0.01 to about 50 mole percent of the ethylene present, preferably about 1 to about 20 mole percent. The relative concentrations of hydrogen and ethylene may be regulated by their partial pressures. Included herein within the definitions of all the polymerization processes are mixtures of starting materials that lead to the formation in situ of the transition metal compounds specified in all of the polymerization processes. In the Examples, various abbreviations are used: acac - acetylacetonate DME - 1 , 2-dimethoxyethane DSC - Differential Scanning calorimetry GPC - Gel Permeation Chromatography Mn - number average molecular weight Mw - weight average molecular weight PE - polyethylene PMAO - methylaluminoxane Melting point was determined by DSC at a heating rate of 10°C/min. The melting point was taken as the peak of the melting endotherm on the second heat. Usually the DSCs of these polymers exhibited broad melting endotherms . Examples 1-5 Preparation of Ligands (I) This procedure illustrates the synthesis of the 2,2'- bipyridinephenylimine ligands. A 100 mL round-bottomed flask was charged with 1.0 g (5.43 mmol) of 2 , 2 ' -bipyridine- 6-carboxaldehyde . Anhydrous ethanol (50 mL) was added forming an orange solution. 2 , 6-Diisopropylaniline (0.96 g, 5.43 mmol) and 3 drops of formic acid were added and the reaction was stirred overnight. A yellow precipitate began forming after approximately 15 min. The reaction mixture was filtered and the product was washed with methanol and dried in vacuo . A yellow solid (1.22 g, 65%), (1-1), was recovered. X H NMR (300 MHz, 20°C, CDC1 3 ) δ 8.69-7.12 (m, 10H, bipyridine and aromatic protons); 8.39 (s, 1H, backbone H) ; 2.99 (septet, 2H, CH(CH 3 ) 2 ); 1.18 (d, 12H, CH(CH 3 ) 2 ). Structures of the various ligands (I) are given Table 1. In all instances R 3 , R 4 , R 3 , R 6 , R 7 , R 8 and R 9 were hydrogen . Table 1 Examples 6-15 Preparation of Fe and Ni Complexes This is a general procedure for the synthesis of NιBr 2 complexes of 2 , 2 ' -bipyπdmephenylimmes . In a drybox, a round bottom flask was charged with (DME)NιBr 2 (0.225 g, 0.728 mmol) . Dichloromethane (10 mL) was added forming a peach suspension. 2 , 2 ' -Bipyridmephenylimme (0.728 mmol) was added and the resulting solution was stirred 12 h. The reaction mixture was filtered (sometimes through Celite®) and the solvent was removed m vacua . The product was wasned with pentane and dried in vacuo . This is a general procedure for the synthesis of Nι(acac) 2 complexes of 2 , 2 ' -bipyridmephenylimmes . In a drybox, a round bottom flask was charged with Nι(acac) 2 (0.100 g, 0.28 mmol). Tetrahydrofuran (30 mL) was added forming a green suspension. 2 , 2 ' -Bipyridmephenylimme (0.728 mmol) was added and the resulting solution was stirred 12 h. The reaction mixture was filtered through Celite® and the solvent was removed m vacuo . The product was washed with pentane and dried in vacuo . This is a general procedure for the synthesis of FeCl 2 complexes of 2 , 2 ' -bipyridmephenylimmes . In a drybox, a round bottom flask was charged with 2,2'- bipyndmephenylimme (0.58 mmol) . Tetrahydrofuran (30 mL) was added forming a yellow solution. FeCl 2 (0.074 g, 0.58 mmol) was added and the resulting suspension was stirred 12 h. The reaction mixture was filtered and the product was washed with tetrahydrofuran and pentane and dried in vacuo . For each of the complexes made, yields and other data are given m Table 2. Table 2 Examples 16-23 Polymerizations with Ethylene This procedure is general for ethylene polymerization. A reactor was charged with Ni or Fe complex (0.03 mmol) . 1 , 2 , 4-Trichlorobenzene (3 mL) was added and the catalyst solution was placed in a -20°C freezer for 15 min. Another layer of 1 , 2 , 4-trichlorobenzene (3 mL) was added and the reactor was again placed m a -20°C freezer for 15 mm. This procedure separated the catalyst solution from the co-catalyst through a layer of frozen solvent. PMAO co-catalyst (1 L) was added and the frozen reactor was brought out of the drybox. The reactor was evacuated, charged with ethylene to 6.9 MPa (1000 psi) and the polymerization run for 16 h. Polyethylene was recovered by precipitation m methanol, washed with 6 M HCl and methanol and dried under high vacuum overnight. Details of the various polymerizations are given m Table 3. By DSC, in Example 16 the Mn was 540 and the Mw was 2569, and in Example 21 the Mn was 1676 and the Mw was 80,000. Table 3

Claims: CLAIMS What is claimed is: 1. A process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene and an active catalyst based on a transition metal complex of an imine- functional ligand, characterized m that said catalyst is a Ni or Fe complex of a ligand of the formula R 8 wherein: R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl ,- R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an imino nitrogen atom has at least two carbon atoms bound to it; and each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 vicinal to one another, or R s and R 7 taken together, 2. The process as recited m claim 1, characterized m that said complex is and also present is: (a) a first compound W, which is a neutral Lewis acid capable of abstracting X " , an alkyl group or a hydride group from M to form WX " , (WR ) " or WH " , and which is also capable of transferring an alkyl group or a hydride to M, provided that WX " is a weakly coordinating anion; or (b) a combination of second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X " , a hydride or an alkyl group from M to form a weakly coordinating anion; wherein: M is Fe or Ni ; each X is an anion; and n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation state of M. 3. The process as recited in claim 1 characterized in that said complex is wherein : each X is an anion; Z 1 is hydride or alkyl or an aniomc ligand into which ethylene can insert ; Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordmatmg anion; P is a divalent polyethylene group containing one or more ethylene molecules; and Z is an end group. 4. The process as recited m any one of claims 1-3, characterized m that R 1 is hydrogen or alkyl containing 1 to 10 carbon atoms, and each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is hydrogen . 5. The process as recited m any one of claims 1-3, characterized m that R 2 is aryl or substituted aryl. 6. The process as recited in claim 4, characterized m that R 2 is phenyl or substituted phenyl. 7. The process as recited m any one of claims 1-3, characterize dm that said temperature about 25°C to about 100°C. 8. The process as recited m any one of claims 1-3, characterized in that at least one other polymerization catalyst is present. 9. The process as recited any one of claims 1-3, characterized m that said process is carried out m the gas phase . 10. The process as recited m any one of claims 1-3, characterized m that said process is carried out m the liquid phase. 11. A compound of the formula R 8 wherein: R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an immo nitrogen atom has at least two carbon atoms bound to it; and each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R ε , R 7 , R 8 and R 9 vicinal to one another, or R 6 and R 7 taken together, 12. A compound of the formula wherein : M is Fe or Ni ; each X is an anion; n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation state of M; R 1 is hydrogen, hydrocarbyl or substituted hydrocarbyl; R 2 is hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom of R 2 bound to an imino nitrogen atom has at least two carbon atoms bound to it; each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, provided that any two of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 vicinal to one another or R 6 and R 7 taken together may form a ring; Z 1 is hydride or alkyl or any other anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; P is a divalent polyethylene group containing one or more ethylene molecules; and Z is an end group. 13. The compound as recited in claim 11 or 12, characterized in that R 1 is hydrogen or alkyl containing 1 to 10 carbon atoms, and each of R 3 , R 4 , R 5 , R s , R 7 , R 8 and R 9 is hydrogen . 14. The compound as recited in claim 11 or 12, characterized in that R 2 is aryl or substituted aryl . 15. The compound as recited in claim 13, characterized in that R 2 is phenyl or substituted phenyl. 16. An olefin polymerization catalyst comprising the compound of claim 12.

Inventors: LENGES GERALDINE MARIE, LENGES, GERALDINE, MARIE
Applicants: DU PONT, LENGES GERALDINE MARIE, E.I. DU PONT DE NEMOURS AND COMPANY, LENGES, GERALDINE, MARIE
Application year: 2000
Main classification: C08F10
IPC codes: C07D213, C07F15, C08F2, C08F4, C08F10