MXPA99005619A - Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis(imines) and novel complexes of pyridinebis(imines) with iron and cobalt - Google Patents

Abstract

Ethylene may be polymerized by contacting it with certain iron or cobalt complexes of selected 2, 6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines). The polymers produced are useful as molding resins. Novel 2,6-pyridinecarboxaldehydebis(imines) and 2, 6-diacylpyridinebis(imines), and novel complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2, 6-diacylpyridinebis(imines) with iron and cobalt are also disclosed.

Description

ETHYLENE POLYMERIZATION WITH SPECIFIC COMPLEXES OF IRON OR COBALT, NOVEDOSAS PIRIDIN-BIS (IMINAS) AND NEW COMPLEXES OF PIRIDIN-BIS (IMINAS) WITH IRON AND COBALT FIELD OF THE INVENTION The selected iron and cobalt complexes of 2,6-pyridinecarboxaldehydebis (imine) and 2,6-diacylpyridinebis (asbestos) are catalysts for the polymerization of ethylene. Also described herein are the novel 2,6-pyridinecarboxaldehydebis (imine =) and 2,6-diacylpyridinebis (imines), and the cobalt and iron complexes of such compounds.

FIELD OF THE INVENTION Ethylene polymers are important articles of commerce, being produced annually hundreds of tons. These polymers are used in a large number of ways, from the low molecular weight polyethylene (PE) that is used as a lubricant and for the release of molds, to higher molecular weight grades that are used for REF. : 30177 fibers, films, molding resins, etc. In some cases ethylene is polymerized using a catalyst, often a compound or transition metal complex. These catalysts vary in cost per unit weight of PE produced, the polymer structure produced, the possible need to remove the PE catalyst, the toxicity of the catalyst, etc. Due to the commercial importance of the polymerization of ethylene, several polymerization catalysts are constantly being sought. L. Sacconi, et al. / J. Chem. Soc. (A), 1968 p. 1510-1515 report the synthesis of certain cobalt complexes of 2,6-diacetylpyridinbis (imines). None of these cobalt complexes or the 2,6-diacetylpyridinebis (imines) described in these references are claimed herein. P.E. Figgins, et al., J. Am. Chem. Soc., Vol. 82, p. 820-824, and / or F. Lions, et al., J. Am. Chem. Soc., Vol. 79, p. 2733-2738 report the synthesis of certain 2,6-diacetylpyridinbis (imines) and certain iron and cobalt complexes of these tridentate ligands. The structures of the tridentate ligands reported in these references are different from those claimed herein, and all the iron and cobalt complexes contain 2 molecules of the 2,6-diacetylpyridinbis (imines). Japanese Patent Application No. 89-045,712 reports the compound T.W. Bell et al., J. Am. Chem. Soc., Vol. 113, p. 3115-3122 (1991) report the compound and Japanese Patent Application No. 02-078,663 reports the compound and an iron (II) complex of the latter compound in which two molecules of 2,6-diacetylpyridinbis (imine) are present in the complex. None of these complexes are claimed in the present.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to a first process for the polymerization of ethylene comprising, contacting, at a temperature of about -100 ° C to about + 200 ° C, a compound of the formula (ID with ethylene and; (a) a first compound, which is a neutral Lewis acid capable of subtracting a group X "and alkyl or a hydride group of M to form WX ~, (WR20)" or WH "and which is also capable of transferring an alkyl group or a hydride at M, with the proviso that WX ~ is a weakly coordinating anion, or (b) a combination of the second compound which is capable of transferring an alkyl or hydride group to M and a third compound the which is a neutral Lewis acid, which is capable of abstracting X ", a hydride or an alkyl group of M to form an anion of weak coordination; where: M is cobalt or iron; each X is an anion; n is 1, 2 or 3, so that the total number of negative charges on the anion or anions is equal to the oxidation state of a copper-or cobalt 4e atom present in (II); R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; and R20 is alkyl. Also described herein is a compound of the formula (II) where: M is copper or iron; each X is an anion; n is 1, 2 or 3, so that the total number of negative charges on the anion or anions is equal to the oxidation state of the Fe or Co atom present in (II); R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 is (X) R7 is (XI); R? and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together, can form a ring. This invention includes a compound of the formula (III) wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R8, R12, R13 and R17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the condition that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 which are adjacent to each other, taken together, can form a ring. This invention also relates to a second process for the polymerization of ethylene, which comprises contacting, at a temperature of about -100 ° C to about + 200 ° C, a complex of Co (II), Co (III), Faith { I I) or Fe (III) of a tridentate ligand of the formula (I) with ethylene, wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and R6 and R7 are aryl or substituted aryl; and with the proviso that an atom of Co (II), Co (III), Fe (II) or Fe (III.) Also have bound thereto an empty coordination site or a ligand that can be displaced by ethylene, and a ligand that can be added to ethylene. This invention also includes a compound of the formula (VII) :? x) where: M is Co or Fe; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; T1 is hydride or alkyl or any other anionic ligand into which ethylene can be inserted; And it 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 poly (ethylene) group of the formula - (CH 2 CH 2) X - wherein x is an integer of 1 or more; and T2 is an extreme group. The invention also relates to a third process for the polymerization of ethylene, comprising, contacting at a temperature of about -100 ° C to about + 200 ° C, ethylene and a compound of the formula (VII) (IX) where: M is Co or Fe; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and R6 and R7 are aryl or substituted aryl; T1 is hydride or alkyl or any other anionic ligand into which ethylene can be inserted; And it 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 poly (ethylene) group of the formula - (CH 2 CH 2) X - wherein x is an integer of 1 or more; and T2 is an extreme group.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 and 2 are two different views of the crystallographic structure of the X-rays of the compound made in Example 7.

DETAILS OF THE INVENTION In this, certain terms are used. Some of them are: • A "hydrocarbyl group" is a univalent group that contains only carbon and hydrogen. If not stated otherwise, it is preferred that the hydrocarbyl groups herein contain 1 to about 30 carbon atoms. • "Substituted hydrocarbyl" is herein meant a hydrocarbyl group which contains one or more substituent groups which are inert under the conditions of the process to which the compound containing these groups is subject. The substituent group does not substantially interfere with the process either. If not stated otherwise, it is preferred that the hydrocarbyl groups substituted therein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are the heteroaromatic rings. • By "functional group (inert)" is meant herein a different group of hydrocarbyl or substituted hydrocarbyl, which is inert under the conditions of the process to which the compound containing the group is subjected. The functional group also does not substantially interfere with any process described herein in which the compound in which they are present may take part. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as -OR18 wherein R18 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be close to a cobalt or iron atom, such as R4, R5, R8, R12, R13 and R17 the functional group should not coordinate to the metal atom more strongly than the groups in the compounds containing R4, R5, R8, R12, R13 and R17, which are shown to coordinate to the metal atom, ie, they must not displace the desired coordination group. • An "aluminum alkyl compound" is understood as a compound in which at least one alkyl group is attached to an aluminum atom. Other groups such as alkoxide, hydride and halogen, may also be attached to the aluminum atoms in the compound. • "Neutral Lewis base" means a compound, which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitriles. • "Cationic Lewis acid" means a cation that can act as an acid Lewis. Examples of such cations are sodium and silver cations. • By relatively non-coordinating anions (or weak coordination) we mean those anions as are generally referred to in the art in this way, and the ability to coordinate such anions, is known and has been discussed in the literature, see example W. BecJc., et al., Chem. Rev., vol. 88, p. 1405-1421 (1988), and S.H. Stares, Chem. Rev., vol. 93, p. 27-942 (1993), which are incorporated by reference herein. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X "including R193A1X", R192A1CIX ", R19A1C12X", and R19A10X wherein R19 is alkyl. Other useful non-coordination anions include BAF ". {BAF = tetrakis [3,5-bis (trifluoromethyl) phenyljborate.,., SbF6", PF6", and BFV, trifluoromethanesulfonate, p-toluenesulfonate, RfS02) 2N", and (C6F5) 4B ~. • an empty coordination site means a potential coordination site that does not have a ligand linked to it. In this way, if an ethylene molecule is in proximity to the empty coordination site, the ethylene molecule can be coordinated to the metal atom. • A ligand that can be added to ethylene is a ligand coordinated to a metal atom into which an ethylene molecule (or a coordinated ethylene molecule) can be inserted to begin or continue a polymerization. For example, this can take the form of the reaction (where L is a ligand): / CMICHI \ y Notice the similarity of the structure on the left side of this equation to the compound (IX) (see below). The compounds useful as ligands herein in iron and cobalt complexes are 2,6-pyridinedicarboxaldehyde diimines or 2,6-diacylpyridines of the general formula (iv; wherein R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl. (IV) can be elaborated by the reaction of a compound of the formula (SAW) with a compound of the formula H 2 NR 6, or H 2 NR 7, wherein R 1, R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, R 4 and R 5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl, R 4 and R 5 are each hydrocarbyl or substituted hydrocarbyl, and R6 and R7 are aryl or substituted aryl- These reactions are often catalyzed by carboxylic acids, such as formic acid. Reactions such as these are described in Examples 1-6. The preferred compounds of the formula (IV) and the compounds in which (IV) is a ligand, are those of the compound (III) [note that (III) is a subgroup of (IV)], whether present in the compounds such as (I), (II), (IV), (VII), (IX) and (XII). In (III), and therefore in (I), (II), (IV), (VII), (IX) and (XII) that conform to the formula of (III), it is preferred that: R1, R2 and R3 are hydrogen; and / or R1 and R3 are hydrogen and R2 is trifluoromethyl; and / or R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen, and it is more preferred that each of these is hydrogen; and / or R10, and R15 are methyl; and / or R8 and R13 are each independently halogen, phenyl or alkyl containing from 1 to 6 carbon atoms, and it is especially preferred that each R8 and R13 is alkyl containing 1 to 6 carbon atoms, and it is more preferred that R8 and R13 are i-propyl or t-butyl (but R8 and R12 or R13 and R17 can not be t-butyl in the same compound, R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each R12 and R17 is alkyl containing 1 to 6 carbon atoms, and it is more preferred that R12 and R17 are i-propyl, R4 and R5 are each independently halogen, thioalkyl, hydrogen or alkyl containing from 1 to 6 carbon atoms, and it is especially preferred that R4 and R5 are each independently hydrogen or methyl.Also in (III) and therefore in (I); (II); (VII), (IX) and (XII) that conform to formula (III), it is preferred that: R6 be (X); R 'be (XI); R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any of Re, R9, R10, R11, R12, R13, R14 R15, R16 and R17 which are neighbors to each other, taken together may form a ring. The specific compounds of (III) (and also in (I), (II), (IV), (VII), (IX) and (XII) are: R1, R2, R3, R9, R11, R14 and R16 are hydrogen, and R4, R5, R8, R10, R12, R13, R15 and R17 are methyl, R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R8 and R13 are chloro, and R4, R5, R12 and R17 are methyl, R1, R2, R3, R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are phenyl, R1, R2, R3 , R4, R5, R9 and R10, R11, R14, R15 and R16 are hydrogen, R8, R12, R13 and R17 are i-propyl, R1, R2, R3, R9, R10, R11, R14 R15 and R, 116"are hydrogen, R4 and R5 are methyl, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methylthio (CH3S-), and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14 R15 and R16 are hydrogen, R4 and R5 are 1-imidazolyl, and R8, R12, R13 and R17 are i-propyl; R1, R3, R9, R10, R11, R14 R15 and R16 are hydrogen, R4 and R5 are methyl, and R2 is trifluoromethyl, and R8, R12, R13 and R17 are i-propyl; and R1, R2, R3, R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are t-butyl. In the polymerization processes described herein, it can be observed from the results that it is preferred that there be at least some steric hindrance caused by the tridentate ligand around the cobalt or iron atom. Therefore, it is preferred that the groups near the metal atom be relatively large. It is relatively simple to control the steric hindrance if (III) is the tridentate ligand, since the control of the steric hindrance can be achieved simply by controlling the size of R8, R12, R13 and R16. These groups can also be part of the fused ring systems, such as 9-anthracenyl. In the first polymerization process, it is preferred that X be chloride, bromine and tetrafluoroborate. It is also preferred that M is FE (II), Fe (III), or Co (II). In the first polymerization process described herein, an iron or cobalt (II) complex is contacted with ethylene and a neutral Lewis acid W capable of abstracting X ", hydride or alkyl from (II) to form a anion of weak coordination, and must alkylate or be able to add a hydride ion to the metal atom, or an additional alkylating agent or an agent capable of adding a hydride anion to the metal atom must be present.The neutral Lewis acid is originally uncharged (eg, non-ionic.) Suitable neutral Lewis acids include SbF5, Ar3B (where Ar is aryl), and BF3, Suitable cationic Lewis acids or Bronsted acid include NaBAF, silver trifluoroethansulfonate, HBF, or [C6H5N (CH3) 2] + [B (C6F5) 4] ". In those cases in which (II) (and similar catalysts that require the presence of a Lewis acid or a Lewis or Bronsted cationic acid), it does not contain an alkyl or hydride group already attached to the metal atom, the Neutral Lewis or a cationic acid or Bronsted acid also alkylates or adds a hydride to the metal or a separate alkylation or hydrating agent, is present, for example, causes an alkyl group or a hydride to become bound to the metal atom. It is preferred that R20 contains from 1 to 4 carbon atoms, and it is more preferred that R20 is methyl or ethyl. For example, the aluminum alkyl compounds (see next paragraph) can be alkylated (II). However, not all aluminum alkyl compounds can be Lewis acids strong enough to abstract x- or an alkyl group from the metal atom. In that case, a separate Lewis acid, strong enough to perform the abstraction, must be present. For example, in Example 37, polymethylaluminoxane is used as the Lewis acid "only", it alkylates and performs the abstraction of the metal atom. In Examples 60 and 61 the triethylaluminum alkyls the metal atom, but it is not a Lewis acid strong enough to abstract an anion from the metal atom, so that another Lewis acid (stronger) was also added to the polymerization. B (C6F5) 3. Without the stronger Lewis acid B (C6F5) 3 present, the polymerization does not proceed. A preferred neutral Lewis acid, which can be alkylated to the metal, is a selected aluminum alkyl compound, such as R193A1, R19A1C12, R192A1C1, and "R19A10" (alkylaluoxanes), wherein R19 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable aluminum alkyl compounds include methylaluminoxane (which is an oligomer with the general formula [MeA10] "), (C2H5) 2A1C1, C2H5A1C12, and [(CH3) 2CHCH2] 3A1. Metal hydrides such as NaBH 4 can be used to link the hydride groups to the metal M. In the second polymerization process described herein, either a cobalt or iron (I) complex is added to the polymerization process, or Shape in if you in the process. In fact, more than one such complex can be formed during the course of the process, for example the formation of an initial complex and then the reaction of that complex to form a growing polymer containing such a complex.

Examples of such complexes that can be initially formed in si t u include (VII) and (XII) wherein R1 to R7 and M are as defined above, T1 is hydride or alkyl or any other anionic ligand into which ethylene can be inserted, and is a neutral ligand capable of being displaced by ethylene or a vacant coordination, the "parallel lines" are an ethylene molecule coordinated to the metal, and Q is an anion that is relatively uncoordinated. The complexes can be added directly to the process or formed in si t u. For example, (VII) can be formed between the reaction of (II) with a neutral Lewis acid such as an aluminum alkyl compound. Yet another method for the formation of the complex metal in itself is the addition of a suitable cobalt or iron compound such as cobalt (II) acetylacetonate (see Example 18), (I) and an aluminum alkyl compound. Other metal salts in which anions similar to acetylacetonate are present, and which can be removed by reaction with Lewis or Bronsted acid. For example, carboxylates (such as acetates) and metal halides can be used, particularly if they are slightly soluble in the process medium. It is preferred that these metal precursor salts are at least somewhat soluble in the process medium. After polymerization of the ethylene has been initiated, the complex may be in a form such as (ix) where R1 to R7, M and Q are as they are. defined above, and P is a divalent (poly) ethylene group of the formula - (CH2CH2) X- wherein x is an integer of 1 or more, and T2 is an end group, for example the groups listed for T1 above. Those skilled in the art will note that (IX) is essentially a polymer containing a so-called growing end. It is preferred that M be in an oxidation state +2 in (VII), (VIII) and (IX). The compounds such as (VII), (IX) and (XII) may or may not be stable away from an environment similar to that of the polymerization process, but these may be detected by nuclear magnetic spectroscopy (NMR), particularly one or both of 1 H and 13 C NMR, and particularly at lower temperatures. Such techniques, especially for polymerization "intermediates" of this type are known, see for example International Patent Application 96/23010, especially in Examples 197-203, which is incorporated by reference herein. (VII), (IX) and (XII) can 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. they may be the same as for the first and second polymerization process, and preferred conditions for those processes are also preferred for the third polymerization process. In all polymerization processes herein, the temperature at which the polymerization of the ethylene is carried out is from about -100 ° C to about + 200 ° C, preferably from about -60 ° C to about 150 ° C. , more preferably from about -50 ° C to about 100 ° C. The ethylene pressure at which the polymerization is carried out is not critical, the atmospheric pressure is about 275 MPa which is a suitable range. The polymerization processes herein can be run in the presence of various liquids, particularly of aprotic organic liquids. The catalyst system, ethylene, and polyethylene can be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene. Polymerizations of ethylene herein can also be initially carried out in the solid state (assuming (II), (III), (IV) or (VII) which is a solid), for example by the support of (II) , (III), (IV) or (VII) on a substrate such as silica or alumina, activating it with Lewis acid (such as W, for example an alkylaluminum compound) or of Bronsted and exposing it to ethylene. The support may also be able to take the place of the Lewis or Bronsted acid, for example, an acidic clay such as montmorillonite. Yet another method for making a supported catalyst is to start a polymerization or at least make an iron or cobalt complex of another olefin or oligomer, from an olefin such as cyclopentene on a support such as silica or alumina. These "heterogeneous" catalysts can be used to catalyze the polymerization in the gas phase or in the liquid phase. By gaseous phase it is understood that ethylene is transported to make contact with the catalyst particle, while ethylene is in the gas phase. Preparations of these types of heterogeneous catalysts are found in examples 43-46. In all the polymerization processes described herein oligomers and polymers of ethylene are prepared. These may be in the molecular weight range from the oligomeric olefins (see Example 32, which is mainly tens), to lower molecular weight polyethylene eras and oils, to higher molecular weight polyethylenes. A 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 average number of repeating units "monomers" in a polymer molecule.

In the examples, the given pressures are gauge pressures. The following abbreviations and terms are used: Branch - reported as the number of methyl groups per 1000 methylene groups in the polymer. Not corrected for extreme groups. This is determined by 1 H NMR.

Dispersion - the weight average molecular weight divided by the average molecular weight ΔMn) " DSC - differential explosion calorimetry FW - formula by weight GC - gas chromatography GPC - gel permeation chromatography ? H - heat of fusion (of polyethylene) Mn - molecular weight average in number MeOH - methanol PMAO - polymethylaluminoxane RT - room temperature THF - tetrahydrofuran Tm - melting point # of ~ R-en-di-.ili en-t-o - el -núme o -de m l-es polymerized ethylene per mole of cobalt or iron compound present. The structures were determined by X-ray crystallogue using a Rigaku RU300 instrument with an R-AXIS image plate detector using MoKa radiation. The structure was solved by direct methods (SHELXS or .MULTAN), using a least squares refinement of a complete matrix on F.

The analyzes of the metals of the heterogeneous catalysts were carried out by analysis of Atomic Absorption of Inductively Coupled Plasma (ICP).

In the examples, the apparatus for the polymerization run at approximately an ethylene pressure of 34.5 kPa., Was run in Schlenk tubes. In general, the metal complex (or the metal compound and the ligand) was dissolved or suspended in dry "solvent" under nitrogen. The capped flask was then brought to the desired reaction temperature, jet wash thoroughly with ethylene, placed under a pressure of about 34.5 kPa of ethylene and vigorously stirred. The other or the other catalyst components were then added and the polymerization was allowed to proceed.

Polymerizations run at higher pressures were performed in a 100 ml Parr® autoclave with agitation. The procedure was similar to that used in the Schlenk tubes (above).

Example 1 2,6-diacetylpyridinbis (2,4,6-trimethylphenyl imine) In a 200 ml round bottom flask, 5.0 g of 2,6-diacetylpyridine (FW 163.18, 0.036 mol) and 75 ml of methanol were placed. Then 8.28 g of 2,4,6-trimethylaniline (FW 135.21, 0.0612 mol) and three drops of formic acid were added and the solution was stirred at room temperature under nitrogen atmosphere for 16 hours, at which time precipitate was observed yellow. This was filtered and washed with cold methanol. 5.42 g (yield 44.5%) of a yellow solid was collected which was recrystallized from methanol with a minimum amount of methylene chloride to yield 4.10 g of the pure title compound. The filtrate was placed in the original flask and stirred for one day. More yellow precipitate appeared which was filtered and washed with cold methanol. 6.63 grams were collected (another yield of 29.8%). This material was recrystallized to yield 3.11 g of yellow crystals. X H NMR (ppm, CDC13): 2.2 (s, 12H), 2.25 (s, 6H), 2.3 (s, 6H), 6.9 (s, 4H), 7.9 (t, 1H), 8.5 (d, 2H).

Example 2 2,6-diacetylpyridinbis (2-chloro-6-methylphenylimine) In a 200 ml round bottom flask, 2.0 g of 2,6-diacetylpyridine (FW 163.18, 0.0122 mol) and 50 ml methanol were placed. Then, 3.45 g of 2-chloro-6-methylaniline (FW 141.60, 0.0245 mol) was added followed by three drops of formic acid and the solution was stirred at room temperature under nitrogen atmosphere for four days, at which time It did not form precipitate. The reaction was then heated to reflux for 24 h. GC analysis indicated that the reaction was incomplete. Heating to reflux was continued for a total of 1 week. The solvent was removed from the reaction mixture by rotary evaporation. Flash chromatography through a column of basic alumina (eluted with hexane / ethyl acetate 20: 1) led to the isolation of an oil. The oil was then crystallized from methanol / methylene chloride. 0.21 g (yield 4.2%) of pale yellow crystals were collected. 1K NMR (ppm, CDC13): 2.12 (s, 6H), 2.32 (s, 6H), 6.95 (t, 2H), 7.13 (d, 2H), 7.30 (d, 2H), 7.92 (t, 1H), 8.5 (d, 2H).

Example 3 2,6-diacetylpyridinbis (2-biphenylimine) Into a 100 ml round bottom flask, 0.48 g of 2,6-diacetylpyridine (FW 163.18, 0.00295 mole), 1.0 g of 2-aminobiphenyl (FW 169.23, 0.0059 mole) and 20 ml of methanol were placed. 3 drops of formic acid were added and the resulting solution was stirred under a nitrogen atmosphere. A precipitate formed after one day. This was filtered, washed with cold methanol and dried. 0.84 g (61% yield) of a pale yellow solid was collected. 1 E NMR (ppm, CDC13): 2.15 (s, 6H), 6.8 (d, 2H), 7.15-7.50 (m, 16H), 7.75 (t, 1H), 8.10 (d, 2H).

Example 4 2, 6-pyridinedicarboxaldehydebis (2,6-diisopropylphenylimine) Into a 35 ml round bottom flask, 0.28 g of 2,6-pyridinedicarboxaldehyde (FW 135.12, 0.00207 moles), 0.73 g of 2,6-diisopropylaniline (FW 177.29, 0.00414 moles), and 15 ml of methanol were placed. Three drops of formic acid were then added and the solution was stirred. A precipitate formed within 5 min. The agitation continued throughout the night. The solid was filtered, washed with cold methanol and dried. 0.86 g (yield 91.5%) of a pale yellow solid was collected. XH NMR (ppm, CDC13): 1.2 (d, 24H), 3.0 (m, 4H), 7.0-2.2 (m, 6H), 8.0 (t, 1H), 8.35 (s, 2H), 8.4 (d, 2H) ).

Example 5 2,6-diacetylpyridinbis (2,6-diisopropylphenylimine) In a 200 ml round bottom flask, 2.0 g of 2,6-diacetylpyridine (FW 163.18, 0.0122 mol) in 50 ml of methanol was placed. Then, 4.32 g of 2., 6-diisopropylaniline (FW 177.29, 0.0244 moles) and 3 drops of formic acid were added. The solution was stirred at room temperature overnight. The next morning a white precipitate formed. Stirring was continued for one more day before filtering the solid, washing with cold methanol and drying. 3.63 g (61.8% yield) of a pale yellow solid was collected. NMR revealed that the monoimine and diimine product were present. The solid was then placed in a flask with 200 ml of methanol and the methanol was brought to a boil. The solid was not soluble, so chloroform was added to the hot stirring mixture until the solid came into solution. An additional 4.50 g of 2,6-diisopropylaniline was then added and the solution was heated to 50 ° C. After a total of 7 days of heating, a precipitate formed which was filtered, washed with cold methanol and dried. 1.28 g of a yellow solid was collected. The additional heating produced 2.48 g of the pure title product.

X H NMR (ppm, CDCl 3): 1.2 (d, 24H), 2.28 (s, 6H), 2.8 (m, 4H), 7.05 - 7.25 (m, 6H), 7.92 (t, 1H), 8.5 (d, 2H) ).

Example 6 2,6-diacetylpyridinebis (2-tert-butylphenylimine) In a 200 ml round bottom flask, 2.0 g of 2,6-diacetylpyridine (FW 163.18, 0.0122 mol) was dissolved in 25 ml of methanol. Then 3.66 g of 2-tert-butylaniline (FW 149.24., 0.0245 mole) and 3 drops of formic acid were added. A precipitate began to form after 30 min. The solution was stirred at room temperature overnight. The precipitate was filtered, washed with cold methanol and then dried. 3.88 g (yield 75%) of a yellow solid were collected. The NMR revealed that the solid was mainly the monoimine product. The above solid (3.85 g, FW 294.4, 0.013 mol) was placed in a 200 ml flask. 1.95 g of 2-t-butylaniline, methanol, and 4 drops of formic acid were added. The mixture was refluxed before slowly adding chloroform until all the solids had dissolved. After 48 hours the volume was reduced and the reaction was cooled to precipitate more solids. These were isolated and recrystallized from methanol and a minimum amount of chloroform, yielding 2.8 g of product. XH NMR (ppm, CDC13): 1.4 (s, 18H), 2.4 (s, 6H), 6.55 (d, 2H), 7.1 (t, 2H), 7.2 (t, 2H), 7.45 (d, 2H), 7.9 (t, 1H), 8.4 (d, 2H).

Example 7 [2,6-diacetylpyridinebis (2,6-diisopropylphenylamine) dichloride [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.240 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-Diacetylpyridinbis (2,6-diisopropylphenylimine.) (0.893 g) was added and the solution turned dark and a brown precipitate formed. The mixture was stirred at room temperature for 3 days after which the solid product was filtered, washed with pentane and dried. Performance 1.02 g. X H NMR (ppm, CD2C12): d-84.1 (4, iPr-CH), -18.4 (12, iPr-CH3), -17.0 (12, iPr-CH3), -8.5 (2, Ar-Hp or pY- Hm), 4.5 (6, N = C (CH3)), 9.9 (4, Ar-Hm), 49.6 (1, Py-Hp), 116.5 (2, Ar-Hp or Py-Hm). The structure of the cobalt complex was determined by X-ray crystallography. The compound is triclinic, PS (No. 2), a = 9.786 (1), b = 20.741 (1), c = 8.673 (1) Angstroms, a = 91.69 (1), ß = 113.97 (1),? = 83.62 (1) °. Two views of this molecule are shown in Figures 1 and 2.

Example 8 [2,6-diacetylpyridinebis (2,6-diisopropylphenylimine) dichloride [iron (II)] In an oxygen-free, anhydrous atmosphere, FeCl 2 (anhydrous 0.100 g) was suspended in 10 ml of anhydrous tetrahydrofuran. 2,6-diacetylpyridinebis [2., 6-diisopropylphenimimine] (0.378 g) was added and the solution slowly turned dark and a blue precipitate formed. The mixture was stirred at room temperature for 3 days after which the product was filtered, washed with pentane and dried. Yield 0.489 g. 1 E NMR (ppm, CD2C12): d -36.3 (6, N = C (CH3)), -21.5 (4, iPr-CH), -10.3 (2, Ar-Hp or Py-Hm), -6.0 (12 , iPr-CH3), -5.1 (12, iPr-CH3), 14.6 (4, Ar-Hm), 79.1 (1, Py-Hp), 79.5 (2, Ar-Hp or Py-H) The structure of the complex Iron was determined by X-ray observation, and is similar to the cobalt complex made in example 8. The compound is triclinic, Pi (No. 2), a = 9,789 (2), b = 20,740 (5), c = 8.714 (1) Angstroms, a = 91.72 (2), ß = 114.14 IU_, = 83.25 (1) °.

Example 9 Tribromide of [2,6-diacetylpyridinbis (2,6-di-i-propylphenylimine)] iron (III) In an oxygen-free, anhydrous atmosphere, FeBR3 (anhydrous, 0.321 g) was suspended in 10 ml of anhydrous tetrahydrofuran. 2,6-diacetylpyridinbis (2,6-di-i-propylphenylimine) (0.340 g) was added and the solution slowly turned dark orange brown The mixture was stirred at room temperature for 3 days, after which the volume was reduced and pentane was added to the precipitate to precipitate the product, which was filtered, washed with pentane and dried, yield 0.620 g.

Example 10 [2,6-diacetylpyridinebis (2-chloro-6-methylphenylimine) dichloride [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.062 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-Diacetylpyridinebis (2-chloro-6-methylphenylimine) (0.205 g) was added and the solution turned green and a green precipitate formed. The mixture was stirred at room temperature for 2 days, after which the volume was reduced by half and pentane was added to precipitate the product, which was filtered, washed with pentane and dried. Yield 0.240 g.

Example 11 [2,6-diacetylpyridinbis (2,4,6-trimethylphenylimine) dichloride [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.140 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-Diacetylpyridinbis (2,4,6-trimethylphenylimine) (0.460 g) was added and the solution turned green and a green precipitate formed. The mixture was stirred at room temperature for 4 days, after which the product was filtered, washed with tetrahydrofuran, and then with pentane, dried. Yield 0.480 g.

Example 12 [2,6-diacetylpyridinebis (2-biphenylimine) jcobalt (II) dichloride In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.135 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-diacetylpyridinebis (2-biphenylimine) was added. { 0.500 gj and the solution darkened and a brown precipitate formed. The mixture was stirred at room temperature for 2 days, after which the volume was reduced and pentane was added. The product was filtered, washed with pentane and dried. Yield 0.500 g.

Example 13 [2,6-pyridinedicarboxaldehydebis (2,6-diisopropylphenylamine) dichloride [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.072 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-pyridinedicarboxaldehydebis (2,6-diisopropylphenylimine) (0.256 g) was added and the solution darkened and turned green. The mixture was stirred at room temperature for 4 days, after which the volume was reduced and pentane was added. The product was filtered, washed with benzene and pentane and dried. Yield 0.26 g.

Example 1 [2,6-diacetylpyridinebis (2-t-butylphenylimine) dichloride [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.168 g) was dissolved in a minimum of anhydrous tetrahydrofuran. 2,6-diacetylpyridinebis (2-t-butylphenylimine) (0.553 g) was added and the solution darkened and a brown precipitate formed rapidly. The mixture was stirred at room temperature overnight, after which pentane was added. The product was filtered, washed with pentane and dried. Yield = 0.66 g.

Example 15 [2,6-diacetylpyridinebis (2-t-butylphenylimine) dichloride [iron (II)] In an oxygen-free, anhydrous atmosphere, FeCl 2 (anhydrous, 0.085 g) was suspended in anhydrous tetrahydrofuran (10 ml). 2,6-Diacetylpyridinebis (2-tert-butylphenylimine) (0.285 g) was added and the solution darkened and a blue precipitate formed rapidly. The mixture was stirred at room temperature overnight, after which pentane was added. The product was filtered, washed with pentane and dried. Yield 0.30 g.

Example 16 Dibromide of [2,6-diacetylpyridinbis (2,6-diisopropylphenylimine) [cobalt (II)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.190 g) was suspended in anhydrous tetrahydrofuran (10 ml). 2,6-Diacetylpyridinbis (2,6-diisopropylphenylimine) (0.419 g) was added and the solution darkened to an olive green color and a precipitate formed. The mixture was stirred at room temperature overnight, after which the volume was reduced and pentanp was added. The solid product was filtered, washed with pentane and dried. Yield = 0.65 g.

Example 17 Bis (tetrafluoroborate) of [[2,6-diacetylpyridinbis (2,6-diisopropylphenylimine) [cobalt (II) bis (acetonitrile)] In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.848 g) was dissolved in 20 ml of anhydrous acetonitrile. AgBF4 (2.543 g) was added and the solution was stirred overnight. The solid AgCl was removed by filtration through Celite® and most of the acetonitrile was removed and diethyl ether was added. The solution was stirred and the ether decanted. This was repeated several times until a solid product remained. Yield 2.8 g. The cobalt salt prepared above (0.173 g) was dissolved in methylene chloride. 2,6-Diacetylpyridinbis (2,6-diisopropylphenylimine) (0.188 g) was added to give a light red solution. This was stirred for 2 days at room temperature after which the solvent was removed and pentane was added. The solid was filtered and washed 3 times with pentane and dried. Yield 0.271 g of a red / brown solid.

Example 18 In an oxygen-free, anhydrous atmosphere, Co (acac) 2 (0.03 mmol) was dissolved in 25 ml of anhydrous toluene. 2,6-Diacetylpyridinebis (2,6-diisopropylphenylimine) (0.045 mmol) was added and the solution placed under 34.5 kPa of ethylene at room temperature. PMAO (0.7 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution turned green and the temperature increased to approximately 60 ° C. The solid polymer precipitated quickly. The reaction was allowed to run for 16 hours, at which time the surface of the mixture had formed a solid polymeric lump, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 4.3 g of polyethylene. Productivity No.: 5109 mol CH2-CH2 / mol Co. Mn = 4294 (GPC, trichlorobenzene, 120 ° C, polyethylene standard). Tm (DSC) = 131.95 ° C,? H = 244.7 J / g.

Example 19 In an oxygen-free, anhydrous atmosphere the cobalt complex prepared in Example 17 (0.06 mmol) was dissolved in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened and the temperature increased. The solid polymer precipitated quickly. The mixture was stirred for 16 hours, at which time the reaction was terminated by addition of ethanol / 10% HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 1.85 g of polyethylene. Productivity No.: 1099 mol CH2-CH2 / mol Co. Mn = 4364 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 3.0. Tm (DSC) = 128.8 ° C,? H = 246.4 J / g.

Example 20 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 16 (0.06 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened and the temperature increased. The solid polymer precipitated quickly. The reaction was allowed to run for 16 hours, at which time the surface of the mixture had formed a solid polymeric lump, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 7.25 g of polyethylene. Productivity No .: 4307 mol. CH2 = CH2 / mol Co. Mn = 5094 (GPC, trichlorobenzene, 120 ° C, polyethylene standard) dispersity = 4.0. Tm (DSC) = 130.9 ° C,? H = 226 J / g.

Example 21 In an anhydrous oxygen-free atmosphere, the cobalt complex prepared in Example 14 (0.03 mmol) in 25 ml of anhydrous toluene was suspended and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened and the temperature increased. The solid polymer precipitated quickly. The reaction was allowed to run for 16 hours, at which time the surface of the mixture had formed a solid polymeric lump, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 5.46 g of polyethylene. Productivity No.: 6487 mol CH2 = CH2 / mol Co. Mn = 5031 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 6.2. Tm (DSC) = 132.0 ° C,? H = 252.7 J / g.

Example 22 In an anhydrous, oxygen-free atmosphere, the iron (II) complex prepared in Example 15 (0.03 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened and the temperature increased. The solid polymer precipitated quickly. The reaction was allowed to run for 17 hours, at which time the surface of the mixture had formed a solid polymeric lump, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 7.15 g of polyethylene. Productivity No.: 8495 mol CH2 = CH2 / mol Fe. Mn = 2028 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 73. Tm (DSC) = 131.3 ° C,? H = 226.1 J / g.

Example 23 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 7 (0.006 mmol) and 2,6-diacetylpyridinbis (2,6-diisopropylphenylimin) (0.006 mmol) in 50 ml of anhydrous toluene was suspended and the solution was suspended. placed under 172 kPa of ethylene at room temperature in a Parr® autoclave. PMAO (0.6 ml) (9.5% by weight, of Al in toluene, Akzo) was added with vigorous stirring. The temperature increased to a maximum of 43 ° C. The reaction mixture was stirred for 1 hour at constant pressure (172 kPa) after which the reaction was terminated by the addition of i-PrOH / 10% HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried.

Yield = 9.12 g of polyethylene. Do not give Productivity: 54181 mol CH2 = CH2 / mol Co. Mn = 7725 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 4.1. Tm (DSC) = 133.7 ° C,? H = 251.6 J / g. 24 In an anhydrous, oxygen-free atmosphere, the iron (II) complex prepared in Example 15 (0.01 mmol) was suspended in 40 ml of anhydrous toluene and the solution was placed under 138 kPa of ethylene at room temperature in a Parr® autoclave. . PMAO (0.7 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The temperature increased to a maximum of 56 ° C. The reaction mixture was stirred under constant pressure (131 kPa) for 19 minutes, at which time the reaction was terminated by the addition of 1 -P.rOE / ECl or 10% (15 ml) .. The polymeric product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 7.88 g of polyethylene. Productivity No.: 28088 mol CH2 = CH2 / mol Fe. .Mn = 3076. { GPC, trichlorobenzene ^ 120 ° C, polyethylene standard), dispersity = 31. Tm (DSC) = 132.2 ° C,? H = 233.9 J / g.

Example 25 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 7 (0.007 mmol) was suspended in 50 ml of anhydrous toluene and the solution was placed under 172 kPa of ethylene at room temperature in a Parr® autoclave. PMAO (0.6 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The temperature increased to a maximum of 43 ° C. The reaction mixture was stirred for 2 hours under constant pressure (172 kPa) after which the reaction was terminated by the addition of 10% i-RRQH y.HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 11.1 g of polyethylene. Productivity No.: 56523 mol CH2 = CH2 / mol Co. Mn = 7840 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 3.0. Tm (DSC) = 132.7 ° C,? H = 251.9 J / g.

Example 26 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 7 (0.016 mmol) was suspended in 50 ml of anhydrous toluene and the solution was placed under 689 kPa of ethylene at room temperature in a Parr® autoclave. PMAO (0.4 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The temperature was increased to a maximum of 75 ° C in 6 minutes, at which time the reaction was terminated by the addition of 10% i-PrOH / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 11.1 g of polyethylene. Productivity No.: 18963 mol CH2 = CH2 / mol Co. Mn = 4733 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.85. Tm (DSC) = 131.4 ° C,? H = 244.7 J / g.

Example 27 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 7 (0.06 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.6 ml) (9.5 wt% Al in toluene, Akzo.) Was added with vigorous stirring. The solution darkened and the temperature increased. Rapidly precipitated a solid polymer. The reaction was allowed to run for 17 hours, at which time the surface of the mixture had formed a lump of solid polymer, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 5.21 g of polyethylene. Productivity No.: 3095 mol CH2 = CH2 / mol Co. Mn = 10014 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersion = 4.6. Density (gradient tube) 0.974 ± 0.01%. Methyl and olefin ends (without branches) are visible in the 13 C NMR spectrum (trichlorobenzene, 120 ° C).

Example 28 In an anhydrous oxygen-free atmosphere, the iron (III) complex prepared in Example 9 (0.06 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.6 ml) (9.5% by weight of Al in toluene was added., Akzo) with vigorous agitation. The solution darkened and the temperature increased. The solid polymer precipitated quickly. The mixture was stirred for 17 hours, at which time the reaction was terminated by the addition of methanol / 10% HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 2.0 g of polyethylene. Productivity No.: 1188 mol CH2 = CH2 / mol of Fe. Mn = 2699. { GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 134.

Example 29 In an oxygen-free, anhydrous atmosphere, the iron (II) complex prepared in Example 8 (0.056 mmolj in 25 ml of anhydrous toluene was suspended and the solution was placed under 34.5 kPa of ethylene at room temperature) PMAO ( 0.7 ml) (9.5% by weight of Al in toluene, Akzo) with vigorous stirring The solution turned orange and then darkened, and after a short time of onset the temperature increased.The solid polymer precipitated rapidly. it was allowed to run for 16 hours, at which time the surface of the mixture had formed a lump of solid polymer, thus preventing further polymerization.The reaction was terminated by the addition of methanol / 10% HCl (15 ml) The polymer product was filtered, washed thoroughly with methanol and acetone and dried The yield was 4.56 g of polyethylene Productivity No .: 2902 mol CH2 = CH2 / mol CoMN = 1820 (GPC, trichlorobenzene, 120 ° C, standard of p olyethylene.)., dispersity = 98. Tm (DSC) = 130.6 ° C,? H = 229.0 J / g.

Example 30 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 10 (0.015 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at 0 ° C. PMAO (0.4 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened and the temperature increased. The solid polymer precipitated rapidly. The reaction was allowed to run for 17 hours, at which time the surface of the mixture had formed a lump of solid polymer, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 3.26 g of polyethylene. Do not give Productivity: 7746 mol CH2 = CH2 / mol Co. Mn = 420 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.1.

Example 31 In an anhydrous oxygen-free atmosphere, the cobalt complex prepared in Example 11 (0.06 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened, and the temperature increased. The solid polymer precipitated rapidly. The reaction was allowed to run for 17 hours, at which time the surface of the mixture had formed a lump of solid polymer, thereby preventing further polymerization. The reaction was terminated by the addition of 10% methanol / HCl (15 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 6.6 g of polyethylene. Productivity No.: 3921 mol CH2 = CH2 / mol Co. Mn = 697 (GPC trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.5.

Example 32 In an anhydrous oxygen-free atmosphere, the cobalt complex prepared in Example 12 (0.05 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The solution darkened, and the temperature increased. The solid polymer precipitated rapidly. The mixture was stirred for 17 hours, at which time the reaction was terminated by the addition of methanol / 10% HCl (15 ml). The yield was about 10 g of the oligomeric product. Productivity No.: 7129 mol CH2 = CH2 / mol Co. The oligomers are linear with decene as the major product. The oligomers are mainly linear internal olefins. Using 13C NMR (CDC13) and GC-MS it was found that the distribution of oligomers with 10 or more carbon atoms was as follows: 3-methylene olefin (1.2%), netylene 4+ olefin (0.8%), alpha- olefin (9.0%), trans-2-olefin (16.0%), cis-2-olefin (5.6%), trans-3-olefin (30.2%), ci = -3-olefin (6.5%), trans-4 -olefin (21.1%), the rest of olefins (9.3.%). Based on the gas chromatography analysis, the approximate weight distribution of the oligomers is: Cio - 63%; Ci2 - 25%; C14 - 9%; Cie - 3%. Based on the gas chromatography of the crude reaction mixture, there was also a significant amount of compounds of 8 carbon atoms (C8) present in the original product mixture.

Example 33 In an anhydrous, oxygen-free atmosphere, the cobalt complex prepared in Example 13 (0.06 mmol) was suspended in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo.) Was added with vigorous stirring. The solution darkened, and the reaction was allowed to run for 17 hours, at which time the surface of the mixture had formed a lump of solid polymer, thereby preventing further polymerization. The reaction was terminated by the addition of jae ± anol / HC1 at .10% (J.5 joal). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was 3.6 g of polyethylene. Productivity No.: 2138 mol CH2 = CH2 / mol Co. Mn = 766 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.4.

Example 34 In an oxygen-free, anhydrous atmosphere, the iron (II) complex prepared in Example 8 (0.01 mmol) was suspended in 70 ml of toluene, cooled to -12 ° C and placed under 34.5 kPa of ethylene. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. After several minutes the solid polymer was visible, and the stirring became erratic. The reaction was terminated after 120 minutes by addition of methanol / 10% HCl (20 mL). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. The yield was equal to 5.1 J. Productivity No.: 16832 mol CH2 = CH2 / mol Fe. The branching could not be detected from XH NMR. Mn = 433007 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.9. Tm (DSC) = 134.0 ° C,? H = 197.1 J / g.

Example 35 2,6-diacetyl-4-trifluoromethylpyridinbisj (2j-diisopropyl) phenylimine [ Into a 20 ml bottle, 0.247 g of 2,6-diacetyl-4-trifluoromethyl-pyridine were placed. { FW 232.19 0.00106 mol) and 5 ml of methanol. Then 0.440 g of 2,6-diisopropylaniline was added. { FW 177.29, 0.00248 mol). This reaction solution was stirred overnight. A precipitate formed and was filtered, washed with methanol and dried in vacuo. 0.17 g was collected. The filtrate was placed back into the original vial and stirred for a further 1 day. More precipitate formed and filtered, washed and dried. Another 0.16 g was collected. XH NMR (ppm, CDC13): 1.2 (multiplet, 24H), 2.85 (ultiplete, 4H), 7.1 - 7.25 (multiplet, 6H), 8.7 (singlet, 2H) Example 36 Chloride of (2,6-diacetyl-4-trifluoromethylpyridinbis. {(2,6-diisopropyl) phenylimin}.] Cobalt (II) In an oxygen-free, anhydrous atmosphere, CoCl2 (anhydrous, 0.040) was dissolved. g) in anhydrous tetrahydrofuran, 2,6-diacetyl-4-trifluoromethylpyridinebisf (2,6-diisopropyl) phenylimine] (0.170 g) was added and the solution turned brown / red.After stirring for 3 days, the volume of the The solution was reduced and pentane was added.The solid product was filtered, washed with pentane and dried.The yield was 0.166 g.

Example 37 In an anhydrous, oxygen-free atmosphere, the cobalt complex ill) prepared in Example 36 (0.03 mmol) was dissolved in 25 ml of anhydrous toluene and the solution was placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The reaction mixture turned blue / black and the temperature increased. The reaction was terminated after 16 hours, by the addition of 10% methanol / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 4.8 g. Productivity No.: 5703 mol CH2 = CH2 / mol Co. Mn = 17950 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 16.5. Tm (DSC) = 133.1 ° C. ? H = 226.0 J / g.

Example 38 N, N '-bisj (2j 6-diisopropylj phenyl) pyridin-2,6-dicarboxamide Within a box under a nitrogen atmosphere, 10.0 g of 2,6-pyridinebis (carbonyl chloride) were placed. { FW 204, 0.049 mol., Aldrich Chemical Co. , 97%) and 75 ml of anhydrous tetrahydrofuran in a 300 ml round bottom flask together with a large magnetic stir bar. The flask was sealed under a nitrogen atmosphere and taken out of the anhydrous box and then coupled to a nitrogen bubbler. Then 12.4 g of triethylamine (FW 101.21, 0.1225 mol) was added quickly. While stirring vigorously, 17.38 g of 2,6-diisopropylaniline (FW 177.29, 0.098 mol) was added via an addition funnel. During the addition a large exotherm occurred and a white precipitate formed immediately. The resulting mixture was stirred for 3 hours, then filtered through a frit to remove NeT3 »HCl, the precipitate. The filtrate was passed rapidly through a frit containing silica gel which was washed thoroughly with hot tetrahydrofuran. The filtrate was reduced in volume and placed inside the refrigerator for crystallization. The precipitate was isolated and dried in vacuo. 15.17 g of a white solid was collected. The remaining liquid was concentrated and cooled but no solids formed. The solvent was then removed and the remaining residue was collected in a minimum amount of methanol with a large hexane access and placed in the refrigerator for recrystallization. 13.91 g of a white solid was collected. The 1 H NMR analysis revealed that these products were pure with a THF molecule that co-crystallizes. XH NMR (ppm, CDC13): 1.22 (doublet, 24H), 3.15 (multiplet, 4H), 7.25 (doublet, 4H), 7.35 (triplet, 2H), 8.2 (triplet, 1H) 8.55. { doublet, 2H), 9.0 (singlet, broad, 2H).

Example 39 N, N'-bis [(2,6-diisopropyl) phenyl] pyridin-2, 6-bis (iminochloride) Within the anhydrous box under a nitrogen atmosphere, 13.91 g of the product of Example 40 (FW 485.7, 0.0286 moles) were placed into a 500 ml three-neck round bottom flask. Then, 300 ml of anhydrous toluene was added followed by 12.2 g of PC15 (FW 203.22, 0.0601 mol). The flask was sealed under a nitrogen atmosphere and brought out of the anhydrous box where a condenser and a nitrogen sparger were attached to one of the necks of the flask, and an adapter going to a KOH solution was coupled to another neck of the flask. flask. Nitrogen was slowly passed through the condenser and out through the adapter and bubbled through the KOH solution. The reaction was then heated to 80 ° C for 2 hours during which HCl was released from the reaction and neutralized in the basic solution. The reaction was then purified from the solvent and the remaining solid was recrystallized from tetrahydrofuran. 4.39 g of a yellow solid was collected. 1 H NMR confirmed that this was the pure product. 1E NMR (ppm, CDCl 3): 1.2 (multiplet, broad, 24H), 2.85 (multiplet, 4H), 7.22 (singlet, 6H), 8.1 (triplet, 1H), 8.55. { doublet., 2H).

Example 40 Pyridin-2,6-bisfN, N '- (2,6-diisopropylphenyl) carboxyimidothioate of S, S'-dimethyl In an oxygen-free, anhydrous atmosphere, the compound prepared in Example 39 was placed. (0.427 g) in tetrahydrofuran (10 ml) and added NaSMe (0.228 g). The mixture was heated at 60 ° C for 3 days, at which time the solids were removed by filtration and the filtrate was evaporated to dryness. The toluene was added and the solution was filtered and evaporated to dryness. The spectrum of H-NMR indicated that the reaction was complete. XH NMR (ppm, THF = d8): 1.05 (doublet, 12H), 1.1 (doublet, 12H), 2.3 (singlet, 6H), 2.9 (multiplet, 4H), 7.0 (triplet., 2H) ^ 7.1. { doublet, 4H) ^ 7.6 and 7.8 (broad, 3H).

Example 41 Pyridin-2,6-bis [N, N '(2,6-diisopropylphenyl) carboxymethothioatetocobalt (II) S, S'-dimethyl chloride In an oxygen-free, anhydrous atmosphere, C0Cl2 was dissolved. { anhydrous., 0.060 g) in anhydrous tetrahydrofuran. Pyridine-2,6-bis [N, N'- (2,6-diisopropylphenyl) carboxyidothioate] of S, S'-dimethyl (0.253 g, 2 eq.) Was added and the solution turned green. After stirring for 3 days a brown solid had precipitated from the solution. The volume of the solution was reduced and pentane was added. The solid product was filtered, washed with pentane and dried. Yield = 0.252 g.

Example 42 In an oxygen-free, anhydrous atmosphere, the cobalt complex was suspended. { ID prepared in Example 41 (0.03 mmol) in 25 ml of toluene and placed under 34.5 kPa of ethylene at room temperature. PMAO (0.8 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The reaction mixture turned blue / green and the temperature increased. The reaction was terminated after 16 hours by the addition of methanol / 10% HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 2.33 g. Productivity No.: 2768 mol CH2 = CH2 / mol Co.

Example 43 Within an anhydrous box under a nitrogen atmosphere, 36.0 mg of the cobalt compound prepared in Example 7 was weighed into a flask and toluene (115 ml) was added. The solution was stirred until the catalyst partially dissolved. MAO supported on silica (0.5 g, 14.3% by weight of Al, Grace Davison) was added to the flask and the solution was stirred for 20 minutes. The solids were filtered, washed with toluene until the washings were colorless and then washed twice with pentane. The product was dried under vacuum and stored in an anhydrous box freezer. 0.473 g of the solid was collected. This contained 13.0% aluminum and 0.52% cobalt. The above solid (160 mg) was suspended in 5 ml of cyclohexane and transferred to a 5 ml disposable syringe. The suspension was removed from the anhydrous box and added to 150 ml of 2, Anhydrous degassed 2,4-trimethylpentane in a 600 ml Parr® reactor under a nitrogen atmosphere. The reactor was sealed, the stirring was started and then heated to 35 ° C and pressurized with ethylene at 1.0 MPa. After 30 minutes the pressure was released and the reaction was quenched with methanol. The polymer was removed, filtered, washed with methanol and then with acetone, and dried. 2.55 g of polyethylene were collected. Tm (DSC, 10 ° C / min, N2) = 134.8 ° C,? H = 182.7 J / g. # of Productivity = 8263.

Example 44 Within an anhydrous box under a nitrogen atmosphere, 36.0 mg of the iron compound prepared in Example 8 was weighed into a flask and (15 ml) of toluene was added. The solution was stirred until the catalyst partially dissolved. It was added to the MAO bottle supported on silica (0.5 g, 14.3% by weight of Al, Grace Davison) and the solution was stirred * for 20 minutes. The solids were filtered, washed with toluene until the washings were colorless and then washed twice with pentane. The product was dried under vacuum and stored in an anhydrous box freezer. 0.502 g of the solid was collected. This contained 13.5% aluminum and 0.40% Fe. The previous solid (160 mg) was suspended in ml of cyclohexane and transferred to a 5 ml disposable syringe. The suspension was removed from the anhydrous box and added to 150 ml of anhydrous degassed 2, 4-trimethylpentane in a 600 ml Parr® reactor under a nitrogen atmosphere. The reactor was sealed, the stirring was started and then heated to 35 ° C and pressurized with ethylene at 1.0 MPa. After 30 minutes, the pressure was released and the reaction was quenched with methanol. The polymer was removed, filtered, washed with methanol and then with acetone, and dried. 1.1 g of polyethylene was collected. Tm (DSC = 10 ° C / min, N2) = 135.6 ° C. # of Productivity = 2800.

Example 45 Within an anhydrous box under a nitrogen atmosphere, 36.0 mg of the cobalt compound prepared in Example 7 was weighed into a flask and (15 ml) of toluene was added. The solution was stirred until the catalyst partially dissolved. Anhydrous cyclopentane (10 eq, 0.046 ml) was added to the flask followed by MAO supported on silica (0.5 g, 14.3 wt% Al_, Grace Davison) and the solution was stirred for 10 minutes. The solids were filtered, washed with toluene until the washes were colorless and then washed twice with pentane. The product was dried under vacuum and stored in an anhydrous box freezer. 0.472 g of a purple solid was collected. This contained 14.5% aluminum and 0.07% Co. The above solid (160 mg) was suspended in 4 ml of cyclohexane and transferred to a 5 ml disposable syringe. The suspension was removed from the anhydrous box and added to 150 ml of degassed, anhydrous 2 ^, 2 ^ -trimethylpentane in a 600 ml Parr® reactor under a nitrogen atmosphere. The reactor was sealed, stirring was started and then heated to 35 ° C and pressurized with ethylene at 1.0.MPa. After 30 minutes, the pressure was released and the reaction was quenched with methanol. The polymer was removed, filtered, washed with methanol and then with acetone, and dried. 1.5 g of polyethylene was collected. Tm (DSC) = 10 ° C / min, N2) = 135.6 ° C,? H = 184.0 J / g. # of Productivity = 2814.

Example 46 Within an anhydrous box under a nitrogen atmosphere, 36.0 mg of the cobalt compound prepared in Example 7 was weighed into a bottle, and added. { 15 ml) of toluene. The solution was stirred until the catalyst partially dissolved. Then 0.6 ml of PMAO-IP (Akzo, 12.9% Al in toluene, an "improved" grade of PMAO whose solution is clear) were added and the solution was stirred for 1 minute. Dehydrated silica (0.5 g, XPO-2402, Grace Davison) was added to the flask and the solution was stirred for an additional 10 minutes. The solids were filtered, washed with toluene until the washings were colorless and then washed twice with pentane. The product was dried under vacuum and stored in an anhydrous box freezer. 0.660 g of the solid was collected. It contained 9.16% aluminum and 0.36% Co. The above solid (160 mg) was suspended in 4 ml of cyclohexane and transferred to a 5 ml disposable syringe. The suspension was removed from the anhydrous box and added to 150 ml of degassed, anhydrous 2, 2, 4-trimethylpentane in a 600 ml Parr® reactor under a nitrogen atmosphere. The reactor was sealed, stirring was started and then heated to 35 ° C and pressurized with ethylene at 1.0 MPa. After 30 minutes, the pressure was released and the reaction was quenched with methanol. The polymer was removed, filtered, washed with methanol and then with acetone, and dried. 2.06 g of polyethylene were collected. Tm (DSC) * 10 ° C / min, N2) = 137.4 ° C,? H = 184.0 J / g. # of Productivity = 7516.

Example 47 The cobalt complex prepared in Example 7 (3.3 mg) was weighed into a flask and dissolved in anhydrous dichloromethane (5 ml). PMAO (4.4 ml, Akzo 9.5% by weight Al) was placed in 500 ml of anhydrous toluene and placed in a 1 L autoclave with stirring under nitrogen atmosphere at room temperature. The cobalt complex was added and at the same time the reactor was pressurized to 43 MPa with ethylene. The reaction was allowed to run for 2 minutes, during which time cold water was admitted to the internal cooling coils to control the internal temperature. After 4 minutes, the temperature had reached 38.7 ° C. The reaction was terminated by the addition of 10% methanol / HCl solution and the polymer was filtered from the solution, washed with methanol and finally with acetone and dried. Yield = 60.4 g. Mn = (GPC, trichlorobenzene, 120 ° C, polyethylene standard) = 8913, dispersity = 2.4. Tm (DSC) = 133.3 ° C. ? H = 226.8 J / g. Productivity No.: 445.508.

Example 48 The iron complex prepared in Example 8 (2.0 mg) was weighed into a flask and dissolved in anhydrous dichloromethane (5 ml). PMAO (3.4 ml, Akzo 9.5 wt% Al) was placed in 500 ml of anhydrous toluene and placed in a 1 L autoclave with stirring, under nitrogen atmosphere at room temperature. The cobalt complex was added and at the same time the reactor was pressurized to 39 MPa with ethylene. The reaction was allowed to run for 2 minutes with cooling with water, after which the temperature had increased to 94 ° C. The reaction was quenched by the addition of 10% methanol / HCl solution and the polymer was filtered from the solution, washed with methanol and finally with acetone and dried. Yield = 64.5 g. Mn =. { GPC, trichlorobenzene, 120 ° C, polyethylene standard) = 11979, dispersity = 3.7. Tm (DSC) = 133.1 ° C. ? H = 225.3 J / g. Productivity No.: 781,539.

Example 49 In an anhydrous, oxygen-free atmosphere, the cobalt (II) complex prepared in Example 7 (0.03 mmol.) Was dissolved in 25 ml of toluene and placed under 34.5 kPa of ethylene at room temperature. Et2AlCl (0.75 mL, 2M in hexane, Aldrich) was added with vigorous stirring. The reaction mixture turned green and finally blue / black, and the temperature increased. The reaction was terminated after 16 hours, by the addition of 10% methanol / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 1.5 g. Do not give Productivity: 1782 mmol CH2 = CH2 / mol Co. , Mn = 4350 (GPC, trichlorobenzene, 12"'° C, polyethylene standard), dispersity = 17.6.

Example 50 In an anhydrous oxygen-free atmosphere, the iron (II) complex prepared in Example 8 (0.0028 mmol) was suspended in 80 ml of toluene, cooled to -12 ° C and placed under 34.5 kPa of ethylene. PMAO (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. After several minutes the solid polymer was visible and the solution became erratic. The reaction was terminated after 180 minutes, at which time the stirring was stopped.

This was quenched by the addition of 10% methanol / HCl (20 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 6.61 g. Productivity No.: 84130 mmol CH2 = CH2 / mol Fe. No branching could be detected from 1H NMR. The methyl end groups (no branching) are detected in the 13 C NMR analysis. They are not extreme olefin. This indicates that the low Mn fraction present probably arises due to the chain transfer to Aluminum. Mn = 7458 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 73. Tm (DSC) = 133.6 ° C. ? H = 224.0 J / g.

Example 51 [2,6-Diacetyl-4-trifluoromethylpyridinbis Chloride. { (2,6-diisopropyl) phenylimino} iron (II) In an oxygen-free, anhydrous atmosphere, FeCl2 was dissolved. { anhydrous., 0.020 g) anhydrous tetrahydrofuran. 2,6-Diacetyl-4-trifluoromethylpyridinebisf (2,6-diisopropyl) phenylimine] (0.096 g) was added and the solution turned dark blue / green. After stirring for 3 days, the solvent was removed and the solids were taken up in anhydrous methylene chloride. The solution was filtered and the volume reduced and pentane added. The solid product was filtered, washed with pentane and dried. The yield was 0.085 g.

Example 52 In an anhydrous, oxygen-free atmosphere, the cobalt (II) complex prepared in Example 36 (0.0028 mmol) was suspended in 50 ml of anhydrous toluene, and the solution was placed under 700 kPa of ethylene at 45 ° C in a 100 ml stirred Parr ® autoclave. PMAO-IP (0.5 ml.) (12.8% by weight of Al in toluene, Akzo) was added with vigorous stirring. The temperature was increased to 55 ° C. The reaction mixture was stirred for 10 minutes at constant pressure (700 kPa) after which the reaction was terminated by the addition of methanol / 10% HCl (10 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 4.2 g of polyethylene .. Productivity No.: 53456 mmol CH2 = CH2 / mol Co.

Example 53 In an anhydrous, oxygen-free atmosphere, the iron (II) complex prepared in Example 51 (0.0015 mmol) was suspended in 50 ml of anhydrous toluene, and the solution was placed under 700 kPa of ethylene at 45 ° C in a 100 ml stirred Parr ® autoclave. PMAO-IP (0.5 ml) (12.8% by weight of Al in toluene, Akzo) was added with vigorous stirring. The temperature was increased to 60 ° C. The reaction mixture was stirred for 10 minutes under constant pressure (670 kPa) after which time the reaction was terminated by the addition of 10% methanol / HCl (10 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. 83 Yield = 5.0 g of polyethylene .. Productivity No.: .118793 mmol CH2 = CH2. / Mol Fe.

Example 54 In an oxygen-free, anhydrous atmosphere, the compliment of cobalt (II) prepared in Example 7 (0.008 mmol) in 50 ml of toluene was suspended, cooled to -12 ° C and placed under 34.5 kPa of ethylene. PMAO (0.2 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. After several minutes the solid polymer was visible. The reaction was finished after 23 minutes, at which time the stirring was stopped. This was quenched by the addition of 10% methanol / HCl (10 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 2.46 g .. Productivity No.: 10959 mmol CH2 = CH2 / mol Co. Mn = 41600 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 2.26. Tm (DSC) = 132.9 ° C,? H = 196.2 J / g.

Example 55 The cobalt (II) complex prepared in Example 7 (0.07 mmol) was dissolved in dichloroethane and Si02 (dehydrated at 500 ° C under nitrogen atmosphere) was added. The solution was stirred for 2 hours, after which the solids were filtered, washed thoroughly with DCE and dried. The product was a yellow powder. The ICP analysis:% Co = 0.32%,% Si = 41.8%. The supported cobalt complex prepared above (85 mg, 0.0046 mmol.) Was suspended in anhydrous pentane, and placed under 34.5 kPa of ethylene. PMAO (0.6 ml, 9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The temperature of the reaction mixture increased. After 16 hours, the reaction was quenched by the addition of 10% methanol / HCl (10 ml) and the polymer product was filtered, washed thoroughly with methanol and finally with acetone and dried. Yield = 1.8 g. Productivity No .: 13945 mmol CH2 = CH2 / mol Co. Tm (DSC) = 131.7 ° C. H = 178.6 J / g. 56 The cobalt (II) complex prepared in Example 7 (0.07 mmol) was dissolved in dichloroethane and Si02 (dehydrated at 500 ° C under nitrogen atmosphere) was added. The solution was stirred for 2 hours, after which the solvent was removed slowly in vacuo and the solids were dried. The product was a yellow / green powder. The ICP analysis:% Co = 0.33%,% Si = 37.3%. The supported cobalt complex prepared above (100 mg, 0.0056 mmol) was suspended in anhydrous pentane, and placed under 34.5 kPa of ethylene. PMAO (0.6 ml, 9.5 wt% Al in toluene, Akzo) was added with stirring. The temperature of the reaction mixture increased. After 16 hours, the reaction was quenched by the addition of 10% methanol / HCl (10 ml) and the polymer product was filtered, washed thoroughly with methanol and finally with acetone and dried. Yield = 1.62 g. Productivity No.: 10310 mmol CH2 = CH2 / mol Co. Tm (DSC) = 136.8 ° C. ? H = 193.1 J / g.

Example 57 In an oxygen-free, anhydrous atmosphere, the compound prepared in Example 39 (0.322 g) was placed in 10 ml of tetrahydrofuran and the sodium imidazole derivative (0.300 g) was added. The mixture was heated at 60 ° C for 10 days, at which time the solids were removed by filtration and the filtrate was evaporated to dryness. Pentane was added to the oily solid and the solution was allowed to stand overnight, after which the oil had solidified. The product was filtered, washed with pentane and dried, to give (xiii) Example 59 In an anhydrous, oxygen-free atmosphere, the iron (II) complex prepared in Example 58 (0.03 mmol) was suspended in 25 ml of toluene and placed under 34.5 kPa of ethylene at room temperature. PMAO (0.6 ml) (9.5 wt% Al in toluene, Akzo) was added with vigorous stirring. The reaction mixture turned red / brown and the temperature increased. The reaction was terminated after 16 hours (after which the solid lump of polymer had formed on the top of the flask) by the addition of 10% methanol / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 2.51 g .. Productivity No.: 2982 mmol CH2 = CH2 / mol Fe. Tm (DSC) = 131.5 ° C. H = 190.9 J / g.

Example 60 In an oxygen-free, anhydrous atmosphere, the cobalt (II) complex prepared in the Example 7 (0.03 mmol) in 25 ml of toluene and placed under 34.5 kPa of ethylene at room temperature. Example 58 In an oxygen-free, anhydrous atmosphere, FeCl 2 (anhydrous, 0.015 g) was dissolved in anhydrous tetrahydrofuran. The ligand prepared in Example 59 (0.060 g) was added and the solution turned yellow. After stirring for 3 days a brown solid had precipitated from the solution. After 7 days the volume of the solution was reduced and pentane was added. The solid product was filtered, washed with pentane and dried. Yield = 0.046 g. of a solid beige of the formula (XIV) added B (C6F5) 3 (0.09 mmol in toluene) with vigorous stirring, no visible change occurred, AlEt3 (0.09 mmol in 3 ml of toluene) was added, the solution turned dark green, then blue / The reaction was terminated after 16 hours by the addition of 10% methanol / HCl (15 ml) The polymer product was filtered, washed thoroughly with methanol and acetone and dried. g .. Productivity No.: 4650 mol CH2 = CH2 / mol Co .. Mn = 7233 (GPC, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 3.3, Tm (DSC) = 135.3 ° C.? H = 240.5 J / g.

Example 61 In an anhydrous oxygen-free atmosphere, the cobalt (II) complex prepared in Example 7 (0.03 mmol) was suspended in 25 ml of toluene and placed under 34.5 kPa of ethylene at room temperature. AlEt3 (0.23 mmol in toluene) was added with vigorous stirring. The mixture changed to a dark purple solution. Then B (C6F5) 3 (0.09 mmol in toluene) was added. The reaction turned dark blue. The reaction was terminated after 16 hours, by the addition of 10% methanol / HCl (15 ml). The polymer product was filtered, washed thoroughly with methanol and acetone and dried. Yield = 6.4 g .. Productivity No.: 7557 mmol CH2 = CH2. / Mol Co. .Mn = 6777 (GP.C, trichlorobenzene, 120 ° C, polyethylene standard), dispersity = 3.4, Tm (DSC) = 134.3 ° C. ? H «235.3 J / g.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (51)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A process for the polymerization of ethylene, characterized in that it comprises, contacting, at a temperature of about -100 ° C to about + 200 ° C, a compound of the formula (II with ethylene and: (a) a first compound W, which is a neutral Lewis acid capable of subtracting a group X ~ and alkyl or a hydride group of M to form WX ", WR20 or WH and which is also capable of transferring an alkyl group or a hydride to M., with the proviso that WX "is an anion of weak coordination; or (b) a combination of a 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 a group alkyl of M to form an anion of weak coordination, where: M is cobalt or iron, each X is an anion, n is 1, 2 or 3, so that the total number of negative charges on the anion or anions is equal to the oxidation state of an iron or cobalt atom present in (II): R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group, or substituted hydrocarbyl, R6 and R7 are aryl or substituted aryl, and R20 is alkyl.

2. A process for the polymerization of ethylene, characterized in that it comprises contacting, at a temperature of about -100 ° C to about + 200 ° C, a complex of Co (II), Co (III), Fe (II) or Fe (III) of a tridentate ligand of the formula (I) with ethylene, wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and R6 and R7 are aryl or substituted aryl; and with the proviso that an atom of Co (II), Co (III), Fe (II) or Fe (III) also has bound thereto an empty coordination site or a ligand that can be displaced by ethylene, and a ligand that can be added to ethylene.

3. The process according to claim 1 or 2., characterized in that: R6 is (X); R7 is (XD; R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together may form a ring.

4. The process according to claim 3, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing from 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing from 1 to 6 carbon atoms; R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R 4 and R 5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms.

5. The process according to claim 4, characterized in that R9, R10, R11, R14, R15 and R16 are each hydrogen.

6. The process according to claim 4, characterized in that R8, R1 (R13 and R17 are each alkyl containing from 1 to 6 carbon atoms.

7. The process according to claim 4, characterized in that R4 and R5 are each hydrogen or methyl.

8. The process according to claim 4, characterized in that: R1, R2, R3, R9, R11, R14 and R16 are hydrogen, and R \ R5, R8, R10, R12, R13, R15 and R17 are methyl; R1, R: R; R9, R10, R11, R14, R15 and R are hydrogen, R8 and R13 are chloro, and R, 4q, D R53, R tj122 and R, 117 'are methyl; pl p2 3 p4 p5 9 plO pl pl2 p14 pl5 Rib and R, 117 'are hydrogen, and R 8β, T5l3 RXJ and R, 17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methylthio, and R8, R12, R13 and R17 are i-propyl; R1, R2, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are 1-imidazolyl, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methyl, and R8, R12, R13 and R17 are i-propyl; or R1, R2, R3, R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are t-butyl.

9. The process according to claim 4, characterized in that X is chloride, bromide or tetraf luoroborate.

10. The process according to claim 4, characterized in that the neutral Lewis acid is an aluminum alkyl compound.

11. The process according to claim 10, characterized in that the aluminum alkyl compound is polymethylaluminoxane.

12. The process according to claim 4, characterized in that the temperature is from about -50 ° C to about 100 ° C.

13. The process according to claim 1 or 2, characterized in that a pressure of ethylene is from about atmospheric pressure to about 275 MPa.

14. The process according to claim 1 or 2, characterized in that the polyethylene is produced with an average DP of 40 or more.

15. The compound of the formula (III) wherein: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R8, R12, R13 and R17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional inert group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together may form a ring.

16. The compound according to claim 15, characterized in that R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing from 1 to 6 carbon atoms, or hydrogen; R8, R12, R13 and R17 are each independently halogen, phenyl or alkyl containing from 1 to 6 carbon atoms; R 4 and R 5 are each independently hydrogen or alkyl containing 1 6 carbon atoms.

17. The compound according to claim 16, characterized in that R 10, R 11, R 12, R 14, R 15 and R 16 are each hydrogen.

18. The process according to claim 16 or 17, characterized in that R8, R12, R13 and R17 are each alkyl containing from 1 to 6 carbon atoms.

19. The compound according to claim 16, characterized in that R4 and R5 are each hydrogen or methyl.

20. The process according to claim 16, characterized in that: R1, R2, R3, R9, R10, R11, R14 and R16 are hydrogen, and R4, R5, R8, R10, R12, R13, R15 and R17 are methyl; R \ R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methylthio, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are 1-imidazolyl, and R8, R12, R13 and R17 are i-propyl; R \ R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R8 and R13 are chloro, and R4, R5, R12 and R17 are methyl; or R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methyl, and R8, R12, R13 and R17 are i-propyl.

21. A compound of the formula d i) where: M is copper or iron; each X is an anion; n is 1, 2 or 3, so the number. total of negative charges on the anion or anions is equal to the oxidation state of the Iron or Cobalt atom present in (II); R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 is (X); R 'is (XI); R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or a functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together, can form a ring.

22. The compound according to claim 21, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing from 1 to 6 carbon atoms, or hydrogen; R8, R13, R12 and R17 are each independently halogen, phenyl, or alkyl containing from 1 to 6 carbon atoms; and R4 and R5 are each independently hydrogen or alkyl containing from 1 to 6 carbon atoms.

23. The compound according to claim 21 or 22, characterized in that R9, R10, R11, R14, R15 and R16 are each hydrogen.

24. The compound according to claim 21 or 22, characterized in that R8, R12, R13 and R17 are each alkyl containing from 1 to 6 carbon atoms.

25. The compound according to claim 24, characterized in that R4 and R5 are each hydrogen or methyl.

26. The compound according to claim 21, characterized in that: R1, R2, R3, R9, R11, R14 and R16 are hydrogen, and R4, R5, R8, R10, R12, R13, R15 and R17 are methyl; R1, R2, R3, R9, R10, R11, R14, R15, and R16 are hydrogen, R8 and R13 are chloro, and R4, R5, R12 and R17 are methyl; R1, R2, R3, R9, R10, R11, R12, R14, R15 R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are phenyl; R1, R2, R3, R4, R5, R9, R10, R11, R14, R15, and R16 are hydrogen, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methylthio, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11 R14, R15 and R16 are hydrogen, R4 and R5 are 1-imidazolyl, and R8, R12, R13 and R17 are i-propyl; R1, R2, R3, R9, R10, R11, R14, R15 and R16 are hydrogen, R4 and R5 are methyl, and R8, R12, R13 and R17 are i-propyl; or R2, R3, R9, R10, R11, R12, R14, R15, R16 and R17 are hydrogen, R4 and R5 are methyl, and R8 and R13 are t-butyl.

27. The process according to claim 1, characterized in that R20 contains from 1 to 4 carbon atoms.

28. A compound of the formula (VII) (XII). { IX) characterized in that: M is cobalt or iron; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; T1 is hydride or alkyl or any other anionic ligand into which ethylene can be inserted; And .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 (poly) ethylene group of the formula - (CH2CH2) X- wherein x is an integer of 1 or more; and T2 is an extreme group.

29. The compound according to claim 28, characterized in that: it is R7 is (XI); R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together, can form a ring.

30. The compound according to claim 29, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing from 1 to 6 carbon atoms; R12 and R17 is each independently halogen, phenyl, hydrogen, or alkyl containing from 1 to 6 carbon atoms; and R 4 and R 5 are each independently hydrogen or alkyl containing from 1 to 6 carbon atoms.

31. The compound according to claim 30, characterized in that R9, R10, R11, R14, R15 and R16 are each hydrogen.

32. A process for the polymerization of ethylene, characterized in that it comprises contacting, at a temperature of about -100 ° C to about + 200 ° C, ethylene and a compound of the formula (VII) [IX) where: M is cobalt or iron; R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; R6 and R7 are aryl or substituted aryl; T1 is hydride or alkyl or any other anionic ligand into which ethylene can be inserted; And it 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 (poly) ethylene group of the formula - (CH2CH2) X- wherein x is an integer of 1 or more; and T2 is an extreme group.

33. The process according to claim 32, characterized by the compound is (VII).

34. The process according to claim 32, characterized in that the compound is (IX).

35. The process according to claim 32, characterized in that the compound is (XII).

36. The process according to claim 32, characterized in that: Rb is (X) R7 is (XD; R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and with the proviso that any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 that are neighbors to each other, taken together, can form a ring.

37. The compound according to claim 36, characterized in that: R1, R2 and R3 are hydrogen; R9, R10, R11, R14, R15 and R16 are each independently halogen, alkyl containing from 1 to 6 carbon atoms, or hydrogen; R8 and R13 are each independently halogen, phenyl or alkyl containing from 1 to 6 carbon atoms; R12 and R17 are each independently halogen, phenyl, hydrogen, or alkyl containing from 1 to 6 carbon atoms; and R 4 and R 5 are each independently hydrogen or alkyl containing from 1 to 6 carbon atoms.

38. The compound according to claim 37, characterized in that R9, R10, R11, R14, R15 and R16 are each hydrogen.

39. The process according to claim 32, 33, 34 or 35, characterized by the temperature is from about -50 ° C to about 100 ° C.

40. The process according to claim 32, 33, 34 or 35, characterized in that a pressure of ethylene is from about atmospheric pressure to about 275 MPa.

41. The process according to claim 32, characterized in that polyethylene with an average DP of 40 or more is produced.

42. The compound according to claim 28, characterized in that it is (VII).

43. The compound according to claim 28, characterized in that it is (XII).

44. The compound according to claim 28, characterized in that it is (IX).

45. The process according to claim 1, characterized in that the compound is or becomes part of a heterogeneous catalyst on a solid support.

46. The process according to claim 45, characterized in that it is carried out in gas phase or liquid phase.

47. The process according to claim 2, characterized in that the complex is or becomes part of a heterogeneous catalyst on a solid support.

48. The process according to claim 47, characterized in that it is carried out in gas or liquid phase.

49. The process according to claim 32, characterized in that (VI), (IX) or (XII) is part of a heterogeneous catalyst on a solid support.

50. The process according to claim 49, characterized in that it is carried out in the gaseous or liquid phase.

51. The process according to claim 45, 47 or 49, characterized in that the solid support is silica or alumina.