MXPA00002263A - Polymerisation catalysts - Google Patents

Abstract

Catalyst systems useful for the polymerisation of 1-olefins are disclosed, which contain nitrogen-containing transition metal compounds comprising the skeletal unit depicted in Formula (B), wherein M is Fe[II], Fe[III], Ru[II], Ru[III]or Ru[IV];X represents an atom or group covalently or ionically bonded to the transition metal M;T is the oxidation state of the transition metal M and b is the valency of the atom or group X;R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl;R5 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.

Description

CATA POLYMERIZATION LIFTS FIELD OF THE INVENTION The present invention relates to polymerization catalysts based on transition metals and their use in the polymerization and copolymerization of olefins. STATE OF THE ART The use of certain transition metal compounds to polymerize 1-olefins, for example, ethylene, is a fact already well established in the state of the art. The use of Ziegler-Natta catalysts, for example, those catalysts produced by activation of titanium halides with organometallic compounds, such as triethylaluminum, is fundamental in many commercial processes for the production of polyolefins. During the last 20 or 30 years, technological advances have led to the development of Ziegler-Natta catalysts that have such high activities that can be produced directly, in commercial polymerization processes, polymers and copolymers containing very low concentrations of residual catalyst. The amounts of residual catalyst remaining in the polymer produced are so small that it is unnecessary to separate them for most commercial applications. Said processes can be carried out by polymerizing the monomers in gas phase or in solution or in suspension in a liquid hydrocarbon diluent. The polymerization of the monomers can be carried out in the gas phase (the "gas phase process"), for example by fluidizing, under the polymerization conditions, a bed comprising the target polyolefin powder and particles of the desired catalyst, using a stream of fluidizing gas comprising the gaseous monomer. In the so-called "solution process", the (co) polymerization is carried out by introducing the monomer into a solution or suspension of the catalyst in a liquid hydrocarbon diluent, under conditions of temperature and pressure such that the polyolefin produced is formed as a solution in the hydrocarbon diluent. In the "grouting process", the temperature, pressure and choice of eluent are such that the polymer produced is formed as a suspension in the liquid hydrocarbon diluent. These processes are generally carried out at relatively low pressures (for example, 10-50 bars) and at low temperatures (for example, 50-150 ° C). Commercial polyethylenes are produced on an industrial scale in a variety of different types and qualities. The homopolymerization of ethylene with catalysts based on transition metals leads to the production of so-called "high density" polyethylene grades. These polymers have a relatively high rigidity and are useful for the production of articles where inherent rigidity is required. The copolymerization of ethylene with higher 1-olefins (eg, butene, hexene or octene) is commercially employed to produce a wide variety of copolymers that differ in density and in terms of other important physical properties. Particularly important copolymers prepared by copolymerizing ethylene with higher 1-olefins using catalysts based on transition metals, are the copolymers having a density of 0.91 to 9.93. These copolymers which are generally referred to in the art as "linear low density polyethylene" are in many respects similar to the so-called "low density" polyethylene produced by polymerization of ethylene at high pressure and catalyzed by free radicals. Said polymers and copolymers are used extensively in the manufacture of flexible blown film. In recent years, the use of certain metallocene catalysts (eg, biscyclopentadienylzirconium chloride activated with alumoxane) has resulted in catalysts with potentially high activity. However, metallocene catalysts of this type suffer from various drawbacks, for example, a high sensitivity to impurities when used with monomers, diluents and gas streams commercially available process, the need to use large amounts of expensive alumoxanes to achieve high activity and difficulties in putting the catalyst on a suitable support. Patent application WO 98/27124, published on June 25, 1998, discloses that ethylene can be polymerized by contacting it with certain iron or cobalt complexes of 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis ( iminas) selected.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new catalyst suitable for polymerizing monomers, for example defines, and esplly for polymerizing ethylene by itself or for copolymerizing ethylene with higher 1-olefins. Another object of the invention is to provide an improved process for the polymerization of olefins, esplly of ethylene alone, or for copolymerization of ethylene with higher 1-olefins, to provide homopolymers and copolymers having controllable molecular weights. For example, using the catalysts of the present invention a wide variety of polyolefins can be prepared such as, for example, liquid polyolefins, oligomers, resinous or adherent polyolefins, solid polyolefins suitable for the manufacture of flexible film and solid polyolefins having a high rigidity. DESCRIPTION OF THE INVENTION The present invention provides a polymerization catalyst comprising: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Fe [j3], Fe [HI], Cop], Co [ITj, Co [m], Ru |?], Ru [m], Ru [TV], Mn | T | , Mn [H], Mn [HI] or Mn [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R! -R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Fe, Co, Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Fe, Co, Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are independently chosen between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents. MODALITIES OF THE INVENTION Thus, one embodiment of the present invention provides a polymerization catalyst comprising: (1) a nitrogenous transition metal compound comprising the skeletal unit shown in formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M is Fe [] TJ, FejTlTj, RU [JTJ, RU [JH] O Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and R5 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted bidrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. When any two or more of R * -R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more groups may be linked to form one or more cyclic substituents.

Another embodiment of the present invention provides a polymerization catalyst comprising: (1) a nitrogenous transition metal compound of formula Z; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula Z where M is Fe [II], Fe [m], Co [I], Co [H], Co [m], Mn [I], Mn [H], Mn [IH], Mn [IV] , Ru [II], Ru [DI] or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4. R6 and R19 to R28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the condition that at least one of R19, R, 20, R and R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q is part of a condensed ring polyaromatic system. In this particular aspect of the present invention, in the event that none of the ring systems P and Q are part of a polyaromatic ring system, it is preferable that at least one of R, 19 and R20 and at least one of R21 and R22 is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. In one embodiment of the present invention, R, R, 20 R 21 R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system. Taking into account the above conditions relating to R, R, R and R in the formula Z, the radicals R1 to R4, R6 and R19 to R28 in the compounds illustrated by the formulas B and Z of the present invention are preferably chosen, independently, between hydrogen and hydrocarbyl Ci to Cg, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl and n-octyl. In the formula B, the radicals R5 and R7 are preferably independently selected from alicyclic, heterocyclic or aromatic, substituted or unsubstituted groups, for example phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2-t- butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5-dichloro-2,6-diethylphenyl and 2,6-bis ( 2,6-dimethylphenyl) phenyl, cyclohexyl and pyridinyl. The ring systems P and Q in the formula Z are preferably independently 2,6-hydrocarbylphenyl or fused ring polyaromatic systems, for example, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl. Another embodiment of the present invention provides a polymerization catalyst comprising: (1) a nitrogenous transition metal compound of formula T; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula T where M is Fe [II], Fe [IJJ], Co [I], Co [II], Co [m], Mn [I], Mn [p], Mn [IH], Mn [IV], Ru [p], Ruflirj O RU [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4, R6 and R29 to R32 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. Another embodiment of the present invention provides a polymerization catalyst comprising: (1) a nitrogenous transition metal compound of formula W; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula W wherein X represents an atom or group covalently or ionically linked to the cobalt atom; T is the oxidation state of the cobalt atom and can be Co [I], Copl], Co [m], and b is the valence of the atom or group X; R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when two or more of RJ-R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. In the catalysts of the present invention, the transition metal M in the nitrogenous complex is preferably Fe (IT) or Co (II). Each of the nitrogen atoms N1, N2 and N3 is coordinated to the transition metal M by a "dative" bond, that is, a bond formed by donating a single pair of electrons from the nitrogen atom. The remaining bonds in each nitrogen atom are covalent bonds formed by the electron sharing between the nitrogen atoms and the organic ligand as shown in the formulas defined for the transition metal complexes illustrated above. The atom or group represented by X in the compounds of formulas B, Z, T and * W can be selected, for example, from halide, sulfate, nitrate, thiolate, thiocarboxylate, BF ", PFd", hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl. Examples of such atoms or groups are chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxide and benzoate.

Preferred examples of the atom or group X in the compounds of formula B, Z, T and W are halide, for example, chloride, bromide; hydride; hydrocarbyloxide, for example, methoxide, ethoxide, isopropoxide, phenoxide; carboxylate, for example, format, acetate, benzoate; hydrocarbyl, for example, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl; substituted hydrocarbyl; heterohydrocarbyl; tosylate; and triflate. Preferably, X is selected from halide, hydride and hydrocarbyl. In particular, chloride is preferred. The following are examples of nitrogenous transition metal complexes that can be used in the catalyst of the present invention: 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl 2 2,6-diacetylpyridine (2,6-diisopropylanil) MnCl 2 2,6-diacetylpyridine (2,6-diisopropylanil) CoCl2 2,6-diacetylpyridinebis (2-tert.-butylanil) FeCl2.6-diacetylpyridinebis (2,3-dimethylanil) FeCl2.6-diacetylpyridinebis (2-methylanil) FeCl 2 2,6-diacetylpyridinbis (2,4-dimethylanil) FeCl 2 2,6-diacetylpyridinbis (2,6-dimethylanil) FeCl 2 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 2,6-dialdiminpyridinbis (2, 6-dimethylanil) FeCl 2 2,6-dialdiminopyridinebis (2,6-diethylanil) FeCl 2 2,6-dialdiminopyridinebis (2,6-diisopropylanil) FeCl 2 2,6-dialdiminopyridinebis (1 -naphthyl) FeCl 2 and 2,6-bis (1 , 1-diphenylhydrazone) pyridine.FeCi2. A preferred complex of the present invention is 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2. The activating compound for the catalyst of the present invention is suitably chosen from organoaluminum compounds and hydrocarbylboro compounds.

Suitable organoaluminum compounds include trialkylaluminum compounds, for example, trimethylaluminum, triethylaluminum, tributylaluminum, tri-n-octylaluminum, ethylaluminum dichloride, diethylaluminum chloride, and alumoxanes. Alumoxanes are well known in the art usually as oligomeric compounds which can be prepared by the controlled addition of water to an aluminum alkyl compound, for example trimethylaluminium. Said compounds can be linear, cyclic or mixtures thereof. The commercially available alumoxanes are apparently generally mixtures of linear and cyclic compounds. The cyclic alumoxanes can be represented by the formula [R16AlO] s and the linear alumoxanes by the formula R17 (RI8AlO) s wherein s is a number from about 2 to 50 and wherein R16, R17 and R18 represent hydrocarbyl groups, preferably Ci to Ce alkyl groups, for example methyl, ethyl or butyl groups. Examples of suitable hydrocarbyl boron compounds are: dimethylphenylammonium tetra (phenyl) borate, triflyl tetra (phenyl) borate, triphenylboron, dimethylphenylammonium tetra (pentafluorophenyl) borate, tetrakis [(bis-3,5-trifluoromethyl) phenyl] borate sodium, FÍ + (OEt 2) [(bis-3,5-trifluoromethyl) phenyl] borate, tetra (pentafluorophenyl) borate of triphenyl and tris (pentafluorophenyl) boron. In the preparation of the catalysts of the present invention, the amount of activating compound selected from organoaluminum compounds and hydrocarbylboron compounds to be used, is easily determined by simple tests, for example, by the preparation of small test samples that can be used to polymerize small amounts of the monomer or monomers and thus determine the activity of the catalyst produced. In general, it has been found that the amount used must be sufficient to provide from 0.1 to 20,000 atoms, preferably from the 2,000 aluminum or boron atoms per metal atom Fe, Co, Mn or Ru in the compound of formula B, Z, T or W. In the compound of formula B of the present invention, M is preferably Fe [irj. In the compounds of formula Z or of formula T of the present invention, M is preferably Fe [JJ], Mn [U] or Co [p]. Another aspect of the present invention provides a polymerization catalyst system comprising (1) as the transition metal compound, a compound having the formula B, Z, T or W; (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds; and (3) a neutral Lewis base. In this other aspect of the present invention, the iron and cobalt compounds are preferred. The preferences regarding the activating compound are the same as those expressed above with respect to the catalysts of the present invention. The Lewis neutral bases are well known in polymerization technology with Ziegler-Natta catalysts. Examples of neutral Lewis base classes suitably used in the present invention are unsaturated hydrocarbons, for example, alkenes (other than 1-olefins) or alkynes, primary, secondary and tertiary amines, amides, phosphoramides, phosphines, phosphites, ethers, thioethers, nitriles, carbonyl compounds, for example esters, ketones, aldehydes, carbon monoxide and carbon dioxide, sulfoxides, sulfones and boroxines. Although 1-olefins are capable of acting as neutral Lewis bases, for the purposes of the present invention they are considered as monomeric or comonomeric 1-olefins and not as neutral Lewis bases per se. However, alkenes which are internal olefins, for example, 2-butene and cyclohexene, are considered as neutral Lewis bases in the present invention. Preferred Lewis bases are tertiary amines and aromatic esters, for example, dimethylaniline, diethylaniline, tributylamine, ethyl benzoate and benzyl benzoate. In this particular aspect of the present invention, the components (1), (2) and (3) of the catalyst system can be brought into contact with each other simultaneously or in any desired order. However, if the components (2) and (3) are compounds that strongly interact with each other, for example, forming a stable compound between them, it is preferable to put any of the components (1) and (2) in contact with each other. ) or of components (1) and (3) in an initial stage before introducing the defined final component. Preferably, the components (1) and (3) are brought into contact with each other before introducing the component (2). The amounts used of the components (1) and (2) in the preparation of the catalyst system are suitably as described above in relation to the catalysts of the present invention. The amount of the neutral Lewis base [component (3)] is preferably such as to provide a component (1): component (3) ratio of the order of 100: 1 to 1: 1000, more preferably 1: 1 to 1:20 The components (1), (2) and (3) of the catalyst system can be brought into contact with each other, for example, as the pure materials, as a suspension or as a solution of the materials in a suitable diluent or solvent ( example, a liquid hydrocarbon) or, if at least one of the components is volatile, using the vapor of said component. The components can be brought into contact with each other at any desired temperature. In general, the mixing of the components with one another at room temperature is satisfactory. If desired, heating can be carried out at higher temperatures, for example up to 120 ° C, for example, to achieve a better mixing of the components. It is preferable to contact components (1), (2) and (3) together in an inert atmosphere (for example, dry nitrogen) or in a vacuum. In case it is desirable to use the catalyst on a support material (see below), this can be achieved, for example, by previously forming the catalyst system comprising the components (1), (2) and (3) and impregnating the support material preferably with a solution thereof, or introducing one or more of the components simultaneously or sequentially into the support material. If desired, the support material itself may have the properties of a neutral Lewis base and may be used as or in place of component (3). An example of a support material having neutral Lewis base properties is poly (aminostyrene) or a styrene-amino-styrene copolymer (ie, vinylaniline).

The catalysts of the present invention may comprise, if desired, more than one of the transition metal compounds defined above. The catalyst may comprise, for example, a mixture of 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl 2 complex and 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 complex or a mixture of 2, 6-diacetylpyridine (2,6-diisopropylanyl) CoCl2 and 2,6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl2. In addition to said or said transition metal compounds as defined above, the catalysts of the present invention may also include one or more different types of transition metal compounds or catalysts, for example, transition metal compounds of the type used in the systems conventional Ziegler-Natta catalysts, catalysts based on metallocenes or chromium oxide catalysts supported and thermally activated (for example, Phillips-type catalysts). The catalysts of the present invention may be unsupported or supported on a support material, for example, silica, alumina or zirconia, or on a polymer or prepolymer, for example, polyethylene, polystyrene or poly (aminostyrene).

Thus, a preferred embodiment of the present invention provides a catalyst comprising: (1) a nitrogenated transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Fe [irj, Fe [Hrj, Co | TJ, Co [H], Co [rJTJ, RU [?], Ru [m], RU [TV], Mn [TJ, Mn [H, Mn [HI] or Mn [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when two or more of R,? -R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Fe, Co, Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R, R, R and R is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Fe, Co, Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are independently chosen between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4 R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents; - characterized in that the catalyst is supported on a support material. If desired, the catalysts can be formed in situ in the presence of the support material, or else the support material may be pre-impregnated or mixed, simultaneously or sequentially, with one or more of the catalyst components. If desired, the catalysts of the present invention can be supported on a heterogeneous catalyst, for example, a Ziegler-Natta catalyst supported on magnesium halide, a supported catalyst of the Phillips type (chromium oxide) or a supported metallocene catalyst. The formation of the supported catalyst can be achieved, for example, by treating the transition metal compounds of the present invention with alumoxane in a suitable inert diluent, for example a volatile hydrocarbon, by grinding a particulate support material with the product and evaporating the volatile diluent. The produced supported catalyst is preferably in the form of a free flowing powder. The amount of support material used can vary widely, for example, from 100,000 to 1 g per g of metal present in the transition metal compound. The present invention further provides a process for the polymerization and copolymerization of 1-olefins comprising contacting the monomeric olefin, under polymerization conditions, with the polymerization catalyst of the present invention. In the polymerization process of the present invention, the polymerization catalyst is preferably based on compounds of formula B, T, W or Z as described above. The polymerization conditions can be, for example, polymerization conditions in the solution phase, in the slurry phase or in the gas phase. If desired, the catalyst can be used to polymerize ethylene under high pressure / high temperature conditions in the process, wherein the polymeric material is formed as a supercritical ethylene melt. Preferably, the polymerization is carried out under the conditions of fluidized bed and gas phase. The slurry phase polymerization conditions or the gas phase polymerization conditions are particularly useful for the production of high density polyethylene grades. In these processes, the polymerization conditions can be discontinuous, continuous or semi-continuous process conditions. In the process in the slurry phase and in the gas phase process, the catalyst is generally fed to the polymerization zone in the form of a particulate solid. This solid can be, for example, an undiluted solid catalyst system, formed from a nitrogenous complex and an activator, or it can be the solid complex by itself. In this latter situation, the activator can be fed to the polymerization zone, for example, as a solution, separately from the solid complex or together with the latter. Preferably, the catalyst system or the transition metal complex component of the catalyst system, used in the slurry phase polymerization and in the gas phase polymerization, is supported on a support material. More preferably, the catalyst system is supported on a support material before its introduction into the polymerization zone. Suitable support materials are, for example, silica, alumina, zirconia, talc, kieselguhr or magnesia. The impregnation of the support material can be carried out by conventional techniques, for example, by forming a solution or suspension of the catalyst components in a suitable diluent or solvent and sandwiching the support material therewith. The carrier material thus impregnated with catalyst can then be separated from the diluent, for example by filtration or evaporation techniques. In the slurry polymerization process, the solid particles of catalyst, or supported catalyst, are fed to a polymerization zone either as a dry powder or as a slurry in the polymerization diluent. Preferably, the particles are fed to a polymerization zone as a suspension in the polymerization diluent. The polymerization zone can be, for example, an autoclave or similar reaction vessel, or a continuous loop reactor, for example of the type well known in the production of polyethylene by the Phillips Process. When the polymerization process of the present invention is carried out under slurry conditions, the polymerization is preferably carried out at a temperature above 0 ° C, more preferably above 15 ° C. The polymerization temperature is preferably maintained below the temperature at which the polymer begins to soften or sinter in the presence of the polymerization diluent. If the temperature is allowed to rise above this latter temperature, it can happen that the reactor becomes dirty. The adjustment of the polymerization within these defined temperature ranges can be a useful means for controlling the average molecular weight of the polymer produced. Another useful means for controlling molecular weight is to carry out the polymerization in the presence of hydrogen gas which acts as a chain transfer agent. In general, the higher the concentration of hydrogen used, the lower the average molecular weight of the polymer produced. The use of hydrogen gas as a means to control the average molecular weight of the polymer or copolymer is of general application to the polymerization process of the present invention. For example, hydrogen can be used to reduce the average molecular weight of the polymers or copolymers prepared using gas phase, slurry or solution phase polymerization conditions. The amount of hydrogen gas to be employed to provide the desired average molecular weight can be determined by simple "trial and error" polymerization tests. The polymerization process of the present invention provides polymers and copolymers, especially ethylene polymers, with remarkably high productivity (based on the amount of polymer or copolymer produced per unit weight of nitrogenous transition metal complex used in the catalyst system ). This means that relatively small amounts of transition metal complex are consumed in the commercial processes using the process of the present invention. It also means that when the polymerization process of the present invention is carried out under polymer recovery conditions that do not use a catalyst separation step, thus leaving the catalyst or residues thereof in the polymer (for example, as in most of commercial polymerization processes in slurry phase and gas phase), the amount of transition metal complex in the polymer produced can be very small. Experiments conducted with the catalyst of the present invention have shown that, for example, the polymerization of ethylene under slurry polymerization conditions can provide a particulate polyethylene product containing catalyst so diluted by the polyethylene produced that the concentration of metal The transition temperature is here, for example, to 1 ppm or less where "ppm" is defined as parts by weight of transition metal per million parts by weight of polymer. Thus, the polyethylene produced within a polymerization reactor by the process of the present invention can contain catalyst diluted with the polyethylene to a degree such that its transition metal content is, for example, 1-0,0001 ppm , preferably 1-0.001 ppm. Using a catalyst comprising a nitrogenous Fe complex according to the present invention, for example, in a slurry polymerization, it is possible to obtain polyethylene powder wherein the concentration of Fe is, for example, from 1.03 to 0.11 parts. in weight of Fe per million parts by weight of polyethylene.

Suitable monomers for use in the polymerization process of the present invention are, for example, ethylene, propylene, butene, hexene, methyl methacrylate, methylery acrylate, butyl acrylate, acrylonitrile, vinyl acetate and styrene. Preferred monomers for homopolymerization processes are ethylene and propylene. The catalyst can also be used for the copolymerization of ethylene with other 1-olefins such as propylene, 1-butene, 1-hexene, 4-methylpentene-1-and octene. Thus, the present invention further provides a process comprising contacting ethylene and one or more other 1-olefins with a catalyst comprising: (1) a nitrogenated transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B wherein M [T] is Fe [II], Fe [m], Co [I], Co [p], Co [m], Ru [II], Ru [DT], Ru [TV], Mn [I], Mn [U], Mn [III] or Mn [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R * -R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of Rx-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Fe, Co, Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R a R, 28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Fe, Co, Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are independently chosen between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents. The catalyst of the present invention can also be used for the copolymerization of ethylene with other monomeric materials, for example, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate and styrene. A preferred embodiment of the present invention comprises a process for the polymerization and copolymerization of 1-olefmas comprising contacting the monomeric olefin, under polymerization conditions, with a polymerization catalyst comprising: (1) a transition metal compound nitrogen that has the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B wherein M [T] is Fe [HJ, Fe [m], Co [TJ, Co [p], Co [ IH], Ru [II], Ru [TJTJ, Ru [IV], Mn [I], Mn [II], Mn [TII] or Mn [rV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R-R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Fe, Co, Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Fe, Co, Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are independently chosen between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents; - characterized in that the polymerization conditions are gas phase polymerization conditions. The methods for carrying out gas phase polymerization processes are well known in the art. Such methods generally comprise stirring (eg, by vibration or fluidization) a catalyst bed or a bed of the target polymer (ie, polymer having the same or similar physical properties as that desired to be produced in the polymerization process) that contains a catalyst, and feed thereto a monomer stream at least partially in the gas phase, under conditions such that at least part of the monomer polymerizes in contact with the bed catalyst. The bed is generally cooled by the addition of cold gas, (for example, recycled gaseous monomer) and / or volatile liquid (for example, an inert volatile hydrocarbon or gaseous monomer that has condensed to form a liquid). The polymer produced in, isolated from, the gas phase processes directly forms a solid in the polymerization zone and is free or substantially free of liquid. As is well known to those skilled in the art, in the event that any liquid in the polymerization zone of a gas phase polymerization process is allowed to enter, the amount of liquid will be small relative to the amount of polymer present. in the polymerization zone. This is in clear contrast to the processes in "solution phase" where the polymer forms dissolved in a solvent, and with the processes in "slurry phase" where the polymer is formed as a suspension in a liquid diluent. The gas phase process can be carried out in discontinuous, semi-continuous conditions or in the so-called "continuous" conditions. It is preferable to work under conditions such that the monomer is recycled continuously to a stirred polymerization zone containing polymerization catalyst, replacement monomer being provided to replace the polymerized monomer, and continuously or intermittently extracting the polymer produced from the polymerization zone at a rate comparable to the rate of formation of the polymer, new catalyst being added to the polymerization zone to replace the catalyst extracted from the polymerization zone with the polymer produced. In a preferred embodiment of the gas phase polymerization process of the present invention, the gas phase polymerization conditions are preferably fluidized bed and gas phase polymerization conditions.

Methods for performing fluidized bed and gas phase processes for the production of polyethylene and ethylene copolymers are well known in the art. The process can be done, for example, in a vertical cylindrical reactor equipped with a perforated distributor plate to support the bed and to distribute the incoming fluidizing gas stream through the bed. The fluidizing gas circulating through the bed serves to dissipate the polymerization heat of the bed and to supply monomer for the polymerization in the bed. Thus, the fluidizing gas generally comprises the monomer or monomers normally together with some inert gas (for example, nitrogen) and optionally with hydrogen as a molecular weight modifier. The hot fluidizing gas leaving the top of the bed is optionally conducted through a velocity reducing zone (this may be a cylindrical portion of the reactor having a wider diameter) and, if desired, a cyclone or filters , to separate fine solid particles from the gas stream. The hot gas is then fed to a heat exchanger to dissipate at least part of the polymerization heat. The catalyst is fed to the bed preferably continuously or at regular intervals. In the start-up of the process, the bed comprises a fluid-curable polymer which is preferably similar to the target polymer. The polymer is produced continuously within the bed by the polymerization of the monomer or monomers. Preferably, means are provided for discharging the polymer from the bed continuously or at regular intervals, to thereby maintain the fluidized bed at the desired height. The process is generally carried out at a relatively low pressure, for example, at 10-50 bar, and at temperatures comprised, for example, between 50 and 120 ° C. The temperature of the bed is maintained below the sintering temperature of the fluidized polymer to avoid problems of agglomeration. In the fluidized bed and gaseous phase process for the polymerization of olefins, the heat developed by the exothermic polymerization reaction is normally dissipated from the polymerization zone (ie, the fluidized bed) by means of the fluidizing gas stream as above. It has been described. The hot gas from the reactor leaving the top of the bed is conducted through one or more heat exchangers where the gas is cooled. The cooled gas from the reactor, together with any replacement gas, is then recycled to the base of the bed. In the fluidized bed and gas phase polymerization process of the present invention it is convenient to provide additional bed cooling (and thereby improve the space-time performance of the process) by feeding a volatile liquid to the bed under conditions such that the The liquid evaporates in the bed, thus absorbing more heat from the polymerization of the bed through the effect of the "latent heat of evaporation". When the hot recycle gas from the bed enters the heat exchanger, the volatile liquid can condense. In one embodiment of the present invention, the volatile liquid is separated from the recycle gas and reintroduced separately into the bed. Thus, for example, the volatile liquid can be separated and pulverized in the bed. In another embodiment of the present invention, the volatile liquid is recycled to the bed with the recycle gas. In this way, the volatile liquid can be condensed from the stream of fluidizing gas leaving the reactor and can be recycled to the bed with the recycle gas, or it can be separated from the recycle gas and sprayed back into the bed. The method of condensation of liquid in the recycle gas stream and the return of the gas and liquid mixture entrained to the bed is described in EP-A-0089691 and EP-A-0241947. It is preferable to re-introduce the condensed liquid into the bed separately from the recycle gas, using the process described in US Pat. No. 5,541,270, which is incorporated herein for reference purposes only. When the catalysts of the present invention are employed under gas phase polymerization conditions, the catalyst, or one or more of the components used to form the catalyst, can be introduced, for example, into the polymerization reaction zone in liquid form, for example, as a solution in an inert liquid diluent. Thus, for example, the transition metal component or the activating component, or both components, can be dissolved or slurried in a liquid diluent and fed into the polymerization zone. Under these circumstances, it is preferable that the liquid containing the component or components is sprayed in the form of fine droplets in the polymerization zone. The diameter of the droplets is preferably within the range of 1 to 1,000 microns. EP-A-0593083, which is incorporated herein by reference, describes a process for introducing a polymerization catalyst into a gas phase polymerization. The methods described in EP-A-0593083 can be suitably used, if desired, in the polymerization process of the present invention. The present invention also provides a novel nitrogenous transition metal compound comprising the skeletal unit illustrated in the formula Z: Formula Z wherein M is Fe [II], Ferpi], Cop], Co [rJJ, Co [m], Mn [I], Mn [lTJ, Mn [m], Mn [IV], Ru [ITJ, Ru [m] or Ru | TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4. R6 and R19 to R28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted bidrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the condition that at least one of R19, R, R and R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q is part of a condensed ring polyaromatic system. In this particular aspect of the present invention, in the event that none of the ring systems P and Q forms part of a polyaromatic ring system, it is preferable that at least one of R19 and R20 and at least one of R21 and R22 is chosen from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. In one embodiment of the present invention, R, R, R and R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system. Taking into account the above conditions relating to R19, R20, R21 and R22 in the formula Z, the radicals R1 to R4, R6 and R19 to R28 in the compounds illustrated by the formulas B and Z of the present invention are preferably chosen, independently, between hydrogen and hydrocarbyl Ci to Cg, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl and n-octyl. In the formula B, the radicals R5 and R7 are preferably independently selected from alicyclic, heterocyclic or aromatic, substituted or unsubstituted groups, for example phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2-t- butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5-dichloro-2,6-diethylphenyl and 2,6-bis ( 2,6-dimethylphenyl) phenyl, cyclohexyl and pyridinyl. The ring systems P and Q in the formula Z are preferably independently 2,6-hydrocarbyl phenyl or fused ring polyaromatic systems, for example 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl. According to yet another aspect of the present invention, a novel nitrogenous transition metal compound comprising the skeletal unit illustrated in the formula T is provided: Formula T where M is Fe [i ?, Fe [m], Co [rj, Co [p], Co [m], Mn [I], Mn [H], MnjTH], Mn [IV], Ru [H] , Ru [HTJ or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4, R6 and R29 to R32 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. Another aspect of the invention comprises the use of the compounds defined above as catalysts for the polymerization or copolymerization of 1-defines. Examples of the novel nitrogenous transition metal complexes of the present invention are given below: 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCi 2 2,6-diacetyl-iridin (2,6-diisopropylanil) MnCl 2 2.6 Diacetylpyridine (2,6-diisopropylanyl) CoCl2 2,6-diacetylpyridinebis (2-tert.-butylanil) FeCl2.6-diacetylpyridinebis (2,3-dimethylanil) FeCl2.6-diacetylpyridinebis (2-methylanil) FeCl2 2, 6-diacetylpyridinbis (2,4-dimethylanil) FeCl 2 2,6-diacetylpyridinbis (2,6-dimethylanil) FeCl 2 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 2,6-dialdiminopyridinebis (2,6-dimethylanil ) FeCl2 2,6-dialdiminpyridinbis (2,6-diethylanil) FeCi2 2,6-dialdiminpyridinbis (2,6-diisopropylanil) FeCl2 2,6-dialdiminpyridinbis (l-naphthyl) FeCl2 and 2,6-bis (l, l- diphenylhydrazone) pyridine.FeCl2. 2,6-diacetylpyridinebis (2,4,6-trimethylanil) FeCl 2 is preferred. The present invention further provides novel compounds useful for the preparation of polymerization catalysts comprising a compound having the following general formula E: Formula E wherein R10, Rp, R12 and R13 are independently selected from Ci to C20 hydrocarbon groups; and R14, R15 and all other ring substituents on the pyridine and benzene rings illustrated in formula E are independently selected from hydrogen and C1 to C20 hydrocarbon groups. The production of ligands for the preparation of the nitrogenous transition metal complexes used in the present invention is carried out through conventional organic chemistry syntheses. For example, ligands of the type illustrated, attached to the transition metal atom in formula B, can be prepared, for example, by reacting together a compound of 2,6-dicarboxaldehydepyridine or 2,6-diacyl-iridine, substituted or unsubstituted (i.e. having the appropriate substituents R1, R2, R3 and R6) with two molar equivalents of a diamine bearing the desired substituents R5 and R7. The present invention also provides novel compounds useful in the preparation of polymerization catalysts comprising a compound having the following general formula P: wherein R1 to R4, R6 and R29 to R32 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. Preferably, R29, R30, R31 and R32 are hydrocarbyl. More preferably, at least one of R29 and R30 and at least one of R31 and R32 are aryl groups, for example, phenyl, naphthyl or substituted phenyl. Ligands of the type shown in formula P can be prepared by well-known methods, for example, by reaction of a compound of 2,6-di (carboxaldehyde) pyridine or 2,6-diacylpyridine, unsubstituted or substituted (ie, has the appropriate substituents R1, R2, R3, R4 and R6) with two molar equivalents of a hydrazine compound bearing the desired substituents R29, R30, R31 and R32. Thus, ligands of the type illustrated, for example, in formulas B, Z, T, E and P, can be prepared in general by condensation reactions between bis (carbonyl) pyridine compounds and suitable amines or bidrazines. Said reactions can be catalyzed, for example, by acids, for example, acetic acid or toluene-p-sulfonic acid. During reactions of this type, it is usually advantageous to separate the water removed by the reaction of the carbonyl groups with the -NHa groups from the reaction zone. In the preparation of ligands using this type of reaction, it is preferable to remove the water by refluxing the reaction mixture with a water-immiscible, azeotrope-forming liquid, and then removing and removing the water from the distillate at a suitable reflux head, for example, in a Dean-Stark head. Suitable liquids for this purpose are, for example, hydrocarbons, especially aromatic hydrocarbons such as toluene or xylene. The present invention is illustrated by the following examples. EXAMPLES Example 1 shows the preparation of an iron compound (see the following formula D), Example 2 shows the preparation of a manganese compound (see the following formula J) and Example 3 shows the preparation of a cobalt compound (see formula K), for the preparation of the catalyst of the present invention. Experiments l.l to l.6, 2.1 to 3.1 and 3.2 illustrate the use of these compounds as catalysts in the polymerization of ethylene according to the catalyst and process of the present invention. In the Examples, all manipulations of the air / moisture sensitive materials were performed in a conventional vacuum / inert gas (nitrogen) line using the standard techniques of the Schlenk line or in a glove box with an inert atmosphere. Example 1 Intermediate A [2,6-diacetylpyridinebis (2,6-diisopropylanil)] was prepared by reaction of intermediate B [2,6-diacetylpyridine] and intermediate C [2,6-diisopropylaniline]. Intermediate A was then reacted with ferrous chloride in butanol to provide the compound of formula D. Preparation of Intermediate Compound A Using a procedure based on a related preparation (EC Alyea and PH Merrell, Synth React Inorg. Metal-Org. Chem., 1974, 4, 535), 2,6-diisopropylamine (3.46 ml, 18.4 mmol) was added dropwise to a solution of 2,6-diacetylpyridine (1.50 g, 9.2 mmol ) in absolute ethanol (25 ml) [the compounds 2,6-diisopropylaniline and 2,6-diacetylpyridine were supplied by Aldrich; the first one was distilled recently before use]. A few drops of glacial acetic acid were added and the solution was refluxed for 48 hours. Concentration of the solution at half volume and cooling to -78 ° C gave intermediate A as pale yellow crystals (80%). Calculated for C33KU3N3; C, 82.3; H, 8.9; N, 8.7; Found: C, 81.9; H, 8.5; 8.7%. FABMS: M + (481). 1H NMR (CDC13): 8.6-7.9 [m, 3H, C5H3N], 7.2-6.9 [m, 6FL C6 (CHMe2) H3], 2.73 [sept, 4H, CHMe2], 2.26 [s, 6TL C5H3N (CMeNAr) 2] and l, 16 [m, 24H, CHMe2]. FABMS is mass spectrometry by bombardment with fast atoms.

Intermediate B Intermediate C Intermediate A Formula D Preparation of the Compound of Formula D [2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl?] FeCl.sub.2 (0.24 g, 1.89 mmol) was dissolved in hot n-butanol (20 ml) at 80 ° C. A suspension of 2,6-diacetylpyrididinebis (2,6-diisopropylanil) (0.92 g, 1.89 mmol) in n-butanol was added dropwise at 80 ° C. The reaction mixture turned blue. After stirring at 80 ° C for 15 minutes, the reaction mixture was allowed to cool to room temperature. The volume of the reaction mixture was reduced to a few ml and petroleum ether (40/60) was added to precipitate the product (a blue powder), which was subsequently washed three times with 10 ml of petroleum ether (40 ml). / 60).

The yield was 0.93 g (81%). Mass spectrum: m / z 607 [M] +, 572 [M-C1] +, 482 [M-FeCl2] +. Analysis - Calculated for CssH ^ FeCb: C, 65.14; H, 7.12; N, 6.91. Found: C, 64.19; H, 6.90; N, 6.70. Experiments 1.1 to 1.6 - Polymerization Assays The polymerization assays described in Experiments 1.1 to 1.6 were conducted using the following procedure. The catalyst of formula D and cocatalyst (methylalumoxane - "MAO") were added to a Schlenk tube and dissolved in toluene (40 ml). The tube was purged with ethylene and the contents were mechanically stirred and maintained under a pressure of 1 bar of ethylene during the polymerization. After half an hour, the polymerization was terminated by the addition of aqueous hydrogen chloride. The solid polyethylene produced was separated by filtration, washed with methanol and dried in a vacuum oven at 50 ° C. In Experiment 1.1, some soluble polyethylene in toluene was recovered from the filtrate by separation of the toluene layer, drying over magnesium sulfate and evaporation of the solvent. The results of the polymerization tests are summarized in the following Table. From the Table it will be seen that the iron compound catalyst provided a high activity in the polymerization of ethylene using methylalumoxane as cocatalyst, but it can also be seen that the use of diethylaluminum chloride as cocatalyst (Experiment 1.4) gave poor activity. The use of a cocatalyst consisting of a perfluorophenylboro compound with triisobutylaluminum provided moderately high activity.

Notes in Table 1. MAO is methylalumoxane (cocatalyst). DEAC is diethylaluminum chloride. The units of "Quantity" are milliequivalents based on the aluminum atoms. The MAO was supplied by Aldrich except in Experiment 1.3 where the MAO was prepared according to the method provided by Gianetti, E .; Nicoletti, G.M .; Mazzocchi, R. Journal of Polymer Science: Part A; Polymer Chemistry 1985, 23, 2117-2133. 2. Recovered from the toluene reaction medium. 3. The activity is expressed as g mmol "1 h" 1 bar "1 (grams of polymer produced per millimole of catalyst per hour per bar of ethylene pressure) 4. In Experiment 1.5, the cocatalyst was provided by a milliequivalent of tris (perfluorophenyl) boron and 20 milliequivalents of triisobutylaluminum Example 2 The manganese compound [ü] illustrated in the following formula was prepared and tested for the catalytic activity in the polymerization of ethylene.

FORMULA J Preparation of Manganese Compound pT | of Formula J | "(2,6-diacetylpyridine (2,6-diisopropylanil) MnCl?] A suspension of MnCl2.4H2? (0.50 g, 2.53 mmol) and Intermediate A (1.22 g, 2.53 mmol ) was refluxed in acetonitrile (50 ml) for 12 hours to give an orange solution.After cooling to room temperature, orange crystals of the compound Mn (II) of formula J were obtained, yield 59%. of the microanalysis gave support to the empirical formula formula J. The FAB mass spectrum showed a higher peak corresponding to an M + -C1 (571) ion.

Polymerization Assay - Experiment 2.1 A 1.8 M solution of diethylaluminum chloride (DEAC) in toluene (0.50 ml, 0.9 mmol, 30 equivalents) was added via syringe to a stirred suspension of the compound of Mn. (II) of formula J (18 mg, 0.03 mmol) in toluene (40 ml). The obtained catalyst solution was degassed under reduced pressure and charged again with an ethylene atmosphere. During a time of the 20-hour experiment, the solution remained open to a supply of ethylene at one atmosphere and vigorously stirred at 25 ° C. The polymerization was terminated by the addition of dilute hydrochloric acid (approximately 40 ml) and then stirred for 30 minutes to dissolve the alkylaluminum residues. Solid polyethylene was removed from the reaction mixture by filtration, which was washed with an acid methanol solution and dried under vacuum at 40 ° C overnight. Yield: 0.011 g. The activity was 0.2 Example 3 Preparation of 2,6-diacetylpyridine (2,6-diisopropylane-CDoCl 7) - Formula k Cobalt chloride (COCl 2 - 0.057 g, 0.44 mmol) was dissolved in hot n-butanol (10 ml) at 80 ° C C. A suspension of Intermediate Compound [2,6-diacetylpyridinebis (2,6-diisopropylanil)] (0.21 g, 0.44 mmol) in n-butanol was added dropwise at 80 ° C. After stirring at 80 ° C for 15 minutes, the obtained reaction mixture was allowed to cool to room temperature, the volume of the reaction mixture was reduced to a few ml and petroleum ether (40/60) was added to precipitate the product. The powdery olive-green precipitate was washed three times with 10 ml aliquots of petroleum ether (40/60) The yield in the cobalt complex (formula K - see below) was 0.18 g ( 67% of the theory.) The mass spectrum showed m / z 575 [M-C1] +, 538 [M-2C1] +. Polymerization Tests - Experiments 3.1 and 3.2 Testing was carried out polymerization in the manner described in Example 1 except that the catalyst was the compound of formula K. The used MAO (supplied by Aldrich - Catalog No. 40,459-4) consisted of a 10 wt% solution in toluene. From the Table it can be seen that the catalyst of formula K, when activated with MAO, was highly active in the polymerization of ethylene.

Notes in the Table: 5. The units of "Quantity" are milliequivalents based on aluminum atoms. 6. The activity is expressed as g mmol "1 h" 1 bar "1 (grams of polymer produced per millimole of catalyst per hour per bar of ethylene pressure).

Examples 4 to 9 - Preparation of Iron Complexes Example 4 4.1 - Preparation of 2,6-diacetylpyridinbis (2-tert-butylanil) To a solution of 2,6-diacetylpyridine (0.54 g, 3.31 mmol) in absolute ethanol ( 20 ml) was added 2-tert-butylaniline (1.23 g, 2.5 equivalents). After the addition of two drops of acetic acid (glacial), the solution was refluxed overnight. After cooling to room temperature, the product crystallized from ethanol. The product was filtered, washed with cold ethanol and dried in a vacuum oven (50 ° C) overnight. The yield was 1.07 g (76%). 1HNMR analysis (CDC13): 8.43, 7.93, 7.44, 7.21, 7.09, 6.56 (m, 7H, ArH, pyrH), 2.43 (s, 6H, N = CCH3 ), 1.39 (s, 18H, CCH3). 4. 2 - Preparation of 2,6-diacetylpyridinbis (2-tert-butylanil) FeCl2. FeCl 2 (0.15 g, 1.18 mmol) was dissolved in hot n-butanol (20 ml) at 80 ° C. A suspension of 2,6-diacetylpyridinebis (2-tert-butylanil) (0.5 g, 1.18 mmol) in n-butanol was then added dropwise at 80 ° C. The reaction mixture turned blue. After stirring at 80 ° C for 15 minutes, the reaction mixture was allowed to cool to room temperature. The volume of the reaction mixture was reduced to a few ml and diethyl ether was added to precipitate the product as a blue powder, which was then washed three times with 10 ml of diethyl ether. The yield was 0.55 g (85%). Analysis - Mass spectrum: m / z 551 [M] +, 516 [M-C1] +, 426 [M-FeCl2] +. Example 5 5.1 - Preparation of 2,6-diacetylpyridinbis (2-methylanD) The procedure was as that of Example 4.1 except that 2-methylaniline was used in place of 2-tert-butylaniline The yield was 0, 42 g (33%). 1H MR (CDCl 3): 8.48 (d, 2H, pyrH), 7.91 (t, 1H, pyrH), 7.28 (m, 4H, ArH), 7.10 (m, 2H, ArH), 6.75 (m, 2H, ArH), 2.42 (s, 6H, N = CCH3), 2.20 (s, 6H, CH3). 5.2 - Preparation of 2,6-diacetylpyridinbis (2-methylanil) FeClg The procedure was as that of Example 4.2 except that 2,6-diacetylpyridinbis (2-methylanil) was used instead of 2,6-diacetylpyridinbis (2-tert-butylanil) . The yield was 77% of the theoretical. Mass spectrum: m / z 467 [M] +, 432 [M-C1] +. Example 6 6.1 - Preparation of 2,6-diacetylpyridinbis (2,3-dimethylanil) The procedure was as that of Example 4.1 except that 2,3-dimethylaniline was used in place of 2-tert-butylaniline. The yield was 80% of the theoretical. 1 H NMR (CDC13): 8.41, 7.89, 7.10, 6.94, 6.55, (m, 9H, ArH, pyrH), 2.33 (m, 6H, N = CCH3, 6H, CCH3), 2.05 (s, 6H, CCH3). Mass spectrum: m / z 369 [M] +. 6.2 - Preparation of 2,6-diacetylpyridinbis (2,3-dimethylanil) FeCl2 The procedure was as that of Example 4.2 except that 2,6-diacetylpyridinebis (2,3-dimethylanil) was used in place of 2,6-diacetylpyridinebis (2-tert-butyl). butylanil). The yield was 83% of the theoretical. Mass spectrum: m / z 496 [M] +, 461 [M-C1] +, 425 [M-C12] +. Example 7 7.1 - Preparation of 2,6-diacetylpyridinbis (2,4-dimethylanil) The procedure was as that of Example 4.1 except that 2,6-dimethylaniline was used in place of 2-tert-butylaniline. The yield was 75% of the theoretical. 1 H NMR (CDC13): 8.41, 7.90, 7.05, 6.90, 6.55, (m, 9H, ArH, pyrH), 2.36 (m, 6H, N = CCH3, 6H, CCH3), 2.13 (s, 6H, CCH3). Mass spectrum: m / z: 369 [M] +. 7.2 - Preparation of 2,6-diacetylpyridinbis (2,4-dimethylanil) FeCl 2 The procedure was as that of Example 4.2 except that 2,6-diacetylpyridinbis (2,4-dimethylanil) was used in place of 2,6-diacetylpyridinbis (2-tert-butyl). butylanil). The yield was 75% of the theoretical. Mass spectrum: m / z: 496 [M] +, 461 [M-C1] +, 425 PVI-C12] +. Example 8 8.1 - Preparation of 2,6-diacetylpyridinbis (2,6-dimethylanil) The procedure was as that of Example 4.1 except that 2,6-dimethylaniline was used in place of 2-tert-butylaniline. The yield was 78% of the theoretical. 1 H NMR (CDC13): 8.48, 8.13, 7.98, 7.08, 6.65, (m, 9H, ArH, pyrH), 2.25 (s, 6H, N = CCH3), 2 , 05 (m, 12H, CCH3). Mass spectrum: m / z: 369 [M] +. 8.2 - Preparation of 2,6-diacetylpyridinbis (2,6-dimethylanil) FeCl3 The procedure was as that of Example 4.2 except that it was used 2,6-diacetylpyridinbis (2,6-dimethylanil) in place of 2,6-diacetylpyridinbis (2-tert-butylanil). The yield was 78% of the theoretical. Mass spectrum: m / z: 496 [Mf, 461 [M-Cl, 425 [M-C12] +.

Example 9 9.1 - Preparation of 2,6-diacetylpyridinbis (2,4,6-trimethylanil) The procedure was as in Example 4.1 except that 2,4,6-trimethylaniline was used in place of 2-tert-butylaniline. The yield was 60% of the theoretical. 1HNMR (CDC13): 8.50, 7.95, 6.94, (m, 7H, ArH, pyrH), 2.33 (s, 6H, N = CH3), 2.28 (s, 6H, CCH3) 2.05 (s, 12H, CCH3). Mass spectrum: m / z: 397 [M] +. 9.2 - Preparation of 2,6-diacetylpyridinbis (2A6-trimethylaminoDFeCl?) The procedure was as that of Example 4.2 except that 2,6-diacetylpyridinbis (2,4,6-trimethylanil) was used in place of 2,6-diacetylpyridinbis (2-tert. -butylanil) The yield was 64% of theory The mass spectrum: m / z: 523 [M] +, 488 [M-C1] +, 453 [M-C12] + Examples 4 to 9 - Testing polymerization on iron complexes Polymerization tests were carried out using the following procedure: The catalysts (iron complexes) prepared in each of Examples 4 to 9 and cocatalyst (methylalumoxane- "MAO") were added to a Schlenk tube and were dissolved in toluene (40 ml) The "MAO" was used as a 10 wt% solution in toluene (supplied by Aldrich, catalog number: 40,459-4) The tube was purged with ethylene and the contents were mechanically stirred and it was kept under 1 bar of ethylene during the polymerization, the polymerization tests were started each of them s at room temperature (20 ° C). After half an hour, the polymerization was terminated by the addition of gaseous hydrogen chloride. The solid polyethylene produced was separated by filtration, washed with methanol and dried in a vacuum oven at 50 ° C. The toluene-soluble fraction (PE sol. Tol.) Was isolated from the filtrate by separating the toluene layer from the aqueous layer, drying over magnesium sulfate and removal of the toluene by distillation. The GC / MS analysis revealed that the toluene-soluble fraction consists of oligomeric products. The results of the polymerization tests are summarized in Table 3.

Analysis regarding solid polyethylene: Analysis regarding soluble polyethylene in toluene: Example 10 10.0 - Preparation of 2,6-pyridinedicarboxaldehyde 2.6-dimethanol pyridine (5.55 g, 0.040 mol - supplied by Aldrich Chemical Co.) and selenium dioxide (4.425 g, 0.040 mol, 1 equivalent) in 1,4-dioxane (100 ml) and refluxed (4 hours). The resulting mixture was filtered to obtain a clean orange solution. The solvent was removed under vacuum and the product was recrystallized from chloroform: petroleum ether (40/60 ° C) 1: 1 to obtain a white powder (7.44 g, 75%). Analysis - Mass spectrum (CI) 136 [M + H] +, 153 [M + NH 3] + 1 H NMR (250 Hz, CDC13) 10.17 (2H, s), 8.19 (2H, d, J = 8.4 Hz), 8.17 (ΔH, t, J = 8.4 Hz). 10.1 - Preparation of 2,6-dialdiminpyridinbis (2,6-dimethylanil) To 2,6-pyridinedicarboxaldehyde (0.80 g), 5.93 mmol) prepared as described above, in absolute ethanol (50 ml), 2.6 was added dimethylaniline redistilled (2.1 eq. 12.45 mmol, 1.5 ml) and glacial acetic acid (catalytic, 3 drops) and the resulting mixture was refluxed (24 hours). Cooling and recrystallization (absolute ethanol) provided a yellow powder (1.654 g, 82%). Analysis - Mass spectrum (CI) 342 [M + H] + 1 H NMR (250 Hz, CDC 13) 8.43 (2 H, s), 8.40 (2 H, d, J = 7.6 Hz), 8, 00 ÍH, t, 7.6 J), 7.10 (4H, d, J = 7.4 Hz), 6.99 (2H, t, J = 7.4 Hz), 2.20 (12 H, s) 13 C NMR (250 Hz, CDC 13) 163.17, 154.45, 150.26, 137.32, 128.16, 126.77, 124.39, 122.68, 18.31. 10.2 - Preparation of 2,6-dialdiminpyridinbis (2,6-dimethylanil) FeCl 3 To FeCk (0.127 g, 1.0 mmol) dissolved in hot dry n-butanol (40 ml) at 80 ° C, was added dropwise, at 80 ° C , a suspension of 2,6-dialdiminopyridinbis (2,6-dimethylanil) (0.341 g, 1.0 mmol, 1 eq) in hot dried n-butanol (10 ml). The reaction mixture turned green. After stirring for 15 minutes at 80 ° C, the mixture was allowed to cool to room temperature and red for a further 12 hours. The volume of reaction solvent was reduced to about 1 ml and the reaction mixture was washed with diethyl ether (3 x 40 ml) to obtain a light green powder (0.279 g, 60%). Mass spectrum (FAB +) m / z: 467 [M] +, 432 [M-C1] +. Example 11 11.1 - Preparation of 2,6-dialdiminpyridinbis (2,6-diethylanil) A 2,6-pyridinedicarboxaldehyde (0.169 g, 1.25 mmol) prepared as described in Example 10.0 above, in absolute ethanol (25 ml), was added 2,6-re-diled diethylaniline (2.1 eq, 2.63 mmol, 0.36 ml) and glacial acetic acid (catalytic, one drop). The resulting mixture was refluxed for 24 hours. Cooling and recrystallization (absolute ethanol) provided a yellow powder (0.371 g, 75%).

Analysis - Mass spectrum (CI) 398 [M + H] + 1 H NMR (250 Hz, CDC 13) 8.44 (2 H, s), 8.40 (2 H, d, J = 7.6 Hz), 8, 00 (1H, t, J = 7.6 Hz), 7.25 (6H, M), 2.55 (8H, q, J = 7.5 Hz), 1.61 (12H, t, J = 7.5 Hz). 11.2 - Preparation of 2,6-dialdiminpyridinbis (2,6-diethylamine) FeCl 2 To FeCk (0.076 g, 0.6 mmol) dissolved in hot dry n-butanol (40 ml) at 80 ° C, added dropwise to 80 ° C, a suspension of 2,6-dialdiminopyridinbis (2,6-diethylanil) (0.240 g, 0.6 mmol, 1 eq) in hot dry n-butanol (10 ml). The reaction mixture turned green. After stirring for 15 minutes at 80 ° C, the mixture was allowed to cool to room temperature and stirred for a further 12 hours. The volume of reaction solvent was reduced to about 1 ml and the reaction mixture was washed with diethyl ether (3 x 40 ml) to obtain a dark green powder (0.238 g, Analysis - Mass spectrum (FAB +) m / z: 523 [M] +, 488 [M-C1] +, 453 [M-C12] +, 398 [M-FeC12] +. Example 12 12.1 - Preparation of 2,6-dialdiminopyridinbis (2,6-diisopropylanil) A 2,6-pyridinedicarboxaldehyde (0.101 g, 0.75 mmol) prepared as described in Example 10.0 above, in absolute ethanol (20 ml ), redistilled 2,6-diisopropylaniline (2.1 eq, 1.57 mmol, 0.26 ml) and glacial acetic acid (catalytic, one drop) was added. The resulting mixture was refluxed for 24 hours. Cooling and recrystallization (absolute ethanol) provided a yellow powder (0.270 g, 80%). Analysis - Mass spectrum (Cl) 454 [M + H] + 1 H NMR (250 Hz, CDC 13) 8.44 (2 H, s), 8.40 (2 H, d, J = 7.6 Hz), 8, 00 (ÍH, t J = 7.6 Hz), 7.23 (6H, M), 3.01 (4H, sept, J = 6.9 Hz), 1.21 (24H, d, J = 6, 9 Hz). 13 C NMR (250 Hz, CDC13) 163.52, 162.69, 154.43, 148.30, 137.36, 137.14, 123.05, 122.76, 27.99, 23.44. 12. 2 - Preparation of 2,6-dialdiminpyridinbis (2,6-diisopropylanil FeCi2 A FeCl2 (0.070 g, 0.55 mmol) dissolved in hot dry n-butanol (40 ml) at 80 ° C, was added dropwise, at 80 ° C, a suspension of 2,6-dialdiminopyridinbis (2,6-diisopropylanil) (0.245 g, 0.55 mmol, 1 eq) in hot dried n-butanol (10 ml) The reaction mixture turned dark green. stirring for 15 minutes at 80 ° C, the mixture was allowed to cool to room temperature and stirred for a further 12 hours.The volume of reaction solvent was reduced to about 1 ml and the reaction mixture was washed with diethyl ether (3 x 40 ml) to obtain a dark green powder (0.205 g, 65%) Analysis - Mass spectrum (FAB +) m / z: 576 [M] +, 544 [M-C1] +, 454 rM-FeCl2] + Example 13 13.1 - Preparation of 2,6-dialdiminopyridinbis (l-naftip A 2,6-pyridinedicarboxaldehyde (0.658 g, 4.81 mmol) prepared as described in Example 10.0 above, in absolute ethanol (40 ml) , 1-ami was added nonaphthalene (2.1 eq, 10.10 mmol, 1.448 g) and glacial acetic acid (catalytic, one drop). The resulting mixture was refluxed for 24 hours. Cooling and recrystallization (absolute ethanol) provided a yellow powder (1.48 g, 80%). Analysis - Mass spectrum (El) 385 [M] + 13.2 - Preparation of 2,6-dialdiminpyridinbisp-naphthyl) FeCl 2 A FeCl 2 (0.20 g, 1.57 mmol) dissolved in hot dry n-butanol (80 ml) at 80 ° C, a suspension of 2,6-dialdiminopyridinbis (1-naphthyl) (0.610 g, 1.57 mmol, 1 eq) in hot dry n-butanol (25 ml) was added dropwise at 80 ° C. The reaction mixture turned green. After stirring for 15 minutes at 80 ° C, the mixture was allowed to cool to room temperature and stirred for a further 12 hours. The volume of reaction solvent was reduced to about 1 ml and the reaction mixture was washed with diethyl ether (3 x 40 ml) to obtain a green powder (0.57 g, 71%). Analysis - Mass spectrum (FAB +) m / z: 511 [M] +, 476 [M-C1] +, 441 [M-C12] +, 386 [M-FeCl2] +. Examples 10 to 13 - Polymerization Assays The iron complexes prepared in Examples 10 to 13 were tested in the polymerization of ethylene under the following standard conditions. To the iron complex (0, 01 mmol) dissolved in toluene (40 ml, dry) in a Schlenk tube, the cocatalyst (methylaluminoxane- [MAO]) (0.065 ml, 10 wt.% In toluene, 100 equivalents (Fe: Al = 1: 100) was added. )) to produce an orange solution. The Schlenk tube was placed in a water bath, purged with ethylene and the contents were magnetically stirred and kept under 1 bar of ethylene during the polymerization. After 30 minutes, the polymerization was terminated by the addition of aqueous hydrogen chloride. The solid, insoluble polyethylene was recovered by filtration, washed with methanol (50 ml) and dried (vacuum oven at 50 ° C). The toluene solution was dried over magnesium sulfate and the solvent was removed under vacuum to obtain traces of waxy material. The GC-MS of the toluene solution showed that the waxy material consisted of α-olefins (vinyl-terminated oligomeric hydrocarbons). The results of the polymerization tests are given in the following Table.

Notes in Table 1) MAO supplied by Aldrich Chemical Co. 2) Recovery from the reaction medium In Example 13, the molecular weight Mw of the soluble PE (polyethylene) was 300. Examples 14 to 25 These Examples are a series of tests wherein ethylene or ethylene / 1 -hexene was polymerized under a pressure of 10 bar of ethylene using the catalysts of the present invention under "slurry" polymerization conditions. Preparation of the catalyst The transition metal complexes used as a catalyst in Examples 14 to 25 were the following: In Examples 14 and 15, the complex was 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl 2 prepared as described in Example 1 (Compound of formula D). In Examples 16 to 20, the complex was 2,6-diacetylpyridinbis (2,6-dimethylanil) FeCl 2 prepared as described in Example 8. In Example 21, the complex was 2,6-diacetylpyridinbis (2,4 -dimethylanil) FeCl 2 prepared as described in Example 7. In Examples 22 to 24, the complex was 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 prepared as described in Example 9. In In Example 25, the complex was 2,6-diacetylpyridinbis (2,6-diisopropylanil) CoCl 2 prepared as described in Example 3 (formula K). Activation of the catalyst The transition metal complex was dissolved in toluene (previously dried over metallic sodium) under a nitrogen atmosphere and an activator solution (cocatalyst) was added at room temperature. The mixture was stirred at room temperature and then an aliquot was transferred to the injection unit of a polymerization reactor. The amounts of reagents used in catalyst activation are summarized in the following Table. All operations were performed under a nitrogen atmosphere unless otherwise indicated. "MAO" is methylaluminoxane (1.78 M in toluene, supplied by Witco). "MMAO" is modified methylaluminoxane (10% w / w in heptane, supplied by Witco) and used in the manner in which they were purchased. Triisobutylaluminum (Al (iBu) 3 as a 1M solution in toluene was supplied by Aldrich.

Polymerisation assays The reagents used in the polymerization tests were grade 3.5 ethylene (supplied by Air Products), hexene (supplied by Aldrich) distilled over sodium / nitrogen and triisobutylaluminum (1M in hexanes, supplied by Aldrich). Ethylene polymerization A 1 liter reactor was previously heated under a nitrogen flow for at least 1 hour at > 85 ° C. The reactor was then cooled to 50 ° C. Isobutane (0.5 liters) and triisobutylaluminum were then added and the reactor was introduced in a glovebox under nitrogen. The alkylaluminium was allowed to sweep poisons from the reactor for at least 1 hour. Ethylene was introduced into the reactor until a predetermined overpressure was reached, after which the catalyst solution was injected under nitrogen. The reactor pressure was kept constant throughout the polymerization experiment by the computer-controlled addition of more ethylene. The polymerization time was 1 hour. At the end of the experiment, the content of the reactor was isolated, washed with acidified methanol (50 ml HCl / 2.51 methanol) and water / ethanol (4: 1 v / v) and dried under vacuum at 40 ° C for 16 hours. Ethylene / 1 -hexene coporanization (Example 19) A 1 liter reactor was previously heated under a nitrogen flow for at least 1 hour at > 85 ° C. The reactor was then cooled to 50 ° C. Isobutane (0.5 liters), 1 -hexene and triisobutylaluminum were then added and the reactor was introduced in a glove box under nitrogen. The alkylaluminium was allowed to sweep poisons from the reactor for at least 1 hour. Ethylene was introduced into the reactor until a predetermined overpressure was reached, after which the catalyst solution was injected under nitrogen. The reactor pressure was kept constant throughout the polymerization experiment by the computer-controlled addition of more ethylene. The polymerization time was 40 minutes. At the end of the experiment, the content of the reactor was isolated, washed with acidified methanol (50 ml HCl 2.51 methanol) and water / ethanol (4: 1 v / v) and dried under vacuum at 40 ° C for 16 hours. The data of the polymerization tests appear in the following Table.

Notes in Table # Example 19 illustrates the copolymerization of ethylene with 1-hexene. 1-hexene (50 ml) was included in the polymerization. The rest Examples were all of them ethylene homopolymerizations. "ppm" is defined as parts by weight of transition metal per million parts by weight of polymer.

The molecular weight data of the polymers obtained in Examples 14 to 25 are given in the following Table.

Examples 26 and 27 Gaseous polymerization tests with supported catalysts Examples 26 and 27 illustrate the use of the catalysts of the present invention supported on a silica support material. Example 26 uses 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl 2 and Example 27 uses 2,6-diacetylpyridinbis (2,4,6.trimethylanil) -FeCl 2 as the transition metal complex compound. EXAMPLE 26 Preparation of supported catalyst 2,6-diacetylpyridinebis (2,6-diisopropylanil) FeCl 2 was prepared in the manner described in Example 1. Silica (1.03 g ES70, supplied by Crosfield), which had been heated under a flow of nitrogen at 700 ° C, in a Schlenk tube and toluene was added (10 ml). The mixture was heated to 50 ° C. To a solution of 2,6-diacetylpyridinbis (2,6-diisopropylanil) FeCl 2 (0.036 g) in toluene (10 ml) was added methylaluminoxane (5 ml, 1.78 M in toluene, supplied by Witco). The mixture was heated to 50 ° C and then transferred to the silica / toluene mixture. The silica / MAO / toluene mixture was maintained at 50 ° C, with regular agitation, for 1 hour before removing the toluene, at 65 ° C, under vacuum, to obtain a free-flowing powder. Example 27 Preparation of the supported catalyst. 2,6-Diacetylpyridinebis (2,4,6-trimethylanil) FeCl 2 was prepared in the manner described in Example 9. Silica (1.38 g ES 70, supplied by Crosfield), was added. was heated under a flow of nitrogen at 700 ° C, to a Schlenk tube and toluene (10 ml) was added. To a solution of 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 (0.041 g) in toluene (10 ml) was added methylaluminoxane (13.2 ml, 1.78 M in toluene, supplied by Witco). This mixture was heated at 40 ° C for 30 minutes to dissolve as much of the iron complex as possible. The solution was then transferred to the silica / toluene mixture. The silica / MAO / toluene mixture was maintained at 40 ° C, with regular agitation, for 30 minutes before removing the toluene, at 40 ° C, under vacuum, to obtain a free flowing powder. Analysis of the solid indicated 16.9% w / w Al and 0.144% w / w Fe. Polymerization Assays - Examples 26 and 27 The reagents used in the polymerization tests were: 6.0 quality hydrogen (supplied by Air Products ): grade 3.5 ethylene (supplied by Air Products): hexene (supplied by Aldrich) distilled over sodium / nitrogen: dry pentane (supplied by Aldrich): methylaluminum (2 M in hexanes, supplied by Aldrich): and triisobutylaluminum (1 M in hexanes, supplied by Aldrich). A 3 liter reactor was preheated under a nitrogen flow for at least 1 hour at 77-85 ° C before adding powdered sodium chloride (300 g, previously dried under vacuum, 160 ° C,> 4 hours). Sodium chloride was used as a start-up charge, fluid / cable / agitable, for gas phase polymerization. To the reactor was added trimethylaluminum (3 ml, 2 M in hexanes) and then introduced into a glove box under nitrogen. The alkylaluminum was allowed to sweep poisons from the reactor for a time comprised between 30 and 60 minutes before being vented using nitrogen purges of 4 x 4 bar. The composition of the gas phase to be used for the polymerization was introduced into the reactor and preheated to 77 ° C before the injection of the catalyst composition. The catalyst (0.18-0.22 g) was injected under nitrogen and the temperature was then adjusted to 80 ° C. The ratio of hexene and / or hydrogen to ethylene during the polymerization was kept constant by controlling the composition of the gas phase by means of a mass spectrometer and adjusting the equilibrium in the required form. The polymerization tests were allowed to continue for a time comprised between 1 and 2 hours before being terminated by purging reactor reactants with nitrogen and reducing the temperature to <30 ° C. The polymer produced was washed with water to remove the sodium chloride, then with acidified methanol (50 ml HCl / 2.5 l methanol) and finally with water / ethanol (4: 1 v / v). The polymer was dried under vacuum, at 40 ° C, for 16 hours. With each of the catalysts of Examples 26 and 27 several experiments were carried out using a variety of operating conditions. All the polymerization tests were carried out at a polymerization temperature of 80 ° C and at an ethylene pressure of 8 bar. The polymerization conditions are given in the following Table.

The data regarding the molecular weight of the polymer products are given in the following Table The polymer obtained in example 27.7 contained short chain branching (SCB) corresponding to 1.6 n-butyl branches / 1000 C. Example 28 28.0 - Preparation of 2,6-dialdiminpyridinbis (2A6-trimethylane) 2,6-dimethanolpyridine (6.53 g, 0.048 mol) in absolute ethanol were mixed together (50 ml), 2,4,6-trimethylaniline (2.5 equivalents, 17 ml, 0.12 mol) and glacial acetic acid (3 drops) and the mixture was refluxed for 24 hours. After cooling of the mixture, yellow crystals of 2,6-dialdiminpyridinbis (2,4,6-trimethylanil) were separated. (14.28 g, 80% yield). Analysis of the crystalline product by 1H NMR: (250 Hz) 8.42 (s, 2H), 8.40 (s, 2H), 8.0 (t, 3J (HH) 8, JH), 7.0 (s) , 4H), 2.33 (s, 6H), 2.19 (s, 12H). Mass spectrum: m / z: 369 [M] +. 28.1 - Preparation of 2,6-dialdiminpyridinbis (2,4,6-trimethylanil) FeCl 3 (Formula G) - see below FeCl 3 (0.10 g, 0.615 mmol) was dissolved in MeCN (25 mL) at room temperature and 2.6 was added Dialdiminpyridinbis (2,4,6-trimethylanil) (0.227 g, 0.615 mmol). After stirring 24 hours at room temperature, a precipitate of 2,6-dialdiminopyridinbis (2,4,6-trimethylanil) FeCl 3 (0.192 g, 60%) was collected and dried. Analysis of the product: Mass spectrum: m / z: 531 [M] +, 496 [M-C1] +, 462 [M-2C1] +. 28.2 - Polymerization assay The 2,6-dialdiminopyridinbis (2,4,6-trimethylanil) FeCl 3 (0.02 mmol) prepared as above was dissolved in toluene (40 ml) in a Schlenck tube, to obtain a red solution and the cocatalyst (methylalumoxane, MAO) (8 mmol, 400 equivalents) was introduced (the formation of an orange solution was observed). The MAO was supplied by Aldrich (catalog number: 40.459-4). The tube was purged with ethylene and the content stirred under 1 bar of ethylene during the polymerization. After half an hour, the experiment was stopped by the addition of an aqueous solution of hydrochloric acid. Solid polyethylene (1.5 g) was collected by filtration, after which it was washed with methanol and dried in a vacuum oven at 50 ° C. Polyethylene soluble in toluene was isolated from the filtrate by separation of the toluene layer from the aqueous layer, drying over magnesium sulfate and separation of the toluene by distillation. The weight of soluble polyethylene in toluene obtained was 2.46 g. The activity of the catalyst (based on the total weight of polyethylene obtained) was 396 g mmorVbar "1.

Example 29 Preparation of a catalyst from 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 was prepared in the manner described in Example 9. Al 2, 6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 (17 mg, 0.03 mmol) dissolved in Et 2 O (20 ml), at -78 ° C, was added dropwise a solution of trimethylsilylmethylmagnesium chloride (0.164 mmol , 1M solution in Et2?). The solution was stirred for 10 minutes and then allowed to warm to 0 ° C and stirred for a further 5 minutes. The reaction solvent was removed under reduced pressure. To the iron complex was added trifly tetra (pentafluorophenyl) borate (151 mg, 0.164 mmol) and toluene (20 ml, dry) to obtain a red solution. The Schlenk tube was purged with ethylene and the content was magnetically stirred and kept under 1 bar of ethylene during the polymerization. After 60 minutes, the polymerization was terminated by addition of acidified methanol (50 ml HCl / 2.5 l methanol). The solid, insoluble polyethylene was recovered by filtration, washed with methanol / water (1: 4 v / v) and dried (vacuum oven at 40 ° C). The yield in solid polyethylene was 0.90 g and the polymerization activity was 28 gmmor "1 ^ 1. The reagents used in Example 29 were as follows: Trimethylsilylmethylmagnesium chloride (supplied by Aldrich as a 1M solution in Et. O); Tetra (pentafluorophenyl) borate trifile (supplied by Boulder); Diethyl ether (supplied by Aldrich, dried over sodium); Toluene (supplied by Aldrich, dried over sodium) Examples 30 and 31 In these Examples, they were synthesized and tested as catalysts for the polymerization of olefins, iron (p) complexes comprising pyridine hydrazone tridentate ligands according to the present invention 30.1 - Preparation of 2,6-bis (l-methyl-1-phenylhydrazone ^ pyridine) together 2,6-diacetylpyridine (5.0 g, 30.6 mmol) [Aldrich Chemicals] and 1-methyl, 1-phenylhydrazine (7.21 ml, 61.3 mmol) [Aldrich Chemicals] in absolute ethanol and then refluxed for 12 hours. After reducing the volume of the solution by evaporation of part of the ethanol and cooling to -20 ° C, yellow needles of 2,6-bis (l-methyl, 1-phenylhydrazone) pyridine were obtained and separated by filtration. Yield 90% approximately. Mass spectrum: m / z: M * 372. Analysis by 1 H NMR (300 MHz, CDC 13, 298 K) d: 2.52 (s, 6 H, CH 3 C = N), 3.32 (s, 6 H, CH 3 - N), 6.95-8.31 (multiplets, 13H, arils). 30.2 - Preparation of the 2.6-bis (l-methyl-phenylhydrazone) pyridine complex. FeCl? FeCl2.4H2O (0.21 g, 1.06 mmol) and 2,6-bis (l-methyl, 1-phenylhydrazone) pyridine (0.39 g, 1.06 mmol) were stirred together in anhydrous n-butanol ( 10 ml) and heated at 80 ° C for 2 hours. The reaction mixture was then allowed to cool to room temperature. Volatiles separation under vacuum, extraction with hot MeCN (30 ml) and cooling (-20 ° C) provided the desired iron complex (formula L given below) as large brown needles. Performance 85% approximately. 31.1 - Preparation of 2,6-bis (l-diphenylhydrazone) pyridine This compound was prepared in a manner analogous to that indicated in Example 30.1 using 2,6-diacetylpyridine (1 g, 6.13 mol) and 1,1-diphenylhydrazine hydrochloride (2.7 g, 12. 3 mmol) [Aldrich Chemicals]. Performance 85% approximately. Analysis by 1 H NMR (300 MHz, CDCl 3, 298 K) d: 2.12 (s, 6 H, CH 3 C = N), 7.09 - 8.35 (multiplets, 23 H, aryls). 31.2 - Preparation of the 2,6-bis (l.l-diphenylhydrazone) pyridine complex. FeCl ?. This complex (see formula M below) was prepared in a manner analogous to that indicated in Example 30.2 from FeCl2.4H2O (0.5 g, 2.51 mmol) and 2,6-bis (l, 1-diphenylhydrazone ) pyridine (1.19 g, 2.52 mmol). Yield 70% approximately. Mass spectrum: mz: Mf1"- Cl 586. 30.3 and 30.4 - Polymerization tests The iron complexes prepared in Examples 30.2 and 31.2 were tested in the polymerization of ethylene under the following standard conditions. toluene (40 ml, dried over sodium wire) in a Schlenk tube, the cocatalyst (methylaluminoxane- "MAO") was added.The "MAO" was supplied by Witco as a 1.78 M solution in toluene.The Schlenk tube was purged with ethylene and the content was magnetically stirred and maintained under 1 bar of ethylene during the polymerization.After 60 minutes, the polymerization was terminated by addition of acidified methanol (50 ml HCl / 2.5 liters methanol). Insoluble was recovered by filtration, washed with methanol / water (1: 4 v / v) and dried (vacuum oven at 50 ° C.) For Example 30, the obtained polyethylene solution was dried over magnesium sulfate and the solvent was removed under vacuum to provide traces of a waxy material. The results of the polymerization tests are given in the following Table.

Example 32 32.1 - Preparation of a supported Ziegler catalyst component Silica (20 kg) of quality ES 70, supplied by Crosfield, which had been dried at 800 ° C for 5 hours in a flow of nitrogen, was entached in hexane (110 liters) ) and hexamethyldisilazane (30 mol) supplied by Fluka was added with stirring at 50 ° C. Dry hexane (120 liters) was added with stirring, the solid was allowed to settle, the supernatant liquid was separated by decantation and more dry hexane (130 liters) was added with stirring. Washing with hexane was repeated three more times. Dibutylmagnesium (30 moles) supplied by FMC was added and stirred for 1 hour at 50 ° C. Tere-butyl chloride (60 mol) was added and stirred for 1 hour at 50 ° C. To this slurry was added an equimolar mixture of titanium tetrachloride (3 moles) and titanium tetra-n-propoxide (3 moles) with stirring at 50 ° C for 2 hours, followed by 5 washes with dry hexane (130 liters). The slurry was dried under a stream of nitrogen to obtain a Ziegler solid catalyst component supported on silica. 32. 2 - Preparation of a mixed catalyst containing a Ziegler component and a transition metal compound of the present invention _ A solution of methylaluminoxane ("MAO", 10.2 mmol) was added as a 10 wt% solution in toluene , supplied by Witco, to a suspension of 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2 (0.07 mmol in 5 ml of dry toluene), prepared as in Example 9, and the mixture was shaken for 5 minutes. This solution was then added to 2 g of the silica-supported Ziegler catalyst prepared above (Example 32.1), the mixture was shaken for 2 hours at 20 ° C and then the solvent was removed under reduced pressure at 20 ° C, to obtain the catalyst mixed as a free flowing powder. 32.3 - Polymerization of an ethylene / hexane mixture using the mixed catalyst A 3 liter reactor equipped with a helical stirrer was heated at 95 ° C for 1 hour with a flow of dry nitrogen therethrough. The temperature was reduced to 50 ° C and then dry sodium chloride (300 g) was added with trimethylaluminum solution (TMA) (2 ml of 2 molar TMA in hexane) and the reactor was heated to room temperature. 85 ° C for 2 hours. The reactor was purged with nitrogen, cooled to 50 ° C and TMA solution (3 ml of 2 molar TMA in hexane) was added. The temperature was raised to 77 ° C and hydrogen (0.5 bar) and ethylene (8 bar) were added before the addition of 1 -hexene (2.6 ml). The reaction was initiated by injection into the mixed catalyst reactor (0.20 g) prepared above. The temperature was maintained at 80 ° C and ethylene was added to maintain the constant pressure. The gas phase was controlled by a mass spectrometer and hydrogen and 1-hexene were added in the necessary amount to maintain constant gas phase concentrations of these components. The polymerization was carried out for 90 minutes. The polymer was washed with water to remove the sodium chloride, then with acidified methanol (50 ml HCl / 2.5 liters methanol) and finally with water / ethanol (4: 1 v / v). The polymer was dried under vacuum at 40 ° C for 16 hours. 111 g of dry polymer was obtained. The polymer had a broad molecular weight distribution (as determined by gel permeation chromatography). The polydispersity (Mw / Mn) was 28.5. Example 33 33.1 - Pre-impregnation of a support with activating compound All the following operations were carried out under a nitrogen atmosphere unless otherwise indicated. Silica was heated (Crosfield quality ES70X) under a flow of nitrogen at 250 ° C for 16 hours. A sample of this silica (2.5 g) was placed in a Schlenk tube and 12.1 ml of 1.78 M methylaluminoxane, MAO (supplied by Witco), was added to form a slurry. The slurry was heated for 4 hours at 50 ° C before being left for 10 days at room temperature. The supernatant liquid above the silica was separated and the silica / MAO mixture was washed three times with toluene (3 x 10 ml) at room temperature, separating the supernatant solution each time. 33.2 - Operation to support the catalyst 2,6-diacetylpyridinebis (2,4,6-trimethylanil) iron dichloride (0.101 g) (prepared as described in Example 9) in toluene (20 ml) was filled at room temperature. environment, and was added to the silica / MAO mixture. The mixture was shaken occasionally for 1 hour. The supernatant solution was separated and the silica / MAO / Fe complex was washed with toluene until the filtrate was colorless. The solid was dried under vacuum at 50 ° C. 33.3 - Polymerization of ethylene in gas phase A 3 liter reactor was previously heated under a nitrogen flow for at least 1 hour at 77 ° C before adding sodium chloride (300 g, particles of less than 1 mm diameter, previously dried under vacuum, 160 ° C, for more than 4 hours). Sodium chloride was used simply as a standard "charge powder" for the gas phase polymerization reactor. Trimethylaluminum (3 ml) was added to the reactor, 2M in hexanes, supplied by Aldrich and the reactor was then closed. The alkylaluminium was allowed to sweep poisons from the reactor for half an hour before being ventilated by successive pressurization and purging of the reactor with 4 bar of nitrogen. Ethylene (quality 3.5, supplied by Air Products) was added to the reactor to give a pressure of 8 bar, at 77 ° C, before the injection of the catalyst. The supported catalyst (0.215 g) prepared as described in Example 33.2 was injected into the reactor under nitrogen and the temperature was then adjusted to 80 ° C. The polymerization was allowed to continue for 5 hours before being terminated by purging the ethylene from the reactor, using nitrogen, and reducing the temperature below 30 ° C. The polymer was washed with water to remove the sodium chloride, then with acidified methanol (50 ml HCl / 2.5 liters methanol) and finally with water / ethanol (4: 1 v / v). The polymer was dried under vacuum at 40 ° C for 16 hours. 161 g of dry polymer were obtained. Example 34 - Modified Polymerization Catalyst with a Neutral Lewis Base The 2,6-diacetylpyridinebis (2,6-diisopropylanyl) FeCl2 complex prepared in Example 1 was tested in the polymerization of ethylene under the following standard conditions. To the iron complex (8 μmol) dissolved in dry toluene (10 ml) in a Schlenk tube, a solution of N, N-dimethylaniline in toluene (10 ml) and then the cocatalyst (methylaluminoxane- "MAO", 8 mmol) was added. of a 1.88 M MAO solution in toluene, supplied by Witco, reference AL 5100 / 10T). The contents of the Schlenk tube were magnetically stirred and kept under 1 bar of ethylene during the polymerization. After 60 minutes, the polymer produced was washed with acidified methanol (50 ml HCl / 2.5 liters methanol) and finally with water / ethanol (4: 1 v / v). The polymer was dried under reduced pressure at 40 ° C for 16 hours. Several experiments were conducted using a variety of operating conditions, and the polymerization conditions are given in the following Table.

Notes in the Table DMA is N, N-dimethylaniline; The activity is expressed as g of polymer "1 transition metal li ^ bar" 1; C = Comparative Test without using DMA Examples 35 to 38 These examples illustrate the preparation of supported catalysts according to the present invention and their use in the polymerization of ethylene under "slurry" polymerization conditions. EXAMPLE 35.1 - Preparation of 2,6-diacetylpyridinbis (2,4,6-trimethylanil) iron dichloride supported on MAO / silica Silica support material (quality ES70X, supplied by Crosf? Eld) under a nitrogen flow at 250 ° C for 16 hours. A sample of this silica was placed in a Schlenk tube and 12.1 ml of 1.78 M methylaluminoxane ("MAO" supplied by Witco) was added thereto to form a slurry.

The slurry was heated for 4 hours at 50 ° C before being left for 10 days at room temperature. The supernatant liquid above the silica was then separated and the silica / MAO mixture was washed three times with toluene (10 ml) at room temperature, separating the supernatant solution each time. 2,6-Diacetylpyridinbis (2,4,6-trimethylanil) iron dichloride complex (0.105 g) was enquered in toluene (20 ml) at room temperature and added to the silica / MAO mixture. The mixture was shaken occasionally for 1 hour. The supernatant solution was separated and the MAO / Fe complex supported on silica thus obtained was washed with toluene until the initial washings, which were a light orange color, were clean and free of color. The solid catalyst supported on silica thus obtained was dried under vacuum at 50 ° C. 35.2 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow (2 liters / minute) for 1 hour at 95 ° C. The reactor was cooled to 40 ° C and 500 ml of isobutane was added. The reactor temperature was raised to 80 ° C and ethylene was admitted to the reactor to give a partial pressure of 10 bar. The supported catalyst prepared in 35.1 above (0.201 g, slurried in 10 ml of toluene) was injected under nitrogen and the increase in pressure in the reactor in controlling the reactor pressure during the polymerization test was taken into account. The assay was finished after 1 hour and the polymer was dried under vacuum at 40 ° C. 5.9 g of polymer was recovered. Analysis of the polymer by GPC indicated that the Mw and Mn values were 124000 and 15000 respectively. 35.3 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 3 hours at 80 ° C. The reactor was cooled to less than 30 ° C and 500 ml of isobutane was added. Trimethylaluminum (3 ml of 2M in hexanes) was added to the reactor and this was heated to 80 ° C. The reactor pressure increased to 13.8 bar and then ethylene was admitted to provide a total pressure of 23.8 bar. The supported catalyst prepared in 35.1 above (0.201 g of solid supported catalyst in a slurry in toluene) was injected into the reactor under nitrogen causing the reactor pressure to increase to . 4 bars The activity of the catalyst was too high, slightly, so that the inflow of ethylene maintained the constant pressure and, therefore, it was allowed to descend to 23.2 bar. The ethylene pressure present in the reactor during most of the polymerization was estimated to be 7.8 bar. The assay was terminated after 1.75 hours and the polymer was washed with methanol / HCl (2.5 liters / 50 ml), then with water / ethanol (4: 1 v / v) and dried under vacuum at 40 °. C. 166 g of dry polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 182000 and 11000 respectively.

Example 36 36.1 -Preparation of 2,6-diacetylpyridinbis (2A6-trimethylanil) iron dichloride supported on MAO / silica __ A portion (approximately 1-1.5 g) of the supported catalyst prepared in Example 35.1 was washed with 5 aliquots of 10 ml of toluene at 100 ° C. The initial washes had a color intense orange and this coloration reached less with each of the subsequent washings until the final wash was clean of color. The solid was dried under vacuum at 100 ° C to provide a solid, free-flowing supported catalyst. 36.2 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 1 hour at 75 ° C. Trimethylaluminum (3 ml of 2M in hexanes) was added to the reactor and this was then cooled to 50 ° C. Isobutane (500 ml) was added to the reactor and the temperature increased to 76 ° C. The reactor pressure increased to 13 bar. Ethylene was admitted to the reactor to obtain a total pressure of 21 bar (8 bars of ethylene). The supported catalyst prepared in 26.1 above (0, 11 g in slurry in toluene) was injected into the reactor and the increase in pressure in controlling the reactor pressure during the test was taken into account. The temperature was increased to 80 ° C. After 1 hour, another aliquot of the same catalyst (0.22 g in slurry in hexane) was injected and the assay continued for a further 3.5 hours. 25 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 343000 and 35000 respectively. Example 37 37.1 - Preparation of 2,6-diacetylpyridinbis (2A6-trimethylanil) iron dichloride supported on MAO / silica Methylaluminoxane (24 ml of 1.78 M in toluene, supplied by Witco to silica (5 g of quality ES70X, supplied by Crosfield that had been heated under a flow of nitrogen at 250 ° C. The silica / MAO mixture was heated at 80 ° C for 1 hour before washing with toluene (5 parts aliquots of 10 ml.) Half of the obtained silica / MAO slurry, cooled to room temperature, was used for the next step of catalyst preparation (the other half was left aside for use in Example 38). 2,6-diacetylpyridinbis (2,4,6-trimethylanil) iron dichloride (73 mg) in toluene and the slurry was transferred to the silica / MAO / toluene moiety and allowed to react for 2 hours with occasional mixing. of silica / MAO / Fe was washed with toluene (3 parts aliquots of 10 ml) at room temperature and then with hexane (2 parts aliquots of 10 ml) at room temperature, to separate the toluene before finally washing with hexane at 80 °. C (3 parts aliquots of 10 ml) The catalytic solid supported The product was dried under vacuum at room temperature. The solid contained 0.107% by weight of Fe. 37.2 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C.

The reactor was cooled to less than 30 ° C and 500 ml of isobutane was added. The reactor was heated to 77 ° C and the pressure increased to 13.8 bar. Ethylene was added to obtain a total pressure of 21.8 bar (8 bars of ethylene). To the reactor, triisobutylaluminum (5 ml of 1M in hexanes) was added and after 20 minutes the supported catalyst prepared in 37.1 above (0.14 g in slurry in hexane) was injected into the reactor and the increase in pressure was taken into account. Control of reactor pressure during the test. The temperature was increased to 80 ° C. After 5 hours, the polymerization was terminated. 138 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 567000 and 53000 respectively. The polymer produced contained 1.02 ppm of Fe derived from the catalyst. 37.3 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 1 hour at 78 ° C. The reactor was cooled to less than 30 ° C and 500 ml of isobutane was added. Triisobutylaluminum (3 ml of 1M in hexanes) was added to the reactor which was then heated to 78 ° C, increasing the pressure to 12.1 bar. Ethylene was added to obtain a total pressure of 32 bar (19.9 bars of ethylene). The supported catalyst prepared in 37.1 above (0.0925 g, slurried in hexane) was injected into the reactor and the total pressure was controlled at 31.2 bar. It was estimated that the ethylene pressure during the polymerization was approximately 19.1 bars. The polymerization was allowed to continue for 80 minutes. 181 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 595000 and 44000 respectively. The polymer contained 0.51 ppm Fe derived from the catalyst. 37.4 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to below 30 ° C. To the reactor was added triisobutylaluminum (3 ml of 1M in hexanes) followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure increased to 13.5 bar. Ethylene was added to obtain a total pressure of 17.6 bar (4.1 bars of ethylene). The supported catalyst prepared in 37.1 above (0.15 g, slurried in hexane) was then injected into the reactor. It was estimated that the ethylene pressure during the polymerization was approximately 4.7 bar. The polymerization was allowed to continue for 80 minutes. 21 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 347000 and 26000 respectively. Example 38 38.1 - Preparation of 2,6-diacetylpyridinbis (2,6-diisopropylanyl) cobalt dichloride supported on MAO / silica The second half of the silica / MAO mixture prepared in Example 37.1 was dried under vacuum. An aliquot of the dry silica / MAO mixture (1 g) was placed in a Schlenk tube and the latter was added, as a dry powder, 2,6-diacetylpyridinbis (2,6-diisopropylanil) cobalt dichloride. Hexane (10 ml) was added to the Schlenk tube and the cobalt complex and the silica / MAO mixture were co-enclosed for 1 hour at room temperature. The mixture was dried under vacuum at room temperature to leave the supported catalyst obtained as a free flowing dry powder. 38.2 - Polymerization of ethylene A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to 30 ° C. To the reactor were added hexene (250 ml), triisobutylaluminum (3 ml of 1M in hexanes) and 250 ml of isobutane. The reactor was heated to 80 ° C and the pressure increased to 7.1 bar. Ethylene was added to obtain a total pressure of 19.2 bar (12.1 bars of ethylene). The supported catalyst prepared in 38.1 above (0.245 g, slurried in hexane) was injected into the reactor and the pressure increase in controlling the reactor pressure during the test was taken into account. The polymerization was allowed to continue for 330 minutes. 3.3 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw = 5300 and Mn = 1500. Example 39 - Polymerization of ethylene in slurry phase using a supported catalyst A series of polymerization tests were carried out using a catalyst a, base of a dichloride of 2. , 6-diacetylpyridinbis (2,4,6-trimethylanil) iron supported. Example 39.1 A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to 30 ° C. To the reactor was added isobutane (500 ml) followed by triisobutylaluminum (3 ml of 1M in hexanes). The reactor was heated to 78 ° C and the pressure increased to 13.2 bar. Ethylene was added to obtain a total pressure of 26.2 bar. The catalyst of Example 37.1 (0.097 g, slurried in hexane) was injected into the reactor. The reactor pressure was controlled at 26 bar during the test (the ethylene pressure was estimated to be about 12.8 bar) and the temperature was adjusted to 80 ° C. The polymerization was allowed to continue for 60 minutes. 78 g of polymer was recovered. The analysis of the polymer by GPC indicated values Mw and Mn of 528000 and 40000 respectively. Example 39.2 A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to 30 ° C. To the reactor was added isobutane (500 ml) followed by triisobutylaluminum (3 ml of 1M in hexanes). The reactor was heated to 78 ° C and the pressure increased to 13.4 bar. Ethylene was added to obtain a total pressure of 21.2 bar. The catalyst of Example 37.1 (0.124 g, slurried in hexane) was injected into the reactor. The ethylene pressure was estimated at approximately 8.1 bar during the polymerization and the temperature was adjusted to 80 ° C. The polymerization was allowed to continue for 60 minutes. 47 g of polymer was recovered. The analysis of the polymer by GPC indicated Mw and Mn values of 376000 and 40000 respectively.

Example 39.3 A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to 30 ° C. To the reactor was added triisobutylaluminum (3 ml of 1M in hexanes) followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure increased to 13 bar. Ethylene was added to give a total pressure of 26 bar. The catalyst of Example 37.1 (0.0966 g, slurried in hexane and 0.25 ml of N, N-dimethylaniline for 20 minutes) was injected into the reactor. The pressure in the reactor was allowed to drop to 22.5 bar to reduce catalyst activity. The ethylene pressure in the reactor during most of the polymerization was estimated at 9 bars. The polymerization was allowed to continue for 60 minutes. 88 g of polymer was recovered. Analysis of the polymer by GPC indicated Mw and Mn values of 430000 and 35000 respectively. Example 39.4 A 1 liter reactor was heated under a nitrogen flow for 1 hour at 80 ° C before cooling to 30 ° C. To the reactor was added triisobutylaluminum (3 ml of 1M in hexanes) followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure increased to 12.7 bar. Ethylene was added to give a total pressure of 14.7 bar. The catalyst of Example 37.1 (0.104 g, slurried in hexane) was injected into the reactor. It was estimated that the ethylene pressure during the polymerization was about 2.2 bar. The polymerization was allowed to continue for 60 minutes. 4.8 g of polymer was recovered. The analysis of the polymer by GPC indicated values Mw and Mn of 340000 and 36000 respectively. Example 40.1 - Preparation of 2,6-diacetylpyridinbis (triphenylmethylimine To a solution of 2,6-diacetylpyridine (0.34 g, 2.1 mmol) in toluene (75 ml) was added triphenylmethylamine (1.20 g, 4.6 mmol After the addition of toluenesulfonic acid monohydrate (0.05 g), the solution was refluxed overnight through a Dean-Stark apparatus, after cooling to room temperature, the volatile components of the mixture were removed in vacuo. The product was filtered, washed with cold methanol and dried in a vacuum oven (30 ° C) overnight.The yield was 1.02 g (33%). of 2,6-diacetylpyridibis (triphenylmethylimine) FeBr? FeBr2 (0.182 g, 0.84 mmol) was dissolved in warm n-butanol (30 ml) at 80 ° C and solid 2,6-diacetylpyridinbis (triphenylmethylamine) was added in several portions ( 0.60 g, 0.93 mmol) The reaction mixture turned purple, after stirring at 80 ° C for 60 minutes. minutes, the reaction mixture was allowed to cool to room temperature. Stirring was continued for 25 hours. The volatile components of the solution were removed under reduced pressure and the resulting purple solid was washed with pentane (2 x 20 cm3) and dried in vacuo. The yield was 0.362 g (64% of theory). 40.3 - Polymerization Test A polymerization test was carried out using the following procedure. The 2,6-diacetylpyridinbis (triphenylmethylamine) FeBr2 catalyst (0.008 mmol) was added to a Schlenk tube, suspended in toluene (15 ml), and methylalumoxane cocatalyst ("MAO") was added to provide a molar ratio of MAO complex : Faith of 1000: 1. The tube was purged with ethylene and the contents were mechanically stirred and kept under 1 bar of ethylene during the polymerization. After 90 minutes, the polymerization was terminated by the addition of aqueous hydrogen chloride. The solid polyethylene produced was separated by filtration, washed with methanol and dried in a vacuum oven at 50 ° C. The polyethylene yield was 0.185 g. This corresponds to a catalytic activity of 16 g. No attempt was made to measure the amount of any soluble polymer that may have been produced in this Example.

Claims (59)

1. NOVELTY OF THE INVENTION Having described the invention, it is claimed and, therefore, what is contained in the following claims is considered as property: 1. A polymerization catalyst characterized in that it comprises: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Ru [irj, Ru [prj, Ru [TV], Mn [I], Mn [ITj, Mn \ ¡or Mn [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of RR7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Mn or Ru, then R is a group having the formula -NR T *. and R is a group having the formula -NR R wherein R a R are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents.
2. 2. A catalyst according to claim 1, characterized in that in formula B, M [T] is RuPTJ, Ru [HTJ or Ru [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents.
3. 3. A catalyst according to claim 1, characterized in that the compound of formula B has the following formula Z Formula Z where M is Mn [TJ, Mn [lTJ, Mn [BTJ, Mn [TV], RuflI], Ru [m] or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4. R6 and R19 to R28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q is part of a condensed ring polyaromatic system.
4. 4. A catalyst according to any of the preceding claims, characterized in that the catalyst is supported on a support material. 5. - A catalyst according to claim 4, characterized in that the support material comprises silica, alumina or zirconia or a polymer or prepolymer. 6. A polymerization catalyst characterized in that it comprises: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Fe [II], Fe [m], Cofrj, Co [II], Co [m], Ru [H "], RuruT], Ru [TV], Mn [I], Mn [II], Mn [ip] or MnflV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more of R ^ R7 may be linked to form one or more cyclic substituents, or in such a way that (2) when M is Fe, Co, Mn or Ru, in then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R, R, R and R is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when any of the ring systems P and Q is part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Fe, Co, Mn or Ru, then R5 is a group having the formula -NR 9R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are chosen independently between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents. 7. A catalyst according to claim 6, characterized in that in formula B, MTT] is Fe [H], Fe [m], Ru [lTJ, Ru [p? or Ru [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. 8. A catalyst according to claim 6, characterized in that the compound of formula B has the following formula Z Formula Z where M is Fe [H], Fe [m], Co [I], Cop ?, Co [l?], Mnfl], Mn [U], Mn [m], Mn | TV], RupT] , Ru [IH] or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4. R6 and R19 to R28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the condition that at least one of R19, R 20 R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system. 9. A catalyst according to claim 3 to 8, characterized in that none of the ring systems P and Q is part of a polyaromatic ring system and that at least one of R19 and R20 and at least one of R21 and R22 is chosen between hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. 10. - A catalyst according to claim 3 or 8, characterized in that none of the ring systems P and Q is part of a condensed ring polyaromatic system and that each of R19, R20, R21 and R22 is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. 11. A polymerization catalyst, characterized in that it comprises: (1) a compound of the following formula T; (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula T where M is Fe [II], Fe [HI], Co [I], Co [lTJ, Co [HTJ, Mn [I], Mn [H], Mn [HT], Mn [IV], Ru [II], Ru [HTJ or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4, R6 and R29 to R32 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. 12. - A catalyst according to claim 6, characterized in that the compound of formula B has the following formula W Formula W wherein X represents an atom or group cavalently or ionically linked to the cobalt atom; T is the oxidation state of the cobalt atom and can be Co [I], Co [H], Copai], and b is the valence of the atom or group X; R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when two or more of Rx-R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. 13. A catalyst according to any of the preceding claims, characterized in that X is selected from halide, sulfate, nitrate, thiolate, thiocarboxylate, BF4, PFß ", hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted bidrocarbyl and heterohydrocarbyl. A catalyst according to any of claims 1 to 12, characterized in that X is selected from chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxide and benzoate 15. A catalyst according to any of the preceding claims, characterized in that the organoaluminum compound is a trialkylaluminum compound. 16. A catalyst according to any of the preceding claims, characterized in that the organoaluminum compound is an alumoxane 17. A catalyst according to any of claims 1 to 14, characterized in that the hydrocarbylboro compound is selected from tetra (phenyl) borate of dimethylphenylammonium, tetra (phenyl) borate of trifile, trifenilboro, tetra (pentafluorophenyl) borate of dimethylphenylammonium, tetrakis [( sodium bis-3,5-trifluoromethyl) phenyl] borate, H + (OEt 2) [(bis-3,5-trifluoromethyl) phenyl] borate, tetra (pentafluorophenyl) borate, trifyl and tris (pentafluorophenyl) boron. 18. A catalyst according to claim 4 to 17, characterized in that the formation of the supported catalyst is achieved by treating the nitrogenous transition metal compound defined above with alumoxane in an inert volatile hydrocarbon diluent, by grouting the particulate support material with the product. and evaporating the volatile diluent. 19. A supported polymerization catalyst because it comprises: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, where M [T] is Fe [lTJ, Fe [pTj, Co | TJ, Co [lTJ, Co [m], Ru [E], Ru [HT], Ru [TV], Mn [T], Mn [ H], Mn [m] or Mn [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Fe, Co or Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R-R are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R! -R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Mn or Ru, then R is a group having the formula -NR TI and R is a group having the formula -NR R wherein R a R is independently selected from hydrogen , halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4 R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents; and characterized in that the formation of the supported catalyst is achieved by treating the nitrogenous transition metal compound defined above with alumoxane in an inert volatile hydrocarbon diluent, by grinding the particulate support material with the product and evaporating the volatile diluent. 20. A catalyst according to claim 18 or 19, characterized in that it has the form of a free-flowing powder. 21. A catalytic system characterized in that it comprises the catalyst claimed in any of the preceding claims and in addition it comprises (3) a neutral Lewis base. 22. A polymerization catalyst characterized in that it comprises: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds; and (3) a neutral Lewis base - (T / b) .X where M [T] is Fe |?], Fe [m], Co [I], Co [lT], Co [m], Ru [H], Ru [l?], Ru [TV], Mn [ I], Mn [lT], Mn [ip] or Mn [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of Rx-R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R ^ R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when any of the ring systems P and Q is part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Mn or Ru, then R is a group having the formula -NR Tl and R is a group having the formula -NR31R32 wherein R29 to R32 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents. 23. A catalytic system comprising the catalyst claimed in claim 21 or 22, characterized in that the neutral Lewis base is a tertiary amine or an aromatic ester. 24. A process for the polymerization of 1 -defines, characterized in that it comprises contacting the monomeric olefin under polymerization conditions with the polymerization catalyst claimed in any of the preceding claims. 25. A process according to claim 24, characterized in that the monomer is ethylene, propylene, butene, hexene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate or styrene. 26. A process for the copolymerization of 1-olefins, characterized in that it comprises contacting the monomeric olefins, under polymerization conditions, with a polymerization catalyst comprising: (1) a nitrogenous transition metal compound having the following Formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Fe [II], Fe [m], Co [I], Co [H], Co [m], Ru [E], Rupp], Ru [TV], Mn [I ], Mn [II], Mn [III] or Mn [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R'-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R19, R20, R21 and R22 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR R wherein R to R are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents. 27. A process according to claim 26, characterized in that the compound of formula B is defined as in any of claims 1 to 22. 28.- A process according to claim 26 or 27, characterized in that the activating compound comprises a compound of trialkylaluminum, preferably an alumoxane, or tetra (phenyl) borate dimethylphenylammonium, tetra (phenyl) borate TRIFILO, triphenylboron, tetra (pentafluorophenyl) borate dimethylphenylammonium, tetrakis [(bis-3, 5-trifluoromethyl) phenyl] borate, H + (OEt2) [(bis-3,5-trifluoromethyl) phenyl] borate, tetra (pentafluorophenyl) borate, trifyl and tris (pentafluorophenyl) boron. 29. A process according to any of claims 26 to 28, characterized in that the ethylene is copolymerized with another 1-olefin selected from propylene, 1-butene, 1-hexene, 4-methylpentene-1 and octene. 30. A process according to any of claims 24 to 29, characterized in that hydrogen gas is added to the polymerization to control the average molecular weight of the polymer produced. 31.- A process for the polymerization of 1-olefins, which comprises contacting the monomeric olefin, under polymerization conditions, with a polymerization catalyst comprising: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, Formula B where M [T] is Fe [H], Fe [HT], Co | TJ, Co [H], Co [HTJ, Ru [lT], Ru [IH], RupV], Mn [I], Mh | rj, Mn [lilj or Mn [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Ru, then R3 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of R ^ R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R5 is represented by the group "P" and R7 is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R? o, R p, R * 7 and R? J is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when neither of the ring systems P and Q forms part of a polyaromatic system condensed rings; - or in such a way that (3) when M is Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R32 are independently selected from hydrogen, halogen , hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents; characterized in that hydrogen gas is added to the polymerization to control the average molecular weight of the polymer produced. 32. A process according to any of claims 24 to 31, characterized in that the polymerization temperature is from 50 to 120 ° C and the pressure is from 10 to 50 bar. 33. A process according to any of claims 24 to 32, characterized in that the polymerization conditions are phase conditions in solution, phase in slurry or gas phase. 34.- A process for the polymerization of 1-olefins, which comprises contacting the monomeric olefin, under polymerization conditions, with a polymerization catalyst comprising: (1) a nitrogenous transition metal compound having the following formula B; and (2) an activating amount of an activating compound selected from organoaluminum compounds and hydrocarbylboro compounds, where M [T] is Fe [H], FefllT], Co | TJ, Co [ü], Co [m], Ru [lTJ, Ru [lTI], Ru [TV], Mn | TJ, Mn [H ], Mn [DTJ or Mn [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and R6 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; - and in such a way that (1) when M is Ru, then R5 and R7 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more any of Rx-R7 may be linked to form one or more cyclic substituents; - or in such a way that (2) when M is Mn or Ru, then R is represented by the group "P" and R is represented by the group "Q" as follows: wherein R19 to R28 are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R, R, R and R is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q forms part of a condensed ring polyaromatic system; - or in such a way that (3) when M is Mn or Ru, then R5 is a group having the formula -NR29R30 and R7 is a group having the formula -NR31R32 wherein R29 to R, 3"2 are independently chosen between hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when any two or more of R to R4, R and R2 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, such two or more groups may be linked to form one or more cyclic substituents, characterized in that the polymerization conditions are in the gaseous phase: A process according to claim 33 or 34, characterized in that the polymerization is carried out under gas-phase fluidized-bed conditions. - A process according to claim 35, characterized in that a volatile liquid is fed to the fluidized bed under conditions such that the liquid evaporates in the bed absorbing or with it more heat of polymerization of the bed. 37.- A process according to claim 36, characterized in that the volatile liquid is condensed in a heat exchanger. 38.- A process according to claim 37, characterized in that said volatile liquid is separated from the recycle gas. 39.- A process according to claim 38, characterized in that said volatile liquid is sprayed into the bed. 40.- A process according to claim 37, characterized in that said volatile liquid is recycled to the bed with recycle gas. 41. A process according to claim 35, characterized in that hydrogen gas is added to the polymerization to control the average molecular weight of the polymer produced. 42. A process according to any of claims 35 to 41, characterized in that the fluidizing gas for the fluidized bed contains an inert gas. 43.- A process according to claim 42, characterized in that the inert gas comprises nitrogen or pentane. 44.- A process according to any of claims 35 to 43, characterized in that the catalyst, or one or more of the components used to form the catalyst, are introduced into the polymerization reaction zone in liquid form, and the liquid containing The component (s) is sprayed as fine droplets in the polymerization zone. 45.- A process according to claim 35, characterized in that the polymerization temperature is from 50 to 120 ° C and the pressure is from 10 to 50 bar. 46.- A polyethylene powder containing a catalyst comprising a nitrogenous iron complex, characterized in that the concentration of iron is from 1.03 to 0.11 parts by weight of iron per million parts by weight of polyethylene. 47.- A polyethylene powder according to claim 46, characterized in that the catalyst is the catalyst claimed in any of claims 1 to 23. 48.- A polyethylene powder according to claim 47, characterized in that the complex can be obtained from of a nitrogenous transition metal compound of formula B as defined in claim lo or. 49.- A nitrogenous transition metal compound characterized in that it comprises the skeletal unit illustrated in formula B where M is Ru [H], RuflQ] or Ru [IV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1, R2, R3, R4 and Rd are independently chosen from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and R5 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. 50.- A nitrogenous transition metal compound according to claim 49, characterized in that R1 to R4, R6 and R19 to R28 are independently chosen from hydrogen and hydrocarbyl Ci to Cg. 51. A nitrogenous transition metal compound according to claim 49 or 50, characterized in that R1 to R4, R6 and R19 to R28 are independently selected from methyl, ethyl, n-propyl, n-butyl, n-hexyl and n- octyl. 52. A nitrogenous transition metal compound according to any of claims 49 to 51, characterized in that R5 and R7 are independently chosen from phenyl, 1-naphtyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6- diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2-t-butylphenyl, 2, 6-diphenylphenyl, 2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5-dichloro-2,6-diethylphenyl and 2,6-bis (2,6- dimethylphenyl) phenyl, cyclohexyl and pyridinyl. 53.- The 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl2 complex. 54.- A nitrogenous transition metal compound, characterized in that it comprises the skeletal unit illustrated in formula Z: Formula Z where M is Mn [I], Mn [H], Mn [IlTJ, Mn [rV], Ru [p], Ru [Hrj or Ru [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4. R6 and R19 to R28 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R19 to R28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more such groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R, R, R and R is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems P and Q is part of a condensed ring polyaromatic system. 55.- A nitrogenous transition metal compound according to claim 54, characterized in that R1 to R4, R6 and R19 to R28 are independently chosen from hydrogen and hydrocarbyl G to Cs, such as methyl, ethyl, n-propyl, n-butyl , n-hexyl and n-octyl. 56. A nitrogenous transition metal compound according to claim 54, characterized in that at least one of R19 and R20 and at least one of R21 and R22 is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl and because none of the ring systems P and Q are part of a polyaromatic ring system. 57. A nitrogenous transition metal compound according to claim 54, characterized in that R19, R20, R21 and R22 are each selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. 58. - A nitrogenous transition metal compound, characterized in that it comprises the skeletal unit illustrated in formula T: Formula T where M is Mn | T], Mn [IT], Mn [IH], Mn [IV], Ru [ITJ, Ru [IH] or Ru [TV]; X represents an atom or group bonded covalently or ionically to the transition metal M; T is the oxidation state of the transition metal M and b is the valence of the atom or group X; R1 to R4, R6 and R29 to R32 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more such groups may be linked to form one or more cyclic substituents. 59.- Use of a compound as defined in any of claims 54 to 58 as a catalyst for the polymerization or copolymerization of 1-olefins.