MXPA00012012A

MXPA00012012A - Supported group 8-10 transition metal olefin polymerization catalysts

Info

Publication number: MXPA00012012A
Application number: MXPA/A/2000/012012A
Authority: MX
Inventors: Peter Borden Mackenzie; Leslie Shane Moody; Christopher Moore Killian; Gino Georges Lavoie
Original assignee: Eastman Chemical Company
Priority date: 1998-06-01
Filing date: 2000-11-30
Publication date: 2001-09-07

Abstract

Methods for preparing olefin polymers, and catalysts for preparing olefin polymers are disclosed. The polymers can be prepared by contacting the corresponding monomers with a Group 8-10 transition metal catalyst and a solid support. The polymers are suitable for processing in conventional extrusion processes, and can be formed into high barrier sheets or films, or low molecular weight resins for use in synthetic waxes in wax coatings or as emulsions.

Description

TRANSITION METAL OLEFIN POLYMERIZATION CATALYSTS OF GROUP 8-10 SUPPORTED DESCRIPTION OF THE INVENTION The present invention is directed to complexes containing transition metal of group 8-10, their use in olefin polymerizations, and to novel olefin polymers produced for the same. Olefin polymers are used in a wide variety of products, wire cover and film cable. Olefin polymers are used, for example, in injection or compression molding applications, in extruded or coated films, such as paper extrusion coatings, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have been made possible for better control polymerization processes, and therefore, the properties of the bulk material influence. Increasingly, efforts have been made in accordance with the plastic properties of clarity, strength, corrosion resistance, permeability, optical properties, and the like, for particular uses. Chain length, polymer branching and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic processes for polymerization olefins that allow more efficiency and better controlled polymerization of olefins. Conventional polyolefins are prepared by a variety of polymerization techniques, including homogeneous liquid phase, gas phase, and suspension polymerization. Certain transition metal catalysts, such as those based on titanium compounds (eg, TiCl or TiCl 4) in combination with organoaluminum cocatalysts, are used to make linear and linear low density polyethylenes as well as poly-α-olefins such as polypropylene. These so-called "Ziegler-Natta" catalysts are completely sensitive to oxygen and are ineffective for the copolymerization of polar and non-polar monomers. Recent advances in olefin polymerization catalysis without Ziegler-Natta include the following LK Johnson et al., Patent Application WO 96/23010, describes the polymerization of olefins using cationic nickel, palladium, iron and cobalt complexes, which contain ligands of diimine and bisoxazoline. This document also describes the polymerization of ethylene, acyclic olefins, and / or selected cyclic olefins and optionally selects unsaturated acids or esters such as acrylic acid or alkyl acrylates to provide olefin homopolymers or copolymers.

European Patent Application Serial No. 381,495 describes the polymerization of olefins using palladium and nickel catalysts containing selected bidentate phosphors containing ligands. L.K. Johnson et al., J. Am. Chem. Soc. , 1995, 11 1, 6414, describes the polymerization of olefins such as ethylene, propylene, and 1-hexene using cationic nickel and palladium complexes based on α-diimine. These catalysts have been described for polymerizing ethylene to high molecular weight polyethylene. In addition to ethylene, the Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate. G. F. Schmidt et al., J. Am. Chem. Soc. 1985, 107, 1443, discloses a cobalt (III) cyclopentadienyl catalyst system having the structure [C5Me5 (L) CoCH2CH2-μ-H] +, which is provided for the "living" polymerization of ethylene. M. Brookhart et al., Ma chromolecules 1995, 28, 5378, describes using such "living" catalysts in the synthesis of functionalized end polyethylene homopolymers. U. Klabunde, U.S. Patent Nos. 4,906,754, 4,716,205, 5,030,606 and 5,175,326 describe the conversion of ethylene to polyethylene using anionic phosphors, oxygen donors bound to Ni (II). The polymerization reactions were continued between 25 and 100 ° C with modest yields, producing linear polyethylene having a weight average molecular weight varying between 8K and 350 K. In addition, Klabunde describes the preparation of ethylene copolymers and functional group containing monomers. . Peuckert et al., Organo et. 1983, 2 (5), 594 describes the oligomerization of ethylene using phosphine, Ni (II) -linked carboxylate donors, which show modest catalytic activity (0.14 to 1.83 TO / s). The oligomerizations were carried out at 60 to 95 ° C and from 10 to 80 bars of ethylene in toluene, to produce α-olefins. R. E. Murray, U.S. Patent Nos. 4,689,437, and 4,716,138 describe the oligomerization of ethylene using phosphine, sulfonate donors bound to Ni (II). These complexes show catalytic activities approximately 15 times greater than those reported with phosphine, carboxylate analogues. W. Keim et al., Angew. Chem. Int. Ed. Eng. 1981, , 116, and V.M. Mohring, et al., Angew, Chem. Int. Ed. Eng. 1985, 24, 1001, describes the polymerization of ethylene and the oligomerization of α-olefins with aminobis (imino) phosphorane nickel catalysts; G. Wilke, Angew. Chem. In t. Ed.

Engl. 1988, 21, 185, discloses a nickel allylphosphine complex for the polymerization of ethylene. K.A.O. Starzewski et al., Angew. Chem. In t. Ed.

Engl. 1987 26, 63, and U.S. Patent 4,691,036 describe a series of nickel bis (ylide) complexes, used to polymerize ethylene to provide linear high molecular weight polyethylene. Patent Application WO 97/02298 describes the polymerization of olefins using a variety of neutral N, O, P or S donor ligands, in combination with a nickel compound (0) and an acid. Brown et al., WO 97/17380 discloses the use of Pd a-diimine catalysts for the polymerization of olefins including ethylene in the presence of air and moisture. Fink et al., Patent of the United States No. 4,724,273, have described the polymerization of α-olefins using aminobis (imino) phosphorane nickel catalysts and the resulting poly (α-olefin) compositions. Recently, Vaughan et al. WO 9748736, Dentón et al. WO 9748742, and Sugimura et al. WO 9738024 has described the polymerization of ethylene using supported silica from α-diimine nickel catalysts. Additional recent developments are described by Sugimura et al., In JP96-84344, JP96-84343, by Yorisue et al., In JP96-70332, by Canich et al. WO 9748735, McLain et al. WO 9803559, Weinberg et al. WO 9803521 and by Matsunaga et al. WO 9748737. Notwithstanding these advances in catalysis without Ziegler-Natta, there is a need for efficient and effective group 8-10 transition metal catalysts to effect polymerization in olefins. In addition, there is a need for novel methods of polymerization olefins employing such effective Group 8-10 transition metal catalysts. In particular, there is a need for the Group 8-10 transition metal olefin polymerization catalysts with improved temperature stability and functional group compatibility. In addition, there is a need for a polymerization olefin method using effective Group 8-10 transition metal catalysts in combination with a Lewis acid as well as to obtain a catalyst that is more active and more selective. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of the weight fraction and fraction-L? N of cumulative weight versus temperature in degrees Celsius for four polyethylene samples. The following general procedure was used to generate this graph: These data were collected using a Polymics ™ CAP-TREF system (Fractionation of Temperature Elevation Elution), preparing first a percent of polymer solution in 1, 2, 4-trichlorobenzene. The samples were dissolved at 150 ° C for two hours. An appropriate amount of CHROMASORB ™ P was added to the solution, placed in a temperature controlled oven and cooled at a rate of 2 ° C per hour from 150 ° C to 30 ° C. The TREF analysis was performed by heating the material at 200 ° C per hour at a solvent flow rate (1, 2, 4-trichlorobenzene) of 20 mL per minute. The weight fraction was determined by the transmittance in percent of an infrared beam (3.41 μm). Curve 1 is the weight fraction as a function of temperature of a polyethylene made in solution using catalyst XXVII, at 80 ° C and 600 psig (ethylene) as per Example 196. The average branch of 45 branches / 1000 carbon atoms , as determined by XH NMR. Curve 2 is the weight fraction as a function of temperature of a polyethylene made in solution using catalyst XXVII, at 80 ° C and 600 psig (ethylene) as per Example 197. The average branch of 45 branches / 1000 carbon atoms , as determined by XH NMR. Curve 3 is the fraction by weight as a function of temperature of a polyethylene made in the gas phase using the catalyst XXVII supported with silica, at 100 ° C and 100 psig (ethylene), as per Example 136. The branch-average of 45 branches / 1000 carbon atoms, as determined by 1 H NMR. Curve 4 is the weight fraction as a function of temperature of a polyethylene made in the gas phase using catalyst XXVII supported in silica, at 100 ° C and 100 psig (ethylene), as for Example 150. The average branching of 47 branches / 1000 carbon atoms, as determined by 1 H NMR. The curve la is the cumulative weight fraction as a function of temperature for a polyethylene prepared in solution using catalyst XXVII, at 0 ° C and 600 psig (ethylene), as per Example 196. The average branch of 45 branches / 1000 atoms of carbon, as determined by 1H NMR. Curve 2a is the cumulative weight fraction as a function of temperature for a polyethylene prepared in solution using catalyst XXVII, at 80 ° C and 600 psig (ethylene) as per Example 197. The average branch of 45 branches / 1000 carbon atoms. carbon, as determined by XH NMR. Curve 3a is the cumulative weight fraction as a function of temperature for a polyethylene prepared in the gas phase using catalyst XXVII supported on silica, at 100 ° C and 100 psig (ethylene), as for Example 136. The average branch of 45 branches / 1000 carbon atoms, as determined by 1 H NMR. Curve 4a is the cumulative weight fraction as a function of temperature for a polyethylene prepared in the gas phase using catalyst XXVII supported on silica, at 100 ° C and 100 psig (ethylene), as for Example 150. The average branch of 47 branches / 1000 carbon atoms, as determined by 1 H NMR. Figure 1 illustrates the only compositions prepared in the gas phase using supported catalysts of the present invention. The polymers prepared using homogeneous catalyst in solution (ie, 1 and 2) dissolved over a relatively narrow temperature ra while that prepared using a supported catalyst -in the gas phase (ie, 3 and 4) dissolved over a raof much wider temperature. Thus, the comparison of curves 1 and 2 against curves 3 and 4 indicates the existence of a narrow composition distribution rafor polyethylene made in solution, in contrast defined with polyethylenes prepared using gas phase polymerization while using the same Transition metal complex when attached to a solid support. As can be seen in Figure 1, curves 3 and 4 represent dissolution over a much larger temperature ra evidence of a much wider composition distribution. In this regard, such polymer compositions provide a unique blend of properties, i.e., an impact balance, strength, elasticity, tear resistance, and puncture resistance, which are particularly desired for such extreme uses as film, packaging , coating, etc. In one embodiment, the present invention provides a catalyst for the polymerization of olefins comprising a complex comprising (a) a ligand of the formula X, (b) a transition metal of the group 8-10, and optionally (c) a Bronsted or Lewis acid. 1 R and R are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl; N represents nitrogen; and A and B are each, independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is attached to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order to form the catalyst. In the above catalyst, it should be appreciated that the transition metal of Group 8-10 is coordinated therewith to a bidentate ligand having the formula X and that the Bronsted or Lewis acid is optionally reactive with this metal ligand complex. In addition, Bronsted or Lewis acid can optionally be combined with the X-ligand prior to complexation of the transition metal of Group 8-10. In one embodiment, the invention provides a catalyst for the polymerization of olefins comprising the reaction product of a compound of the formula XII, a compound Y and a solid support: XII R1 and R6 each independently represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q "or W" to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion. As a further aspect of the invention, there is provided a process for the preparation of a supported catalyst comprising contacting a transition metal complex of the group 8-10 of a ligand of the formula X, a solid support, and optionally a Bronsted or Lewis acid. 1 fi wherein R and R are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl; N represents nitrogen; and A and B are each, independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is bound to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order to form the supported catalyst. In a further embodiment, a process is provided for the preparation of a supported catalyst comprising the reaction product of a compound of the formula XII, a compound Y and a solid support; XII R1 and R6 each, independently, represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q ~ or W "to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid , whose conjugate base is a weakly coordinating anion In a further embodiment, a process for the polymerization of olefins is provided, comprising contacting one or more monomers of the formula RCH = CHR8 with a catalyst comprising a metal complex transition group 8-10, a ligand of formula X and optionally a Bronsted or Lewis acid. wherein R and R each independently represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin; R1 and R6 each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl; N represents hydrogen; Y A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is attached to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order. In a preferred embodiment, the present invention provides a process for the polymerization of olefins, which comprises contacting one or more monomers of the formula RCH = CHR8 with the reaction product of a compound of the formula XII, a compound Y and a solid support: XII wherein R and R8 each independently represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin; R1 and R6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q ~ or W "to form a weakly coordinating anion, a cationic Lewis acid, whose counter ion is a weakly coordinating anion, and an acid Bronsted, whose conjugate base is a weakly coordinating anion In a further embodiment, the present invention provides a process for the polymerization of olefins, comprising contacting one or more monomers of the formula RCH = CHR8 with a support catalyst formed by combining a compound of formula XII: XII with a solid support which has been pre-treated with a compound Y, wherein R and R each independently represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and can be linked to form a cyclic olefin R1 and R6 each, independently, represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid, capable of abstracting Q ~ or W ~ to form a weakly coordinating anion, a cationic Lewis acid, whose counter ion is a weakly coordinating anion, and an acid Bronsted whose conjugate base is a weakly coordinating anion. In a further embodiment, a process for the copolymerization of one or more olefin monomers of the RCH = CHR8 type with one or more functional olefin monomers of the formula CH2 = CH (CH2) nJ comprising a catalyst, in a polymerization reaction of olefin comprising combining a complex of formula XII, a solid support, and optionally a compound Y, before the use of such a catalyst in the reaction of. olefin polymerization. wherein R and R8 each independently represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin; n is an integer between 1-20; J is a group selected from ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, arylamine, alkylamido, arylamido, alkylimido, arylimido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxythiol, thioalkoxy , acid, urea, sulfonamido and sulphoester; XII 1 f R and R each independently represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of a neutral Lewis acid, capable of abstracting Q or W ~ to form a weakly coordinating anion, a cationic Lewis acid, whose counter ion is a weakly coordinating anion, and an acid Bronsted whose conjugate base is a weakly coordinating anion. In another preferred embodiment, the present invention provides a process for the copolymerization of ethylene and a comonomer of the formula CH2 = CH (CH2) nC02R1 comprising contacting ethylene and a comonomer of the formula CH2 = CH (CH2) nC02R1 with a supported catalyst formed by combining silica with a compound of formula XII and optionally a compound Y; XII wherein R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, or silyl; n is an integer between 1-20; R1 and R6 each independently represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of a neutral Lewis acid, capable of abstracting QX or W ~ to form a weakly coordinating anion, a cationic Lewis acid, whose counter ion is a weakly coordinating anion, and an acid Bronsted whose conjugate base is a weakly coordinating anion.

In another preferred embodiment, the above process is provided wherein the compound of formula XII is represented by formula XXIV.

XXIV wherein R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, or can collectively form a bridging hydrocarbyl, substituted bridging hydrocarbyl, or a substituted silicon atom; Q is alkyl, chloride, iodide or bromide; W is alkyl, chloride, iodide or bromide; N is nitrogen; Z is sulfur or oxygen; and M is Ni (II). In another preferred embodiment, a supported catalyst comprising the reaction product of a compound of the formula V, VIII, or XV is provided: V VIII XV wherein R1 and R6 each independently represent a sterically hindered aryl; R2 / 3 and R each independently represents hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and moreover can collectively form a bridging hydrocarbyl, substituted bridging hydrocarbyl, or a substituted silicon atom; Q represents a hydrocarbyl, chloride, iodide or bromide; W represents a hydrocarbyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); with a solid support which has been pre-treated with a compound Y, where Y is selected from the group consisting of a neutral Lewis acid capable of abstracting Q ~ or W ~ to form a weakly coordinating anion, a Cationic Lewis acid whose counter ion is a weakly coordinating anion; and a Bronsted acid whose conjugate base is a weakly coordinating anion. In an especially preferred embodiment, the compound of formula XII is selected from the group consisting of XXVII wherein R1 and R6 are 2,6-dimethylphenyl; XXVIII wherein R1 and R6 are 2,6-diisopropylphenyl; XXXII wherein R1 and R6 are 2,6-dimethylphenyl; XXXIII wherein R1 and R6 are 2,6-diisopropylphenyl; XXXVIII wherein R, 1 and R are 2,6-dimethylphenyl; Y XXXIX wherein R1 and R6 are 2,6-diisopropylphenyl. The catalysts used in the processes of the present invention readily convert ethylene and α-olefins to high molecular weight polymers, and allow olefin polymerizations under various conditions, including temperature and ambient pressure, including gas phase and suspension (e.g. of suspension). As noted herein, it is preferred that the compounds of the present invention be attached to a solid support which has been pre-treated with a compound Y, for example, MAO, or mixed with Y in any order. It has been found that when such support catalysts are used in suspension and gas phase ethylene polymerizations, novel polymer compositions are provided insofar as such compositions are mixtures of different polyolefin polymers. It is believed that when such catalysts are attached to a solid support, such as silica, olefin polymerizations using such supported catalyst provide a polymer composition having a broad compositional distribution. This is believed to be due at least in part to the creation of unique reaction sites, and the sensitivity of these catalysts to the ethylene concentration. These unique reaction sites are believed to result from the unique microenvironments created by the location of the catalyst in the support. The resulting polymeric composition, which can be prepared solely from ethylene as an olefin feedstock, in one which is presently a mixture or plurality of polymers having a variety of branched alkyl distributions with some catalytic sites giving less branched polymer high density and other sites giving more low density branched polymer. The present invention also provides novel polyalkene compositions. Thus, in one embodiment, the present invention provides polyethylene composition comprising a mixture of polyethylene polymers, wherein the mixture has an average degree of branching of from 5 to 120 branches of alkyl per 1000 carbon atoms, wherein any individual component of the mixture has a degree of branching from 0 to 150 alkyl branches per 1000 carbon atoms, wherein the polymers are prepared in a reaction vessel, solely from ethylene, and wherein the polymers are prepared using a catalyst of Group 8-10 transition metal supported on a solid support which has been pre-treated with a compound Y selected from the group consisting of methylaluminoxane and other aluminum sesquioxides having the formulas R73A1, R72A1C1, and R7A1C12, in where R7 is alkyl. The transition metal is preferably Ni and the compound Y is methylaluminoxane. A further embodiment of the invention provides a polyethylene composition comprising a mixture of polyethylene polymers, wherein the mixture has an average degree of branching of from 5 to 120 alkyl branches per 1000 carbon atoms, wherein any individual component of the The mixture has a degree of branching of 0 to 150 branches of alkyl per 1000 carbon atoms, wherein the polymers are prepared in a reaction vessel, solely of ethylene, and wherein the polymers are prepared using a Group 8-10 transition metal catalyst, which has been reactive with a solid support and a Y compound, in any order, wherein Y is selected from the group consisting of methylaluminoxane and other aluminum sesquioxides have the formulas R73A1, R72A1C1, and R7A1C12, wherein R7 is alkyl. In addition, the catalyst of this invention when supported in this form and used in a gas phase or suspension process provides polymers that have a broad composition distribution while having an intermediate molecular weight distribution., thus providing certain processing advantages. When fractionated based on solubility using supercritical propane by isothermy increasing profiles and elution fractions of temperature elevation, critical, isobaric, in ten fractions, an analysis for such fractions provides data on the distribution of the relative branching of the components of the composition . Thus, in a further embodiment, a polyolefin is provided which when fractionated based on solubility using supercritical propane by isothermia increasing profiles and fractionation of elution by raising critical, isobaric temperature, in ten fractions between about 40 and about 140 ° C, where a first fraction taken at about 40 ° C has between about 40 and about 100 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 at about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 and about 15% are pentyl or longer branches.; a second fraction taken between about 40-60 ° C has between about 30 and about 90 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 and about 15% are pentyl or longer branches; a third fraction taken between about 60-65 ° C has between about 30 and about 80 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a fourth fraction taken between about 65-70 ° C has between about 20 and about 60 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a fifth fraction taken between about 75-85 ° C has between about 10 and about 50 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a sixth fraction taken between about 85-95 ° C has between about 10 and about 40 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a seventh fraction taken between about 95-100 ° C has between about 5 and about 35 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; an eighth fraction taken between about 100-110 ° C has between about 0 and about 25 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 0 to about 15% are pentyl or longer branches; a ninth fraction taken between about 110-140 ° C has between about 0 and about 30 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 0 to about 15% are pentyl or longer branches; a tenth fraction taken between about 140-150 ° C has between about 0 and about 20 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; and a tenth fraction between about 0 and about 20 branches per 1000 carbon atoms. In contrast to a polymer prepared by solution polymerization, wherein the melting temperature as defined by the endothermic maximum is inversely correlated with the average degree of branching of the polymer, the polymers prepared from the supported catalysts of the present invention exhibit a relatively constant melting temperature (maximum endothermic) over a relatively wide range of average branching. In certain cases, this also provides a free fluid powder which is again, a significant processing advantage in the gas phase. In a preferred embodiment, a polymer derived from essentially single ethylene having more than 30 branches per 1000 carbon atoms and a melting transition (maximum endothermic) in the DSC of more than about 110sC is provided. Preferably, the polymer is a free flowing polymer. In a further embodiment, a single ethylene derivative polymer having a broad composition distribution and a molecular weight distribution of less than 6 and more than 2.5 is provided, wherein the polymer has a branching degree of from 5 to 120 branching. alkyl by 1000 carbon atoms, and wherein any individual component of the polymer has a degree of branching of from 0 to 150 alkyl branches per 1000 carbon atoms. In such polymer compositions, it is preferred that an individual component of the polymer have between about 40 and 100 branches per 1000 carbon atoms, another component has between about 30 and 90 branches per 1000 carbon atoms, another component has between 30 and 80 branches per 1000 carbon atoms, another component has between about 20 and 60 branches per 1000 carbon atoms, another component has between about 10 and 50 branches per 1000 carbon atoms, another component has between about 10 and 40 branches per 1000 carbon atoms , another component has between about 5 and 35 branches per 1000 carbon atoms, another component has between about 0 and 25 branches per 1000 carbon atoms, another component has between about 0 and 30 branches per 1000 carbon atoms, another component has between approximately 0 and 20 branches per 1000 atoms carbon. It is also recognized that by joining a Group 8-10 polymerization catalyst to a solid support one can improve its functional group compatibility over that observed in the homogeneous solution polymerization. In other words, the speed for the copolymerization of one or more olefin monomers of the RCH = CHR8 type with one or more functional olefin monomers of the CH2 = CH (CH2) nJ type is increased over the homogeneous solution polymerization running under other identical conditions. In particular, it has been found that to use a Group 8-10 support catalyst those monomers of the general formula CH2 = CH (CH2) nJ are copolymerized with other olefins (eg, ethylene) at rates of various orders of magnitude greater than those observed by corresponding homogeneous systems. In this regard, examples of Group 8-10 catalysts useful in this process include those described in U.S. Patent Nos. 5,866,663; 5,886,224; 5,891,963; 5,880,323; 5,880,241, are incorporated herein by reference, together with WO9623010, WO9910391, WO 9905189, WO 9856832, WO 9803559, WO 9847934, WO9702298, WO 9830609, WO 9842665, WO 9842664, WO 9847933, WO 9840420, WO 9840374. Thus, in a preferred embodiment, a Group 8-10 transition metal catalyst having an improved speed for the copolymerization of one or more olefin monomers of the RCH = CHR8 type with one or more functional olefin monomers of the formula CH2 is provided. = CH (CH2) nJ in an olefin polymerization reaction comprising combining the catalyst with a solid support, and optionally a Bronsted or Lewis acid in any order, before using the catalyst in the olefin polymerization reaction. wherein R and R8 each independently represent a hydrogen, a hydrocarbyl or fluoroalkyl, and may be linked to form a cyclic olefin; n is an integer between 1-20; J is a group selected from ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, arylamine, alkylamido, arylamido, alkylimido, arylimido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxythiol, thioalkoxy , acid, urea, sulfonamido, and sulfoester. Preferably, the compound of the formula CH2 = CH (CH2) nJ is a compound of the formula CH2 = CH (CH2) nC02R1, wherein R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl; and n is an integer greater than 3; In a further embodiment, the present invention provides a homopolymer of ethylene with a CDB1 of less than 50%, preferably less than 40% and more preferably less than 30%. In a further embodiment, the present invention provides a polyalkylene with a CDB1 of less than 50%, which contains about 80 to about 150 branches per 1000 methylene groups, and which contains per 100 branches which are methyl, about 30 to about 90. ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl branches or longer. More preferably, it is a polyalkene of a CDBl of less than 40%, more preferably less than 30%. More preferred are those polyalkenes containing about 100 to about 130 branches per 1000 methylene groups, and containing for every 100 branches which are methyl, about 50 to about 75 ethyl branches, about 5 to about 15 propyl branches, about 24. to about 40 butyl branches, about 5 to about 10 amyl branches, and about 65 to about 120 hexyl branches or longer. In a further embodiment, a polyalkene is provided with a CDBl of less than 50%, which contains about 20 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 20 branches of ethyl, about 12 ramifications of propyl, 1 about 12 ramifications of butyl, 1 about 10 ramifications of amyl, and 0 about 20 ramifications of hexyl or longer. More preferred are polyalkenes with a CDBl of less than 40%, more preferably less than 30%. More preferred embodiments include polyalkenes containing about 40 to about 100 branches per 1000 methylene groups, and containing for every 100 branches which are methyl, about 6 to about 15 ethyl branches, about 2 to about 10 propyl branches, about 2. to about 10 butyl branches, about 2 to about 8 amyl branches, and about 2 to about 15 hexyl branches or longer. The polymers of the present invention include definition homopolymers, such as polyethylene, polypropylene, and the like, and olefin copolymers, including copolymers containing a functional group. As an example, ethylene homopolymers can be prepared severely linear to highly branched structures by varying the catalytic structure, co-catalytic composition, and reaction conditions, including pressure and temperature. The effect of these parameters is on the structure of the polymer described herein. These polymers and copolymers have a wide variety of applications, including use as packaging material and in adhesives. In this description certain chemical groups or compounds are described by certain terms and symbols. These terms are defined as follows: Symbols ordinarily used to denote elements in the Periodic Table take their ordinary meaning, unless otherwise specified. So, N, 0, S, P, and Si symbolize nitrogen, oxygen, sulfur, phosphorus and silicon, respectively. Examples of neutral Lewis acids include, but are not limited to, methylaluminoxane (hereinafter MAO) and other aluminum sesquioxides R73A1, R72A1C1, R7A1C12 (where R7 is alkyl), organoboron compounds, boron halides, B (C6F5 ) 3, BPh3, and B (3, 5- (CF3) 2C6H3) 3. Examples of ionic compounds comprising a cationic Lewis acid include: R93Sn [BF], (wherein R9 is hydrocarbyl), MgCl2 and H + X ~, where X "is a weakly coordinating anion The term" weakly coordinating anion "is well known in the art per se and generally refers to a long bulky anion capable of delocalising the negative charge of the anion. Suitable weakly coordinating anions include, but are not limited to, PF6X BF4? SbF5X (PH) 4B ~ where Ph = phenyl, "BAr4 where ~ BAr4 = tetrakis [3,5-bis (trifluoromethyl) phenyljborane. The coordination capacity of such anions is known and described in the literature (Strauss, S. et al., Chem. Rev. 1993, 93, 927). Examples of neutral Lewis bases include, but are not limited to, (i) ethers, e.g., diethyl ether or tetrahydrofuran, (ii) organic nitriles, e.g., acetonitrile, (iii) organic sulfides, e.g., dimethylsulfide, or ( iv) monoolefins, for example, ethylene, hexene or cyclopentene. A "hydrocarbyl" group means a monovalent or divalent, linear, branched or cyclic group containing only carbon and hydrogen atoms. Examples of monovalent hydrocarbyls include the following: C 1 -C 2 alkyl; C1-C20 alkyl substituted with one or more groups selected from CI-C2O alkyl? C3-Cs cycloalkyl or aryl; C3-C8 cycloalkyl; C3-C8 cycloalkyl substituted with one or more groups selected from C? -C20 alkyl, C3-C8 cycloalkyl or aryl; C6-C aryl ?; and C6-C aryl? substituted with one or more groups selected from C 1 -C 2 alkyl, C 3 -C 8 cycloalkyl, or aryl; wherein the term "aryl" preferably denotes a phenyl, naphthyl, or anthracenyl group. Examples of divalent (bridge) hydrocarbyls include: -CH2-, -CH2CH2-, -CH2CH2CH-, and 1,2-phenylene. A "silyl" group refers to a SiR3 group wherein Si is silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl, as in Si (SiR3) 3. A "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur, selenium, arsenic, chlorine, bromine, silicon and fluorine. A "substituted hydrocarbyl" refers to a monovalent or divalent hydrocarbyl substituted with one or more heteroatoms. Examples of substituted monovalent hydrocarbyl include: 2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6 -difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl, 4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2,6-dimethyl -4-trifluoromethylphenyl, 2,6-dimethyl-4-trimethylammonium-phenyl (associated with a weakly coordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl, 2-chloronat-1-yl , 4-methoxyphenyl, 4-nitrophenyl, 9-nitroantr-10-yl, -CH2OCH3, cyano, trifluoromethyl or fluoroalkyl. Examples of divalent substituted (bridging) hydrocarbyls include: 4-methoxy-1,2-phenylene, 1-methoxymethyl-l, 2-ethanediyl, X 2 -bis (benzyloxymethyl) -1,2-etenediyl, or 1- (4- methoxyphenyl) -1, 2-ethanediyl. A "stearically hindered aryl" means (i) a phenyl ring with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br or silyl substituents at positions 2 and 6, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br , silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, C02Me, C02H, C (O) CH3, CF3, or fluoroalkyl substituents, (ii) a substituted 2-naphth-1-yl ring, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, C02Me, C02H, C (0) CH3, CF3, or fluoroalkyl substituents, (iii) a 9-anthracenyl ring or 1, 2, 3, 4, 5, 6, 7, 8-octahydro-9-anthracenyl, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, C02Me , C02H, C (0) CH, CF3, or fluoroalkyl substituents, or (iv) an aromatic substituted hydrocarbyl with functionally equivalent spherical properties (in the context of this invention) for one or more of the following stearically hindered aryls: 2, 6 -dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,6-dimethyl-4-nitrophenyl, 2,6-dimethyl-4-phenylsulfonylphenyl, 2-isopropyl-6-methylphenyl, 2,6-bis (trifluoromethyl) phenyl, 2,6-dimethyl-4-methoxyphenyl, 2-methylnaphth-1-yl, 9-anthracenyl, 1, 2, 3, 4, 5, 6, 7, 8-octahydro-9-anthracenyl, , 6-dichlorophenyl, 2,6-dibromophenyl, 2-ter-b util-6-methylphenyl, 2-trimethylsilylnaphth-1-yl, 2-chloro-6-methylphenyl, 4-cyano-2,6-dimethylphenyl, 2,6-diisopropyl-4-methoxyphenyl, 2, 4,6-tri- tert-butylphenyl, and 2-chloro-6-tert-butylphenyl. A "radical mono-connected heteroatom" refers to a mono-radical group in which a heteroatom serves as the point of attachment. Examples include: NH (2,6-dimethylphenyl) and SPh, where Ph is phenyl. Numerous other examples are given herein. A "substituted silicon atom" refers to a group -SiR92-, wherein R9 is a hydrocarbyl or substituted hydrocarbyl. A "substituted phosphorus atom" refers to a group -P (0) (OR9) -, wherein R9 is a hydrocarbyl or substituted hydrocarbyl. A "substituted sulfur atom" refers to a group -S (O) -, -S02-, or -S (NR9) 2-, wherein R9 is a hydrocarbyl or substituted hydrocarbyl. A "bridge group" refers to a divalent hydrocarbyl, substituted divalent hydrocarbyl, -C (O) -, -C (S) -, substituted silicon atom, substituted sulfur atom, substituted phosphorus atom, -CH2C (0 ) -, -C (0) C (0) -, or 3,4,5,6-tetrafluoro-1,2-phenylene. In certain cases, the bridging group, together with groups A and B, can collectively form a divalent heteroatom substituted heterocycle; Examples include: A "monoolefin" refers to a hydrocarbon that contains a carbon-carbon double bond. A "suitable metal precursor" refers to a transition metal compound of Group 8-10, preferably Ni, Co, Pd, and Fe compounds, which may be combined with the X compounds (preferably compounds III, VI, IX, XVII or XVIII, described later), and optionally a Lewis or Bronsted acid, to form an active olefin polymerization catalyst. Examples include: (1,2-dimethoxyethane) nickel (II) dibromide, bis [(μ-chloro) (1, 2, 3-? 3-2-propenyl) nickel (II)], bis [(μ-chloro ) -1, 2, 3-? 3-2-propenyl) palladium (II)], bis [(μ-chloro) (1, 2, 3-? 3-l-trimethyl-silyl.oxi-2-propenyl) nickel (II)], CoBr2, FeBr2, bis (acetylacetonate) Ni (II), and [tetrakis (acetonitrile) Pd (II)] [BF]. A "suitable nickel precursor" refers to a suitable metal precursor wherein the metal is nickel.

A "suitable nickel (0) precursor" refers to a suitable metal precursor which is a zero-valent nickel compound. The term "fluoroalkyl" as used herein refers to an alkyl group of C 2 -C 2 or substituted by one or more fluorine atoms. The term "polymer" as used herein means a species comprised of monomer units and have a degree of polymerization (DP) of ten or greater. The term "α-olefin" as used herein is a 1-alkene with 3 to 40 carbon atoms. A "p-allyl" group refers to a monoanionic group with three sp2 carbon atoms bonded to a metal center in a? 3 form. Any of the three sp2 carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected to the hydrocarbyl, heteroatom connected to the substituted hydrocarbyl, or O-silyl group. Examples of p-allyl groups include: C6H5 OSi (CHC 3) '3 The term p-benzyl group means a p-allyl group, wherein two of the sp2 carbon atoms are part of an aromatic ring. Examples of p-benzyl groups include: A polymer with a "broad composition distribution" refers to a polymer comprising a plurality of compositions (preferably > 5) having varying levels of branching. The polymers can be fractionated and the fractions have branching levels / 1000 carbons that range from about 0 to about 100 branches / 1000 carbons. "Distribution Amplitude Index Composition" or CDBl is defined as the weight percent of the polymer molecules that have a branching content within 50% (that is, 25% on each side of the average total branching) of the total average branching of the sample volume as determined by 1H NMR. CDBl is easily determined using well-known fractionation techniques such as fractionation by elution of temperature rise (TREF). (See also WO 97/48735 and WO 93/03093). Sample calculation: -Volume of polymer has 40 branches / 1000 carbon atoms -30 40 50 (degrees of branching within 50% of the average branch for the sample volume). fractionated polymer using TREF or other technique -calculate the percent by weight of the total polymer that has total branches as determined by NMR between 30 and 50, for example, 5 grams of the 10 total grams charged when fractioned and analyzed have branching between 30 and 50 branches / 1000 carbon atoms. The CDBl for this polymer could be 50%. A "free flowing polymer" refers to a non-tacky polymer that can be transported without significant agglomeration. In this context, this lack of significant agglomeration refers to polymer products which are useful under commercial gas phase reactor conditions. As used herein, the terms "monomer" and "olefin monomer" refer to the olefin compound or other previous monomer that has been polymerized; the term "monomer units" refers to the portions of a polymer that correspond to the monomers after they have been polymerized. In some cases, a compound Y is required as a cocatalyst. Suitable Y compounds include a neutral Lewis acid capable of abstracting Q "or W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is an anion weakly coordinating Preferred Y compounds include: methylaluminoxane (hereinafter MAO) and other aluminum sesquioxides, R73A1, R72A1C1, R7A1C12 (wherein R7 is alkyl), organoboron compounds, boron halides, B (C6F5) 3 , R93Sn [BF4] (where R9 is hydrocarbyl), MgCl2, and H + X ~, where X "is a weakly coordinating anion. Examples of H + X ~ are the hydrogen ether solvate tetrakis [3,5-bis (trifluoromethyl) phenyl] borane and montmorillonite clay. Examples of "solid support" include inorganic oxide support materials such as: talcs, silicas, titanium, silica / chromium, silica / chromium / titanium, silica / alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels , silica xerogels, silica aerogels, montmorillonite clay and silica co-gels, as well as also organic solid supports such as polystyrene and functionalized polystyrene (See, for example, Roscoe, SB, Frechet, JMJ, Walzer, JF; , AJ; "Polyolefin Spheres from Metallocs Supported on Non-Interacting Polystyrene", 1998, Science, 280, 270-273 (1998). An especially preferred solid support is one which has been pre-treated with Y compounds as described in US Pat. present, more preferably with MAO Thus, in a preferred embodiment, the catalysts of the present invention are attached to a solid support (by "binding to a solid support" which means ion coupled with a component on the surface, adsorbed to the surface or covalently bound to the surface) that has been pre-treated with a compound Y. Alternatively, the catalyst, the compound Y, and the solid support can be combined in any order, and any number of compounds Y can be used; In addition, the supported catalyst thus formed can be treated with additional amounts of compounds Y. In an especially preferred embodiment, the compounds of the present invention are bonded to the silica, which has been pre-treated with MAO. Such supported catalysts are prepared by contacting the transition metal compound, in a substantially inert solvent which means a solvent which is either unreactive under the conditions of catalytic preparation, or reactive, acts to usefully modify the activity or catalytic selectivity - with MAO treated silica for a sufficient period of time to generate the supported catalysts. Examples of substantially inert solvents include toluene, volatile minerals, hexane, CH2C12 and CHC13.

It is known to those skilled in the art that a variety of protocols can be used to generate active polymerization catalysts comprising transition metal complexes of various nitrogen, phosphorus, oxygen and sulfur donor ligands. Examples of such protocols include (i) the reaction of a metal dihalide complex of Group 8-10 of a bidentate N-donor ligand with an alkylaluminum reagent, (ii) the reaction of a bidentate N-donor ligand with nickel (1) , 5-cyclooctadiene) 2 and HB (3,5-bis (trifluoromethyl) phenyl) and (iii) the reaction of a metal dialkyl complex of Group 8-10 of a bidentate N-donor ligand with MAO or HB (3 , 5-bis (trifluoromethyl) phenyl). In some cases, it is also possible to react a bidentate N-donor ligand with nickel (1, 5-cyclooctadiene) 2 and B (C6Fs) 3 to obtain an active catalyst. Cationic (ligand) M (p-allyl) complexes with weakly coordinating counterions, where M is a transition metal of Group 8-10, are often suitable as catalytic precursors, requiring only exposure to the olefin monomer and in some cases high temperatures (40-200 ° C) or added Lewis acid, or both, to form an active polymerization catalyst. The salts [(ligand) Ni (methyl) (O (CH2CH3) 2] [B (3,5-bis (trifluoromethyl) phenyl) 4] and [(ligand) Pd (methyl) (O (CH2CH3) 2] [B (3, 5-bis (trifluoromethyl) phenyl) 4] isolates can also serve as a component of catalyst systems.More generally, a variety of complexes (ligand) M (Q) (W), where "ligand" refers to a composed of the formula X, M is a transition metal of the divalent Group 8-10, and Q and W are univalent groups, or can be taken together to form a divalent group, can be reacted with one or more compounds, collectively referred to as compound Y, whose function as cocatalysts or activators, to generate an active catalyst of the form d [(ligand) M (T) (L)] + X ~, where T is a hydrogen or hydrocarbyl atom, L is an olefin or a neutral donor group, capable of being displaced by an olefin, and X ~ is a weakly coordinating anion.When Q and W are both halide, examples of suitable Y compounds include yen: methylaluminoxane (hereafter "MAO") and other aluminum sesquioxides, R ° 3A1, R ° 2A1C1, and R ° A1C12 (wherein R ° is alkyl). When Q and W are both alkyl, examples of suitable Y compounds include: MAO and other aluminum sesquioxides, R ° 3A1, R ° 2A1C1, R ° A1C12 (wherein R ° is alkyl), B (C6F5) 3, R163Sn [BF4], H + X ", wherein X" is a weakly coordinating anion, for example, tetrakis [3,5-bis (trifluoromethyl) phenyl) ] borate, and acidic metal oxides of Lewis and acidic Bronsted, for example, montmorillonite clay. In some cases, for example, when Q and W are both halide or carboxylate, sequential treatment with a metallic hydrocarbyl, followed by reaction with a Lewis acid or Bronsted acid, may be required to generate an active catalyst. Suitable examples of metal hydrocarbyls include: MAO, other aluminum sesquioxides, R ° 3A1, R ° 2A1C1, R ° A1C12 (where R ° is alkyl), Grignard reagents, organolithium reagents, and diorganozinc reagents. Examples of suitable Lewis acids or Bronsted acids include: MAO, other aluminum sesquioxides R ° 3A1, R ° 2A1C1, R ° A1C12 (where R ° is alkyl), B (C6F5) 3, R163Sn [BF4], H + X ~, wherein X "is a weakly coordinating anion, for example, tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate, and acidic metal oxides of Lewis and acidic Bronsted, eg, montmorillonite clay. While not wishing to be bound by a theory, it is believed that the Lewis acid may be temporary to further activate the catalysts provided herein through the coordination of one or more of those heteroatoms that are not directly bound to the metal of M-transition, but which are p-conjugated to the nitrogens that are bound to the transition metal M. Substituents that contain additional Lewis base groups, including, but not limited to, methoxy groups, placed in such a way as to further promote the binding of the acid or from Lewis to such p-conjugated heteroatoms, are also included in this invention. A non-limiting example of secondary Lewis acid binding would include the following: XLIII wherein R1, R2, R5 and R6 are 2,6-dimethylphenyl; and X "is a weakly coordinating anion Polymerizations can be conducted as solution polymerizations, such as suspension type polymerizations without solvent, as suspension polymerizations using one or more of the olefins or other solvent as the polymerization medium, or in the gas phase Someone with ordinary skill in the art, with the present disclosure, will be understood that the catalyst could be supported using a suitable catalyst support and methods known in the art: Substantially inert solvents, such as toluene, hydrocarbons , methylene chloride and the like, can be used, propylene and 1-butene are excellent monomers for use in suspension type copolymerizations and unused monomers can be directed and reused.The olefin temperature and pressure have significant effects on the structure, composition and molecular weight of the polymer. Suitable bristles are preferably from about -100 ° C to about 200 ° C, more preferably in the range from 20 ° C to 150 ° C. After the reaction has continued for a sufficient time to produce the desired polymers, the polymer can be recovered from the reaction mixture by routine isolation and / or purification methods. In general, the polymers of the present invention are useful as components of thermosetting materials, such as elastomers, such as packed materials, films, compatibilizing agents for polyesters and polyolefins, as a component of tackifying compositions, and as a component of adhesive materials. . High molecular weight resins are easily processed using conventional extrusion, injection molding, compression molding, and vacuum forming techniques well known in the art. Useful articles made from films include, fibers, bottles and other containers, coating, molded objects and the like. Low molecular weight resins are useful, for example, as synthetic waxes and can be used in various wax coatings or in the form of an emulsion. They are also particularly useful in mixtures with copolymers of the ethylene / vinyl acetate or ethylene / methyl acrylate type in paper coating or in adhesive applications. Although not required, typical additives used in olefin or vinyl polymers can be used in the novel homopolymers and copolymers of this invention. Typical additives include pigments, dyes, titanium dioxide, carbon black, antioxidants, stabilizers, decay agents, flame retardants, and the like. These additives and their use in polymer systems are known per se in the art. The molecular weight data presented in the following examples is determined at 135 ° C in 1,2,4-trichlorobenzene using refractive index detection, calibrated using poly (styrene) standards of narrow molecular weight distribution. EXAMPLES Other characteristics of the invention will be apparent in the course of the following descriptions of the exemplary embodiments which are given by way of illustration of the invention and are not intended to be limiting thereof. Example 1 Preparation of N, N'-bis (2,6-dimethylphenyl) oxalamide. Dried 2, 6-dimethylaniline, triethylamine and dichloromethane are passed through basic alumina. A 1 L round bottom flask, equipped with a magnetic stir bar and a 125 mL pressure equalized drip funnel capped by a nitrogen inlet adapter, was charged with 53.38 g of 2,6-dimethylaniline, 250 mL of dichloromethane and 44.76 g of triethylamine. A solution of 25.34 g of oxalyl chloride in 80 mL of dichloromethane was added dropwise under nitrogen with stirring and cooled in an ice bath for 1.2 hours to give a thick paste which had to be swirled by hand occasionally to effect mixing . The mixture was allowed to stir at room temperature for 14 hours, then transferred to a separatory funnel, washed 3 times with water, separated and concentrated under reduced pressure (10 mm Hg) to give 63 g of solid without purification. The unpurified product was dissolved in a boiling mixture of 1.30 L of toluene and 2. 85 L of absolute ethanol, cooled to room temperature (approximately 23 ° C) and diluted with 260 mL of water, then allowed to crystallize for 16 hours. The resulting precipitate was isolated by vacuum filtration, washed with methanol (3 x 100 mL) and dried to give 39.1 g (66%) as white crystals. An additional 9.5 g (16.1%) was recovered from the filtrate by additional dilution with approximately 500 mL of water. The field desorption mass spectrometry showed a standard ion peak at 296 m / z. 1H NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.29 (12p, s), 7.15 (6p, m), 8.86 (2p, broad s). Example 2 Preparation of N, N'-bis (2,6-diisopropylphenyl) oxalamide. 2, 6-Diisopropylaniline, triethylamine, and dichloromethane were dried by passing through basic alumina. A 1 L round bottom flask equipped with a magnetic stir bar and a 125 mL pressure equation dropping funnel, plugged by a nitrogen inlet adapter, was charged with 34.73 g of 2,6-diisopropylaniline (previously distilled), 180 mL of dichloromethane, and 18.30 g of triethylamine. A solution of 10.57 g of oxalyl chloride in 43 mL of dichloromethane was added dropwise under nitrogen with stirring and cooled in an ice bath for 38 minutes to give a thick paste which had to be swirled by hand occasionally to effect mixing . The mixture was allowed to stir at room temperature (approximately 23 ° C) for 60 hours, then diluted with 700 mL of water to precipitate the product, which was isolated by filtration, washed with water and recrystallized from boiling isopropanol (4 L) to yield 22.38. g (66%) of white needles. Field desorption mass spectrometry showed a parent ion peak at 408 m / z. 1H NMR (500 MHz, CD2C12, chemical changes in ppm relative to TMS at 0 ppm): 1.22 (24p, d, 6.8 Hz), 3.08 (4p, septet, 6.8 Hz), 7.25 (4p, d, 7.5 Hz), 7.37 (2p, t, 7.5 Hz), 8.86 (2p, s broad). Example 3 Preparation of N ^ N'-bis (4-methoxy-2,6-dimethylphenyl) oxalamide. Triethylamine and dichloromethane were dried by passing through basic alumina. A 50 mL round bottom flask, equipped with a magnetic stir bar, and a small pressure equalized drip funnel capped by an adapted nitrogen inlet, was charged with 1.5 g of 4-methoxy-2,6-dimethylphenylamine. , 8 mL of dichloromethane, and 1.38 g of triethylamine. A solution of 0.39 oxaxolyl chloride in 2 mL of dichloromethane was added dropwise under a nitrogen atmosphere with stirring and cooled in an ice bath for 35 minutes. The mixture was allowed to stir at room temperature for 14 hours, then transferred to a separatory funnel, washed with water, separated and concentrated under reduced pressure (10 mm Hg), to give 1.75 g of solids. The crude product was dissolved in 150 mL of boiling absolute ethanol and crystallized to cooling to room temperature (about 23 ° C). The resulting precipitate was isolated by vacuum filtration, and dried to give 1.39 g (86%) as white crystals. Field desorption mass spectrometry showed a parent ion peak at 356 m / z. Example 4 Preparation of N1, N2-bis (2,6-dimethylphenyl) oxalodiimidoyl chloride, A 1 L round bottom flask was charged with 30.0 g of N, N'-bis (2,6-dimethylphenyl) oxalamide, 58.8 g of phosphorus pentachloride and 150 mL of dry toluene, and equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet adapter connected to a bubbler. The mixture was refluxed for 30 minutes, then refluxed under nitrogen for another 95 minutes to give a yellow solution. The heating was discontinued and the mixture allowed to cool to room temperature (approximately 23 ° C). A short path distillation adapter and a receiving flask were joined in place of the condenser and the volatile compounds were removed under reduced pressure (1 mm Hg) initially at room temperature, then at 100 ° C, to give 20.1 g (60%) of a granular yellow solid. Field desorption mass spectrometry showed a parent ion peak at 332 m / z. tE NMR (300 MHz, C6D6, chemical changes in ppm relative to TMS at 0 ppm): 2.04 (12p, s), 6.91 (6p, s). Example 5 Preparation of N1, N2-b s (2,6-diisopropylphenyl) oxalodiimidoyl dichloride. A 500 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet adapter connected to a sparger was charged with 2.50 g of N, N'-bis (2,6-diisopropylphenyl) ) oxalamide, 3.58 g of phosphorus pentachloride and 36 mL of dry toluene. The mixture was refluxed for 30 minutes, then refluxed under nitrogen for another 210 minutes to produce a light yellow solid. The heating was discontinued and the mixture allowed to cool to room temperature (approximately 23 ° C). A short path distillation adapter and the receiving flask were joined in place of the condenser and the volatile compounds were removed under reduced pressure (1 mm Hg), initially at room temperature, then at 100 ° C, to give a yellow oil, which slowly crystallized until complete cooling. The product was purified by column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60 A, 3% by volume ethyl acetate in hexane) to yield 1.49 g (55%) of yellow crystals. The field desorption mass spectrometry showed a parent ion peak at 444 m / z. Example 6 Preparation of N ~, N2-bis (4-methoxy-2,6-dimethylphenyl) oxalodiimidoyl dichloride. A 50 mL round bottom flask was charged with 1.37 g of N, N'-bis (4-methoxy-2,6-dimethylphenyl) oxalamide 1.88 g of phosphorus pentachloride and 15 mL of dry toluene, and equipped with a bar of magnetic stirring and a reflux condenser capped by a nitrogen inlet adapter connected to a bubbler. The mixture was heated, with stirring, to about 100 ° C until the evolution of HCl ceased. Then, another PCls 0.22 g was added and the mixture was heated another 30 minutes at 80 ° C. After cooling to room temperature the mixture was transferred to a separatory funnel, and some crystallization occurred until transfer. The complete transfer and the re-dissolution of the product was carried out by the addition of dichloromethane. The organic layer was washed with saturated aqueous sodium bicarbonate, then concentrated in vacuo to yield 1.44 g of the crystalline yellow solid. Field desorption mass spectrometry showed a parent ion peak at 392 m / z. Example 7 Preparation of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane.

A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 504 mg of N2, N2-bis (2,6-dimethylphenyl) oxalodiimidoyl dichloride, 136 mg of sodium hydride (60% dispersion of mineral oil), 4.0 mL of dry tetrahydrofuran and 0.140 mL of 1,2-ethanethiol. The mixture was refluxed for 2 hours, after which another 66 mg sodium hydride dispersion was added and the mixture was refluxed for an additional hour. After cooling, the mixture was diluted with water and diethylether, and the ether layer was separated, washed again with water, and dried with magnesium sulfate to produce a yellow-orange oil. Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60A, 15% by volume ethyl acetate in hexane) yielded 296 mg of yellow oil which was crystallized by the addition of hexane and collected by vacuum filtration for give 219 mg of yellow granular crystals. Field desorption mass spectrometry showed a parent ion peak at 354 m / z. 1H? MR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.17 (12p, s), 3.27 (4p, broad s), 6.4-7.12 (6p, m). EXAMPLE 8 Preparation cié 2, 3-bis (2,6-diisopropilfenilimino) - [1, 4"lditiano A 250 mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser capped by an argon inlet charged sequentially with 0.69 g of a 60% dispersion of sodium hydride in mineral oil, 3.34 g of N-? N2-bis (2,6-diisopropylphenyl) oxalodiimidoyl dichloride, 20 mL of dry tetrahydrofuran, and 0.70 mL of 1 2-Ethanethiol The mixture was heated under argon at reflux for 3 hours, then with another 0.25 g sodium hydride dispersion was added and the mixture was refluxed for an additional 2.5 hours. Diluted with water and diethyl ether, and the ether layer was separated, washed with water, and dried with magnesium sulfate to produce a yellow-orange oil.Column chromatography (Si0, 230-400 Merck Grade 9385 mesh, 60 Á; 10% by volume of ethyl acetate in hexane) to produce 3. 14 g of a yellow-orange glass. Field desorption mass spectrometry showed a parent ion peak at 466 m / z. XH ™ MR (500 MHz, CD2C12, chemical changes in ppm relative to TMS at 0 ppm): 1.10-1.22 (12p, m), 1.22-1.40 (12p, m), 2.78-3.05 (4p, m), 3.30 (4p, s broad), 7.05-7.25 (6p, m). Example 9 Preparation of 2,3-bis (phenylimino) - [1,4] dithiane. A 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was charged sequentially with 0.69 g of a 60% sodium hydride dispersion in mineral oil, a freshly prepared solution. of 2.08 g of N ^ N ^ diphenyloxalodiimidoyl dichloride in 20 mL of tetrahydrofuran and 0.70 L of 1,2-ethanethiol. The mixture was heated under argon at reflux for 2 hours, after which another dispersion of sodium hydride of 0.30 g was added and the mixture was refluxed for an additional 3 hours. After cooling, the mixture was diluted with water and diethylether, and the ether layer was separated, washed with water, and dried over magnesium sulfate to produce a yellow-orange gummy solid. Column chromatography (Si02, 230-400 mesh Merck Grade 9385, 60 Á; 10% by volume of ethyl acetate in hexane) yielded 296 mg of a yellow oil which was crystallized by the addition of hexane to give 0.161 g of yellow-orange granular crystals. The field desorption mass spectrometry showed a parent ion peak at 298 m / z. 1H? MR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 3.27 (4p, broad s), 7.02 (4p, apparent d, 8.1 Hz), 7.19 (2p, apparent t, 7.2 Hz) , 7.40 (4p, apparent t, 7.8 Hz). Example 10 Preparation of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydrobenzo [1,4] dithiane.

A 100 mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser capped by an argon inlet was charged sequentially with 0.294 g of a dispersion of 60% sodium hydride in mineral oil, 4 mL of tetrahydrofuran dry, and 0.253 g of 1,2-benzenedithiol. After the bubbling was quenched, 0.600 g of N ^ N-bis (2,6-dimethylphenyl) oxalodiimidoyl dichloride was added. The mixture was stirred at 25 ° C for 45 minutes, then heated to reflux for 15 minutes and refluxed for 1 hour. After cooling, the mixture was diluted with water and diethylether, and the ether layer was separated, washed with water, and dried with magnesium sulfate, and concentrated in vacuo to give a yellow-orange oil. Column chromatography (SiO2, 230-400 Merck Grade 9385 mesh, 60A, 2% by volume ethyl acetate in hexane) yielded 0.412 g of a yellow-orange glass. Field desorption mass spectrometry showed a parent ion peak at 402 m / z 1H? MR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.16 (12p, s), 7.01-7.24 (lOp, m). Example 11 Preparation of 2,3-bis (4-methoxy-2,6-dimethyl-enylimino) - [1,4] dithiane. A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 420 mg of N1, N2-bis (4-methoxy-2,6-dimethylphenyl) dichloride. oxalo-diimidoyl. For a 50 mL beaker flask, 171 mg of sodium hydride (60% dispersion of mineral oil), 1.75 mL of dry tetrahydrofuran, and cautiously, 0.11 mL of ethanethiol were added. The resulting mixture was injected into the solution of N ^ N-bis (4-methoxy-2,6-dimethylphenyl) oxalo-diimidoyl dichloride using 5 mL of dry THF to complete the transfer. The reaction flask was heated to reflux for 3 hours, after which another dispersion of 45 mg sodium hydride and another 20 μl ethanethiol were added and the mixture was refluxed for an additional hour. After cooling, the mixture was diluted with water and diethyl ether, and the ether layer was separated, washed again with water, dried with magnesium sulfate, and concentrated to yield a yellow-orange solid. Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60A, 15% by volume ethyl acetate in hexane) yielded 147 mg of a yellow powder. Field desorption mass spectrometry showed a parent ion peak at 414 m / z. Example 12 Preparation of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane. A 5Q mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 504 mg of N1, N2-bxs (2,6-dimethylphenyl) oxalodiimidoyl dichloride, 66 mg of sodium hydride (60% dispersion of mineral oil), 5.0 mL of tetrahydrofuran, 0.230 mL of triethylamine (dried by passing through alumina) and 0.093 mL of dry ethylene glycol. The mixture was heated to reflux for 105 minutes, after which another 66 mg sodium hydride dispersion was added and the mixture was refluxed for an additional hour. After cooling, the mixture was diluted with water and diethylether, and the ether layer was separated, washed again with water, dried with magnesium sulfate, and concentrated to yield a yellow oil. The crystallization of heptane gave rosettes of whitish crystals (225 mg, 1st grain). Field desorption mass spectrometry showed a parent ion peak at 322 m / z. XH NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.20 (12p, s), 4.35 (4p, s), 6.94 (2p, m), 7.05 (4p, m). Example 13 Preparation of 5-methoxymethyl-2,3-bis (2,6-dimethylphenylimino) - [1,4-dioxane. A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was charged with 504 mg of N ^ N ^ -bis dichloride (2)., 6-dimethylphenyl) oxalodiimidoyl, 155 mg of sodium hydride (60% dispersion of mineral oil), 3.5 mL of dry tetrahydrofuran and 188 mg of 3-methoxy-1,2-propanediol. The mixture was refluxed for 10 minutes and refluxed for 2 hours. After cooling, the mixture was diluted with diethyl ether, and washed with water (2 x 100 mL), and dried with magnesium sulfate and concentrated in vacuo to yield 329 mg of a yellow oil. Column chromatography (Si02, 230-400 mesh Merck Grade 9385, 60 Á; 20 vol.% Ethyl acetate in hexane) yielded 216 mg of a glassy yellow solid. Field desorption mass spectrometry showed a parent ion peak at 366 m / z. XH NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.18 (12p, s), 3.31 (3p, s), 3.45-3.65 (2p, m), 4.20-4.40 (2p, m ), 4.40-4.55 (lp, m), 6.80-7.15 (6p, m). Example 14 Preparation of 2,3-bis (benzyloxymethyl) -5,6-bis (2,6-dimethylphenylimino) - [1,4] dioxane. A 100 mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser capped by an argon inlet was charged with 265 mg of sodium hydride (60% dispersion of mineral oil), 7.5 mL of dry tetrahydrofuran. , 1.0 g of 3-methoxy-l, 2-propanediol and 1.0 g of W ^^ -bis (2,6-dimethylphenyl) oxalodiimidoyl dichloride. The yellow mixture was heated to reflux for 15 minutes and became very viscous. Additional tetrahydrofuran (5 mL) was added and the mixture was stirred with a glass rod, then heated for another 30 minutes. Then, an additional 220 mg of sodium hydride (60% dispersion of mineral oil) and an additional 10 mL of tetrahydrofuran were added. Most of the yellow color was discharged with the second addition of sodium hydride, the very viscous light brown reaction mixture was made. Heating was continued for about 15 more minutes, and after cooling, the mixture was diluted with diethyl ether and washed with water to remove the sodium chloride. Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60A, 2% by volume ethyl acetate in hexane) yielded a beige gum solid. The field desorption mass spectrometry showed a parent ion peak at 562 m / z. 1E NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.17 (12p, s), 3.63 (4p, s broad), 4.38 (2p, d, 12.6 Hz), 4.47 (2p, d , 12.6 Hz), 4.56 (2p, broad s), 6.85-7.4 (16p, m). Example 15 Preparation of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dioxane. A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 1.0 g of N ^ N-bis (2,6-diisopropylphenyl) oxalodiimidoyl dichloride, 268 mg of sodium hydride (60% dispersion of mineral oil), 4.0 mL of dry tetrahydrofuran, and 212 mg of dry ethylene glycol. Under an argon atmosphere, the mixture was heated to 65 ° C maintaining that temperature for 90 minutes. The mixture was then rapidly heated to reflux and refluxed for an additional 30 minutes. After cooling, the mixture was diluted with 50 mL of diethyl ether, and washed with water, dried with magnesium sulfate, and concentrated in vacuo to yield a light straw yellow oil (903 mg). Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60A, 8% by volume ethyl acetate in hexane) yielded 257 mg of a pale green glass. The field desorption mass spectrometry showed a parent ion peak at 434 m / z. XH NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 1.24 (24p, d, 6.6 Hz), 3.00 (4p, septet, 6.6 Hz), 4.31 (4p, broad s), 7.04- 7.20 (6p, m). Example 16 Preparation of 2,3-bis (2,6-diisopropylphenylimino) -4-methylmorpholine. A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet adapter was charged with 503 mg of N:, N-bis (2,6-diisopropylphenyl) oxalodiimidoyl dichloride, 346 mg of triethylamine, 4 mL of dry deoxygenated toluene, and 0.135 mL of 2- (methylamino) ethanol. The mixture was refluxed under nitrogen for 30 minutes and refluxed for another 4.25 hours. After cooling, the mixture was diluted with 45 mL of diethyl ether and washed three times with water (100 mL total). The ether extract was dried with magnesium sulfate, filtered and concentrated under reduced pressure (10 mm Hg) to give a lightly colored solid (512 mg). Recrystallization from heptane / dichloromethane gave 138 mg of pale whitish crystals (first grains). Field desorption mass spectrometry showed a parent ion peak at 335 m / z. H NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 1.73 (6p, s), 2.10 (6p, s), 3.27 (3p, s), 3.55-3.65 (2p, m), 4.16-4.26 (2p, m), 6.65-6.95 (6p, m). Example 17 Preparation of 2,3-bis (2,6-diisopropylphenylimino) -4-methylmorphine. A 50 L round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet adapter was charged with 725 mg of N ^ N-bis (2,6-diisopropylphenyl) oxalodiimidoyl dichloride, 143 mg of sodium hydride (60% dispersion of mineral oil), 4 mL of dry tetrahydrofuran, and 0.144 mL of 2- (methylamino) ethanol. The mixture was stirred at room temperature for 4 hours, and allowed to stand at room temperature for another 5 days. The mixture was diluted with diethyl ether and washed with water. The ether extract was concentrated under reduced pressure (10 mm Hg) to give a yellow oil which is partially crystallized for several hours). Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60A, 12 vol% ethyl acetate in hexane) yielded 156 mg of slightly yellow crystals. The field desorption mass spectrometry showed a parent ion peak at 447 m / z. 1 HOUR NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm). 0.86 (6p, d, 7.2 Hz), 1.04 (tp, d, 7.2 Hz), 1.15 (6p, d, 7.2 Hz), 1.18 (6p, d, 7.2Hz), 2.27 (2p, apparent septet, 7.2 Hz), 2.97 (2p, apparent septet, 7.2 Hz), 3.28 (3p, broad s), 3.55 -3.65 (2p, m), 4.14-4.22 (2p, m), 6.80-7.02 (6p, m). Example 18 Preparation of 1,3-bis (2,6-dimethyl-phenyl) -4,5-bis (2,6-dimethyl-phenylimino) imidazolidin-2-one. A 250 mL round bottom flask, 1.0 g of NI, N, N3, N4-tetrakis (2,6-dimethylphenyl) oxalamidine was dissolved in 35 mL of dry deoxygenated dichloromethane, while stirring under an argon atmosphere. 0.67 mL of dry triethylamine was added, followed by 240 mg of triphosgene. With the addition of triphosgene, the color changed from pale yellow to chrome yellow. The mixture was allowed to stir for 16 h at room temperature, after which an additional 460 mg of triphosgene was added. After approximately 15 minutes, 10 mg of dimethylaminopyridine, and an additional 240 mg of triphosgene were added. After approximately 15 more minutes, another 220 mg of triphosgene and approximately 0.5 g of dimethylaminopyridine were added. The mixture was washed with saturated aqueous sodium bicarbonate, then with water, and then concentrated in vacuo to yield a yellow powder. Column chromatography (S102, 230-400 Merck Grade 9385 mesh, 60A, 4% by volume ethyl acetate in hexane) yielded 763 mg of yellow chromium powder. Field desorption mass spectrometry showed a parent ion peak at 528 m / z. 1H NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 2.01 (12p, s) 2.32 (12p, s), 6.4-7.3 (12p, m). Example 19 Preparation of 1,3-bis (4-methoxy-2,6-dimethylphenyl) -4,5-bis (4-methoxy-2,6-dimethylphenylimino) imidazolidin-2-one. A 100 mL round bottom flask equipped with a magnetic stirrer and charged with 0.75 mL of dry triethylamine, 6 mL of deoxygenated and dry dichloromethane, and 0.335 g of N ^ N ^ N '/.? T ^ -tetrakis (4-methoxy-2,6-dimethylphenyl) oxalamidine. With stirring, 178 mg of triphosgene was added, and the flask was quickly capped with a septum. A precipitate formed and the color changed from yellow to orange. After 2.5 days, another 78 mg of triphosgene was added, and the reaction was allowed to stir for another 2 hours. An additional 150 mg of triphosgene was added, and the reaction was allowed to stir for another 16 hours. The reaction mixture was diluted with 50 mL of diethyl ether and washed with water (2 x 50 mL). The aqueous washings were extracted with dichloromethane. The organic layers were combined and dried over magnesium sulfate, and concentrated in vacuo to yield an orange oil. Until the addition of the diethyl ether to the oil, small orange crystals were formed. The compound was isolated on a vacuum filter and washed with diethyl ether to yield 216 mg of yellow-orange microcrystalline powder. Field desorption mass spectrometry showed a parent ion peak at 648 m / z. 1ti NMR (500 MHz, CD2C12, chemical changes in ppm relative to TMS at 0 ppm): 1.98 (12p, broad mound), 2.25 (12p, broad mound), 3.63 (6p, broad mound), 3.75 (6p, broad mound) ), 6.32 (4p, broad mound), 6.59 (4p, broad mound). Example 20 Preparation of N1, N2, N3, lX-tetrakis (2,6-dimethylphenyl) oxalami-dine. A 1 L round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 5.6 g of N, N-bis (2,6-dimethylphenyl) oxalodiimidoyl dichloride, 43 mL of dry toluene and 32.7 g of 2,6-dimethylaniline (dried by passing through alumina). The mixture was refluxed under nitrogen for 30 minutes, then refluxed for another 3 hours. After cooling, the mixture was diluted with 206 g of absolute ethanol and 45 g of water to produce copious amounts of the precipitate. Isolation by vacuum filtration, with ethanol (600 mL) and heptane (600 mL) washed, and subsequently dried, gave 6.1 g (72%) as pale yellow crystals. Field desorption mass spectrometry showed a parent ion peak at 502 m / z. 1H? MR (300 MHz, CDCl3, chemical changes in ppm relative to TMS at 0 ppm): 2.16 (24p, s), 6.75 (12p, s,), 8.6 (2p, broad s). Example 21 Preparation of N '^ N' N ^ N ^ -tetrakis (4-methoxy-2,6-dimethyl-phenyl) oxalamidine. A 500 mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser capped with a nitrogen inlet was charged with 1.0 g of N1, N2-bis (4-methoxy-2,6-dimethylphenyl) dichloride. oxalodiimidoyl, 24 mL of dry toluene and 854 mg of 4-methoxy-2,6-dimethylphenylamine, and 0.90 mL of triethylamine (dried by passing through alumina). The mixture was refluxed under nitrogen for 30 minutes, then refluxed for another 14 hours. After cooling, the mixture was diluted with dichloromethane and washed with water. The impure compound was adsorbed on Si02, and column chromatography (Si02, 230-400 mesh Merck Grade 9385, 60 A; 12.5% by volume of ethyl acetate in hexane) yielded 340 mg of a yellow powder. Field desorption mass spectrometry showed a parent ion peak at 622 m / z. Example 22 Preparation of 1,4-dimethyl-2,3-bis (2,6-dimethylphenylimino) -piperazine. A 25 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet adapter was charged with 0.50 g of N ^ N ^ -bis (2,6-dimethylphenyl) dichloride - oxalodiimidoyl, 1.1 mL of N, N'-dimethylethylenediamine and 4.0 mL of dry toluene. The mixture was refluxed under nitrogen for 15 minutes and refluxed for another 3-0 minutes. After cooling, the mixture was diluted with diethyl ether and washed three times with water. The ether extract was dried with magnesium sulfate, filtered and concentrated under reduced pressure (10 mm Hg) to give a yellow solid (0.50 g). Recrystallization from heptane gave pale yellow crystals. Field desorption mass spectrometry showed a parent ion peak at 348 m / z. 1H? MR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 1.83 (broad s, 12 p), 2-3.4 (two very broad mounds, 4 p), 3.42 (s broad, 6 p) ), 6.66 (t, 2p), 6.84 (d, 4p). Example 23 Preparation of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was loaded with 100 mg of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane and 79 mg of dibromide ( 1,2-dimethoxyethane) nickel (II) under an inert atmosphere. Dry deoxygenated dichloromethane (5 mL) was added and the mixture was stirred under an argon atmosphere, turned brown-red with about 5 minutes and slowly produced a red-brown crystalline precipitate. After 1 hour, 5 mL of dichloromethane was added. The mixture was stirred another 21 hours at 21 ° C, then diluted with 10 mL of dry deoxygenated hexane and stirred another 8 hours. The supernatant was removed through a filter paper cannula, and the residue was dried in vacuo at 1 mm Hg to produce 16 mg of red-brown crystals. Example 24 Preparation of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane. A Schlenk flask equipped with a magnetic stir bar was charged with 79 mg of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane (0.17 mmole) and 49 mg of dibromide (1, 2- dimethoxyethane) nickel (II) (0.16 mmole) under an argon atmosphere. Dry deoxygenated dichloromethane (15 mL) was added and the mixture was stirred under an argon atmosphere, becoming red-brown within about 10 minutes. After 2 hours, the CHC12 was removed in vacuo. The resulting red-brown solid was washed with 2x10 mL of hexane and the solid was dried in vacuo for several hours yielding 76 mg of a brown solid. Example 25 Preparation of the nickel dibromide complex of 2,3-bis (phenylimino) [1,4] dithiane. A 50 mL Schlenk flask with a magnetic stir bar and capped with a septum was loaded with 151 mg of 2,3-bis (phenylimino) - [1,4] dithiane and 123 mg of (1,2-dimethoxyethane) dibromide. ) nickel (II) under an inert atmosphere. Dry deoxygenated dichloromethane (10 mL) was added and the mixture was stirred under an argon atmosphere, becoming dark brown within about 5 minutes and slowly producing a red-brown crystalline precipitate. After 80 minutes, the mixture was concentrated to appear dry under a stream of argon, then further dried in vacuo for 1 hour at 50 mTorr to produce a red-brown powder. Example 26 Preparation of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydrobenzo [1,4] dithmine.

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 110 mg of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydrobenzo [1,4] -diitine and 71 mg of (1,2-dimethoxyethane) nickel (II) dibromide under an inert atmosphere. Dry deoxygenated dichloromethane (8 mL) was added and the mixture was stirred under an argon atmosphere, rapidly becoming red-brown. The mixture was stirred for 1 hour, concentrated to dryness under a stream of argon, then further dried in vacuo for 1 hour at 50 mTorr to produce a red-brown crystalline powder. Example 27 Preparation of the nickel dibromide complex of 2,3-bis (4-methoxy-2,6-dimethylphenylimino) - [1,4] dithiane. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 147 mg of 2,3-bis (4-methoxy-2,6-dimemethylimino) - [1,4] dithiane and 93 mg of (1,2-dimethoxyethane) nickel (II) dibromide under an inert atmosphere. Dry deoxygenated dichloromethane (10 mL) was added and the mixture was stirred under an argon atmosphere, turning dark brown at least immediately, and producing a brown precipitate. After 2 hours, 10 mL were dried and deoxygenated hexane was added to complete the precipitation. The supernatant was removed through a filter paper cannula, the residue was dried in vacuo (0.5 mm Hg) for 14 hours to obtain the product as a brown microcrystalline solid. Example 28 Preparation of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 100 mg of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane and 87 mg of dibromide ( 1,2-dimethoxyethane) nickel (II) under an inert atmosphere. Dried deoxygenated dichloromethane was added (5 mL) and the mixture was stirred under an argon atmosphere, slowly producing a brown crystalline precipitate.

After 1 hour, another 5 mL of dichloromethane was added.

The mixture was stirred another 21 hours at 21 ° C, then diluted with 10 mL of dry deoxygenated hexane, and stirred another 8 hours. The supernatant was removed through a filter paper cannula and the residue was dried in vacuo at 1 mm Hg to produce 117 mg of brown crystals. Example 29 Preparation of the nickel dibromide complex of 2,3-bis (benzyloxymethyl) -5,6-bis (2,6-dimethylphenylimino) - [1,4] dioxane. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was loaded with 172 mg of 2,3-bis (benzyloxymethyl) -5,6-bis (2,6-methylphenylimino) - [1, 4 ] dioxane and 85 mg of (1,2-dimethoxyethane) nickel (II) dibromide under an inert atmosphere. Dry deoxygenated dichloromethane (12 mL) was added and the mixture was stirred under an argon atmosphere, almost immediately turning red-brown. After 1.75 hours, the mixture was concentrated to dryness under a stream of argon for 16 hours, then dried further in vacuo to yield 182 mg of a red-brown crystalline powder. Example 30 Preparation of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -4-methylmorphine. A 25 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 100 mg of 2,3-bis (2,6-dimethylphenylimino) -4-methylmorphine and 84 mg of 1,2-dihydrochloride (1, 2). dimethoxyethane) nickel (II) under an inert atmosphere. Dry deoxygenated dichloromethane (5 mL) was added and the mixture was stirred under an argon atmosphere for 1 hour, after which another 5 mL of dichloromethane was added. After 16 hours, the mixture was diluted with 10 mL of hexane, and the supernatant was removed through a filter paper cannula, and the residue dried in vacuo to obtain 139 mg of green crystals. Example 31 Reaction of 1,3-bis (2,6-dimethyl-phenyl) -4,5-bis (2,6-dimethyl-phenylimino) -imidazolidin-2-one, dibromide of (1), 2-dimethoxyethane) nickel (II) and silver tetrafluoroborate. In a glove box filled with argon, a flame-dried Schlenk flask equipped with a magnetic stir bar was charged with 159.6 mg of 1,3-bis (2,6-dimethyl-phenyl) -4,5-bis- (2,6-dimethyl-phenylimino) -imidazolidin-2-one and 92.7 mg of (1,2-dimethoxyethane dibromide (nickel (II) and 59.4 mg of silver tetrafluoroborate.) The flask was wrapped in aluminum foil, and Schlenk line, under an argon atmosphere, 10 mL of dry tetrahydrofuran was added, a white precipitate was immediately separated, the mixture was stirred for 25 minutes, then the supernatant was transferred through the filter paper cannula to a capped bottle. The dried supernatant was concentrated to dryness under a stream of dry argon for 16 hours to yield 256 mg of a yellow crystalline powder Example 32 Preparation of 1,3-bis (4-methoxy-2) nickel dibromide complex , 6-dimethylphenyl) -4,5-bis (4-methoxy-2,6-dimethylphenylimino) imidazolidin -2-one A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 101 mg of 1,3-bis (4-methoxy-2,6-dimethylphenyl) -4,5- bis (4-methoxy-2,6-dimethylphenylimino) imidazolidin-2-one and 40 mg of (1,2-dimethoxyethane) nickel (II) dibromide under an inert atmosphere. Dry deoxygenated dichloromethane (10 mL) was added and the mixture was stirred under a nitrogen atmosphere, slowly turning dark red-brown for 3 hours. After a further 2 hours, the supernatant was removed to a flame-dried Schlenk flask through a filter paper cannula, diluted with 10 mL of dry deoxygenated hexane, and concentrated to dryness under a stream of nitrogen to give a mixture. of a long, stale microcrystalline powder, well defined dark brown crystals. The latter were separated and used without further purification. Example 33 Preparation of the nickel dibromide complex of 1,4-dimethyl-2,3-bis (2,6-dimethylphenylimino) piperazine. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 48 mg of 1,4-dimethyl-2,3-bis (2,6-dimethylphenylimino) piperazine and 35 mg of dibromide ( 1,2-dimethoxyethane (nickel (II) under an inert atmosphere) Dry deoxygenated dichloromethane (5 mL) was added and the mixture was stirred under an argon atmosphere, turning green within about 5 minutes and slowly producing a green precipitate. from a total of 7 hours, the volatiles were removed under reduced pressure (1 mm Hg) and the residue was washed with 2 x 5 mL of dry deoxygenated diethyl ether The resulting green solid was dried under reduced pressure (1 mm Hg) Example 34 Synthesis of: In the glove box, a Schlenk flask was charged with 500 mg of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane and 250 mg of methyl chloride of (1,5-cyclooctadiene) palladium . The flask was removed from the box and placed under an argon atmosphere. To the solid mixture was added 20 mL of methylene chloride resulting in an orange solution. The mixture was allowed to stir for 4 hours. After 4 hours, 20 mL of hexane was added resulting in the precipitation of an orange solid. The solvent was removed through a filter canula driving a red / orange solid. The solid was subsequently washed 3 x 10 mL of hexane and dried in vacuo resulting in 490 mg of the complex (83% yield). "" "H NMR is consistent with the proposed structure.

Example 35 Synthesis of: XXXV In the glove box, a Schlenk flask was charged with 490 mg of 2,3-bis (2,6-diisopropyl-phenyl-imino) [1,4] -dithiano palladium methyl chloride and 738 mg of NaBAr4 where Ar = 3,5-bis -trifluoromethylphenyl. The flask was removed from the box and placed under an argon atmosphere. To the solid mixture was added 25 mL of methylene chloride and 0.2 mL of acetonitrile resulting in an orange solution. The mixture was allowed to stir for 3 hours. After 3 hours, the solution was transferred through a filter cannula conducting a gray solid (NaCl). The solvent was subsequently removed in vacuo resulting in an orange glass (1.1 g of the complex, 90% yield). 1H NMR is consistent with the proposed structure.

Example 36 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MAO A 200 ml pear-shaped Schlenk flask equipped with a Magnetic stirring bar capped with a septum was loaded with 5.3 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension was cooled to 0 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 15 minutes, then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. A precipitate of white polyethylene (with a reddish-brown hue) was observed in minutes. After 10 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 48 hours to give 2.5 g of a white polyethylene. A similar reaction at 21.5 ° C using 0.104 g of the nickel complex (100 μl of a stored solution of 1.04 mg / mL in o-difluorobenzene) gave 426 mg of polyethylene after 14 minutes of reaction (359,000 rotations per hour (TO / h) 1 H NMR: 24 branches / 1000 carbon atoms GPC: Mn = 810,000, Mw / Mn = 2.3 Example 37 Polymerization of ethylene using a catalyst generated in situ from 2, 3-bis (2, 6-dimethylphenylimino) - [1,] -dithiano, bis (1,5-cyclooctadiene) nickel (0) and HB (Ar) (Ar = 3,5-bis (trifluoromethyl) phenyl) A pear-shaped Schlenk flask of 250 mL equipped with a magnetic stir bar and capped with a septum was charged with 20 mg of bis (1,5-cyclooctadiene) nickel (0), 33 mg of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane, and 83 mg of ether solvate HB (Ar) 4. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene.The resulting intense violet solution was shaken under water. or ethylene at 25 ° C for 30 minutes, then quenched by the addition of acetone (50 mL) and methanol (50 mL). The polyethylene which was separated was isolated by vacuum filtration and washed with acetone, then dried under reduced pressure (0.5 mm Hg) for 18 hours to give 339 mg of white polyethylene (332 TO / h). XH NMR: 47 branches / 1000 carbon atoms. GPC: Mn = 180,000; Mw / Mn = 2.4. Example 38 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4-dithiane in the presence of MAO.

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar was charged with 0.5 mL of stored solution (10 mg in 10 mL of CH2Cl2) of the 2,3-bis (2) nickel dibromide complex. 6-dimethylphenylimino) - [1,4] dithiane. The flask was evacuated and filled with ethylene, and charged with 75 mL of dry deoxygenated toluene. The reaction flask was placed in a water bath (23 ° C) and treated with 1.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. A precipitate of white polyethylene was observed in seconds. After 5 minutes, the mixture was quenched by the addition of acetone, methanol and aqueous 6N HCl. The swollen polyethylene which separated was isolated by vacuum filtration and washed with acetone. The resulting polymer was dried for several hours in a vacuum oven at 80 ° C. 580 mg of a white elastic solid was isolated (285,000 TO / h). DSC: (2 or heat) wide fusion with an endothermic maximum at 87 ° C. 1 H NMR, 37 branches / 1000 carbon atoms, GPC: Mn = 186,000; Mw / Mn = 2.06. Example 39 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of MAO. _ A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar was charged with 0.5 mL of stored solution (10 mg in 10 mL of CH2Cl2) of the nickel dibromide complex of 2, 3-bis (2, 6-diisopropylphenylimino) - [1,4] dithiane. The flask was evacuated and filled with ethylene, and charged with 75 mL of dry deoxygenated toluene. The reaction flask was placed in a water bath and treated with 1.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. After 10 minutes, the mixture was quenched by the addition of acetone, methanol and aqueous 6 N HCl. The swollen polyethylene which was separated was isolated by vacuum filtration and washed with acetone. The resulting polymer was dried for several hours in a vacuum oven at 80 ° C. 210 mg of a white amorphous elastic polymer was isolated (63,000 TO / h). DSC: (2nd heat) wide fusion with an endothermic maximum at 6 ° C. 1 H NMR: 92 branches / 1000 carbon atoms. GPC: Mn = 146,000; Mw / Mn = 1.85. Example 40 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,] dithiane in the presence of MMAO (modified methylaluminoxane, 23% iso-butylaluminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.3 mL of a stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] ditian. The autoclave was heated to 40 ° C and 2 mL of MMAO in heptane (6.42% aluminum) was added. The reactor was rapidly pressurized to 100 psig with ethylene and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated was isolated and dried for several hours in a vacuum oven at 80 ° C. 4.8 g of a white elastic solid was isolated (2,000,000 TO / h). DSC: (2nd heat) wide fusion with an endothermic maximum at 97 ° C. 1 H NMR: 28 branches / 1000 carbon atoms. GPC: Mn = 155,000; Mw / Mn = 2.10. Example 41 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1.4ditiano in the presence of MMAO (23% isobutylaluminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.3 mL of stored solution (10 mg in 10 mL of CH2C1) of the nickel dibromide complex., 3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. The autoclave was cooled to 15 ° C and 2 mL of MMAO in heptane (6.42% aluminum) were added. The reactor was rapidly pressurized to 100 psig with ethylene and the temperature was raised to 25 ° C. After 10 minutes at 25 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated, was isolated and dried for several hours in a vacuum oven at 80 ° C. 4.4 g of a white elastic polyethylene was isolated (1,800,000 TO / h) DSC: (2nd heat) melt with an endothermic maximum at 125 ° C. - * H NMR: 6 branches / 1000 carbon atoms. GPC: Mn = 598,000; Mw / Mn = 2.12. Example 42 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MMAO (23% isobutylaluminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 1.0 mL of stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] ditian. The autoclave was heated to 55 ° C and 2 mL of MMAO in heptane (6.42% by weight of aluminum) were added. The reactor was rapidly pressurized to 100 psig with ethylene and the temperature was raised to 65 ° C. After 10 minutes at 65 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated, was isolated and dried for several hours in a vacuum oven at 80 ° C. 5.3 g of a white elastic solid was isolated (640,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 78 ° C. 1 H NMR: 47 branches / 1000 carbon atoms. GPC: Mn = 86,000; Mw / Mn = 1.95. EXAMPLE 43 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MMAO (23% isobutylaminoxane) A Parr® autoclave of 600 mL heated first to approximately 100 ° C under high vacuum to ensure that the reactor was dried.The reactor was cooled and purged with argon.At an argon atmosphere, the autoclave was charged with 150 mL of toluene and 1.0 mL of stored solution ( 10 mg in 10 mL of CH2C12) of the 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane nickel dibromide complex The autoclave was heated to 70 ° C and 2 mL of MMAO were added in heptane (6.42 wt% aluminum) The reactor was rapidly pressurized to 100 psig with ethylene and the temperature rose to 80 ° C. After 10 minutes at 80 ° C, the reaction was quenched by the addition of acetone , and methanol.The swollen polyethylene which separated, was isolated and dried for several hours in an oven vacuum at 80 ° C. 3.5 g of a white elastic solid was isolated (440,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 67 ° C. 1 H NMR: 53 branches / 1000 carbon atoms. GPC: Mn = 87,000; Mw / Mn = 1.66. Example 44 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,] dithiane in the presence of MMAO (23% isobutylaminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] ditian. The autoclave was heated to 40 ° C and 2 mL of MMAO in heptane (6.42% by weight of aluminum) were added. The reactor was rapidly pressurized to 100 psig with ethylene and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated, was isolated and dried for several hours in a vacuum oven at 80 ° C. 2.4 g of a white elastic solid was isolated (700,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 46 ° C. 1 H NMR: 75 branches / 1000 carbon atoms. GPC: Mn = 966,000; Mw / Mn = 1.70. Example 45 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MMAO (23% isobutylaminoxane) The procedure described in Example 44 it was followed, except that the polymerization was conducted at 80 ° C. 1.4 g of a white elastic solid was isolated (400,000 TO / h).

DSC: (2, do heat) fusion with an endothermic maximum at 0 ° C. H NMR: 95 branches / 1000 carbon atoms. GPC: Mn = 406,000; Mw / Mn = 2.05. Example 46 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 44 was followed except that the polymerization was conducted at 65 ° C. 2.15 g of a white elastic solid was isolated (630,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 15 ° C. 1 H NMR: 89 branches / 1000 carbon atoms. GPC: Mn = 502,000; Mw / Mn = 1.78. Example 47 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 44 was followed except that the polymerization was conducted at 25 ° C. 1.9 g of a white elastic solid was isolated (560,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 90 ° C. 1H NMR; 33 branches / 1000 carbon atoms. GPC: Mn = 839,000; M "/ Mn = 1.37. Example 48 Oligomerization of ethylene to α-olefin with the nickel dibromide complex of 2,3-bis (phenylimino) - [1,4] dithiane in the presence of MAO. A 1 L Fischer-Porter bottle was assembled in a pressure head equipped with a mechanical stirrer and liquid feeder ports, then pressurized to 75 psig of ethylene and relieved at room pressure seven hours. The bottle was immersed in a water bath of 21.5 ° C, then 50 mL of dry deoxygenated toluene, were added by means of a syringe, followed by 100 μL of a stored solution of 15.3 mg of nickel dibromide complex of 2, 3-bis (phenylimino) - [1,4] dithiane in 15.0 mL of dichloromethane, followed by another 50 mL of toluene. The mixture was stirred at 300 rpm under 75 psig of ethylene for 5 minutes to saturate the solution with ethylene, then the pressure was relieved, and 4.0 mL of a 10% by weight solution of MAO in toluene were added rapidly. The flask was immediately re-pressurized to 75 psig of ethylene and stirred at 300 rpm. After 30 minutes, the pressure was relieved and the reaction was quenched by the addition of 10 mL of methanol. After disassembling the apparatus, another 40 mL of methanol, 50 mL of 6 N aqueous HCl and 10 mL of acetone were added and the mixture was stirred to complete the hydrolysis of the MAO. The resulting organic layer was separated, washed with 6 N aqueous HCl (1 x 25 mL), and water (2 x 50 mL), then concentrated under reduced pressure (15 Torr) at 40 ° C to obtain an oil. This was treated with toluene (50 mL) and re-concentrated twice, then treated with acetone 50 mL) and re-concentrated, to obtain a white waxy polyethylene solid. Drying in vacuo at 100 ° C, 250 mm Hg for 14 hours gave 0.180 g of the polymer, approximately Mn = 517, containing approximately 85% α-olefin and 15% internal olefin. Example 49 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydrobenzo [1,4] dithiine in the presence of MAO. A 200 mL pear-shaped Schlenk flask, equipped with a magnetic stir bar and capped with a septum, was charged with 100 mL of dry deoxygenated toluene. The flask was placed in a water bath and allowed to equilibrate at 1 atmosphere of ethylene for 10 minutes, then 0.25 mL of a stored solution prepared from 10.2 mg of nickel dibromide complex of 2,3-bis- (2,6-dimethylphenylimino) -2,3-dihydrobenzo [1,4] dithiin in 13.11 g of dry deoxygenated dichloromethane. The reaction mixture was then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. Ethylene was incorporated and formation of a polyethylene precipitate was observed. After 6.5 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which was separated, was isolated by vacuum filtration, then dried at 80 ° C in va cuo for several hours, 287 mg of a white powder polyethylene was isolated (236,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 88 ° C. 1 H NMR showed this material to contain approximately 36 branches / 1000 carbon atoms. GPC: Mn = 145,000so.

; Mw / Mn = 2.35. Example 50 Polymerization of ethylene using a catalyst formed in situ from 2,3-bis (2,6-diisopropylphenylimino) - [1,4 -dialityl and [Pd (NCCH3) 4] [BFj2. A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar capped with a septum was charged with 0.022 g of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane and 0.019 g of [Pd (NCCH3) 4] BF4] 2. The flask was evacuated and filled with ethylene, then 100 mL of the dried deoxygenated dichloromethane was added via syringe and the resulting mixture was stirred under 1 atmosphere of ethylene at 25 ° C. Very little incorporated ethylene was observed. After 10 minutes, 0.412 g B (C6Fs) 3 were added, resulting in an increased ratio of ethylene incorporated. After a total of 84 minutes, the reaction was treated by evaporation of dichloromethanes under a stream of nitrogen, washing the residue with methanol repeatedly to the extract of B (C6Fs) 3, and drying the residue in vacuo to obtain 0.57 g of the amorphous polyethylene. , approximately Mn = 17,000; Mn / Mw = 1.3. 1 H NMR showed approximately 105 branches per 1000 carbons. Example 51 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (4-methoxy-2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MAO. A 500 mL round bottom flask fitted with a Schlenk adapter and equipped with a magnetic stir bar and capped with a septum was evacuated, dried by flame, then filled with ethylene. The flask was provided with an ambient temperature (approximately 23 ° C) of water bath, then charged with 100 mL of dry deoxygenated toluene and allowed to equilibrate with 1 atmosphere of ethylene for 30 minutes. The reaction mixture was then treated with 4.0 mL of a 10% by weight MAO solution in toluene and stirred under 1 atmosphere of ethylene, then 0.10 mL of a stored solution (prepared from 6.3 mg of the nickel dibromide of 2,3-bis (4-methoxy-2,6-dimethylphenylimino) - [1,] dithiane and 6.5 mL of dichloromethane). After 10 minutes, the reaction mixture was quenched by the addition of acetone, methanol and aqueous 6 N HCl. The polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, dried on the filter for 2 hours, then dried 13 days in a vacuum oven at 80 ° C. 182 mg of white polyethylene was isolated (254,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 124 ° C. ** H NMR: 13 branches / 1000 carbon atoms. GPC: Mn = 145,600; Mw / Mn = 2.6. Example 52 Polymerization of ethylene with nickel dibromide complex of 2,3-bis-2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of (CH3CH2) 2A1C1. A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to ensure that the reactor was dry. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of a stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1, 4] ditian. The autoclave was heated to 45 ° C and 2 mL of (CH3CH2) 2A1C1 (5000 equivalents) in toluene were added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone and methanol. The swollen polyethylene which was separated, was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C resulting in a white elastic solid of 1.9 g (560,000 TO / h). DSC: (2nd heat) wide fusion with an endothermic maximum at 30 ° C. 1 H NMR: 87 branches / 1000 carbon atoms. GPC: Mn = 557,000; Mw / Mn = 1.82. Example 53 Polymerization of ethylene with the complex ^ of nickel dibromide 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of (CH3CH2) 2A1C1. A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of a stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1, 4 ] Ditian The autoclave was heated to 45 ° C and 0.2 mL of (CH3CH2) 2A1C1 (500 equivalents) in toluene were added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C, resulting in 2 g of a white elastic solid (590,000 TO / h). DSC: (2d0 heat) wide fusion with an endothermic maximum at 30 ° C. 1 H NMR: 85 branches / 1000 carbon atoms. CPG: Mn = 515,000; Mw / Mn = 1.81. Example 54 Polymerization of ethylene with nickel dibromide complex of 2, 3-bis. { 2,6-diisopropylphenylimino) - [1,4] dithiane in the presence of (CH3CH2) 2A1C1. A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of a stored solution (10 mg in 10 mL of CH2Cl2) of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1, 4] ditian. The autoclave was heated to 45 ° C and 0.04 mL of (CH3CH2) A1C1 (100 equivalents) in toluene were added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C, resulting in 1.5 g of a white elastic solid (440,000 TO / h). DSC: (2d0 heat) wide fusion with an endothermic maximum at 29 ° C. 1 H NMR: 80 branches / 1000 carbon atoms. GPC: Mn = 422,000; Mw / Mn = 1.97. Example 55 Copolymerization of ethylene and undecenoate. of ethyl with the nickel dibromide _ complex of 2,3-bis (2,6-dimethylphenylimino) [1,4] dithiane in the presence of MMAO (23% iso-butylaluminoxane). A flaked Schlenk flask equipped with a stir bar and a rubber septum was charged with 50 mL of toluene and 5 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] Ditian. The flask was cooled to 0 ° C in a bath with ice and filled with ethylene (1 atmosphere). 2.0 mL of MMAO in heptane was added to the flask (6.42% by weight of aluminum). Within 5 seconds, 5 mL of ethyl undecenoate was added to give a purple solution. The mixture was allowed to stir for 16 hours. Acetone, methanol and 6M HCl were added to quench the reaction and precipitate the polymer. The polymer was collected by suction filtration and washed with copious amounts of acetone to ensure that all the comonomer of ethyl undecenoate was removed resulting in 100 mg of white powdered polymer. The NMR spectroscopic analysis is consistent with the preparation of an ester group containing copdimer. In addition, the ethylene homopolymer, which resulted from the short reaction time, before the addition of the ethyl undecenoate, was presented. 1 H NMR: 7.5% by weight of ethyl undecenoate incorporated. GPC: Mn = 9500, Mw / Mn = 16.6 DSC: Tm = 128 ° C. Example 56 Copolymerization of ethylene and 1,3-tetradecadiene with the nickel-dibromide complex __ of 2,3-bis (2,6-dimethylphenylimino) - [1,4-diititiano in the presence of MAO. A 200 mL pear-shaped Schlenk flask equipped with a magnetic stirring bar and capped with a septum was dried in flame under vacuum, filled with ethylene, and then loaded sequentially with 50 mL of dry deoxygenated toluene, 6.0 mL of 1, 13-deoxygenated tetradecadiene, and 1.0 mL of a stock solution of 11.8 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, "4] dithiane in 10.0 mL of deoxygenated dichloromethane The flask was placed in a water bath at 23 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 5 minutes, then 4.0 mL of a 10% by weight solution of MAO in toluene was added and the mixture was stirred under 1 atmosphere of ethylene The incorporated ethylene was observed and the mixture rapidly became more viscous.After 7 minutes, the reaction was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl. (100 mL).

The copolymer which was separated was isolated by vacuum filtration and dried in vacuo at 100 ° C for 24 hours to obtain 0.72 g of a white elastic polymer, which formed a gel until the attempted re-dissolution in hot o-dichlorobenzene . Example 57 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MAO. A 200 mL pear shaped Schlenk flask equipped with a magnetic stir bar capped with a septum was charged with 3.4 mg of a nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dioxane. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension was cooled to 0 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 15 minutes, then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. A precipitate of white polyethylene (with a faint yellow-orange hue) was observed in minutes. After 38 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene that separated, was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 18 hours to give 6.0 g of a white polyethylene (54,000). To H). XH NMR: 19 branches / 1000 carbon atoms. GPC: Mn = 504,000; Mw / Mn = 2.3. Example 58 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (benzyloxymethyl) -5,6-bis (2,6-dimethylphenylimino) - [1,4-dioxane in the presence of MAO. A 500 mL round bottom flask was fitted with a Schlenk adapter and equipped with a magnetic stirring bar capped with a septum and charged with 100 mL of dry deoxygenated toluene. The flask was placed in a water bath and allowed to equilibrate with 1 atmosphere of ethylene for 19 minutes, then 0.25 mL of a stored solution prepared from 10.0 mg of the nickel dibromide complex was added., 3-bis (benzyloxymethyl) -5,6-bis (2,6-dimethylphenyl-imino) - [1,4] dioxane and 10.0 mL of dichloromethane. The reaction mixture was then treated with 4.0 L of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere of ethylene. The ethylene was incorporated and the formation of a polyethylene precipitate was observed. After 6.5 minutes, the mixture was quenched by the addition of acetone, methanol and 6 N aqueous HCl. The swollen polyethylene which separated, was isolated by filtration, then dried at 80 ° C in vacuo for several hours. 392 mg of white polyethylene was isolated (404,000 TO / h).

DSC: (2nd heat) fusion with an endothermic maximum at 120 C 1 H NMR: 16 branches / 1000 carbon atoms. GPC: Mn = 125,000; Mw / Mn = 2.8. Example 59 Polymerization of ethylene with the nickel dibromide complex of 5-methoxymethyl-2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MAO. A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 318 mg of a nickel dibromide complex of 5-methoxymethyl-2,3-bis (2,6-dimethylphenylimino) ) - [1,] dioxane. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension was cooled to 0 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 15 minutes then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. After 10 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 48 hours to give 1.04 g of a white powder polyethylene. . A similar reaction, also at 0 ° C, was conducted using 0.655 g (equivalent to 0.57 mg of the nickel complex) of a stored solution of 11.6 mg of the nickel dibromide complex of 5-methoxymethyl-2,3-bis- ( 2,6-dimethylphenylimino) - [1,4] dioxane in 13,238 g of dichloromethane to obtain 291 mg of white powdered polyethylene after 15 minutes of reaction. Example 60 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaluminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to ensure that the reactor was dry. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.3 mL of a stored solution (10 mg in 10 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dioxane. The autoclave was heated to 60 ° C and 2 mL of MMAO in heptane (6.42% by weight of aluminum) were added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 65 ° C. After 10 minutes at 65 ° C, the reaction was quenched by the addition of acetone and methanol. The swollen polyethylene which was separated was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. 1.3 g of a white elastic solid was isolated (480,000 TO / h) DSC gone heat! fusion with an endothermic maximum at 76 ° C. H NMR: 33 branches / 1000 carbon atoms. GPC: Mn = 42,000; Mw / Mn = 1.82. Example 61 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaluminoxane). The procedure described in Example 60 was continued, except that the polymerization was conducted at 25 ° C resulting in 0.59 g of polyethylene (226,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 125 ° C. XH NMR: 9 branches / 1000 carbon atoms. GPC: Mn = 237,000; Mw / Mn = 2.15. Example 62 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dioxane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 60 was continued, except that the polymerization was conducted at 80 ° C resulting in 0.29 g of polyethylene (110,000 TO / h). XH NMR: 69 branches / 1000 carbon atoms. GPC: Mn = 23,000; Mw / Mn = 1.65. Example 63 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 60 was continued except that the polymerization was conducted at 50 ° C resulting in 3.1 g of polyethylene (1,200,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 95 ° C. 1H NMR: 48 branches / 1000 carbon atoms »GPC: Mn = 63,000; Mw / Mn = 1.92. Example 64 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaminoxane). A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to ensure that the reactor was dry. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of stored solution (10 mg in 10 mL of CH2Cl2) of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1, 4] dioxane. The autoclave was heated to 60 ° C and 2 mL of MMAO in heptane (6.42% by weight of aluminum) were added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 65 ° C. After 10 minutes at 65 ° C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which was separated was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. 2.5 g of white elastic solid was isolated (660,000 TO / h). DSC: (2nd heat) wide fusion with an endothermic maximum at 30 ° C. 1E NMR: 82 branches / 1000 carbon atoms. GPC: Mn = 147,000; Mw / Mn = 1.91. Example 65 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 64 was continued except that the polymerization was conducted at 50 ° C resulting in 3.4 g of polyethylene (900,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 50 ° C. 1 H NMR: 65 branches / 1000 carbon atoms. GPC: Mn = 219,000; Mw / Mn = 1.85. Example 66 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,] dioxane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 64 was continued except that the polymerization was conducted at 25 ° C resulting in 1.22 g of the polyethylene (320,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 112 ° C. 1 H NMR: 17 branches / 1000 carbon atoms. CPG: Mn = 476,000; Mw / Mn = 2.02.

Example 67 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dioxane in the presence of MMAO (23% isobutylaminoxane). The procedure described in Example 64 was continued except that the polymerization was conducted at 80 ° C resulting in 0.9 g of polyethylene (240,000 TO / h). DSC: (2d0 heat) fusion with an endothermic maximum at 10 ° C. XH NMR: 99 branches / 1000 carbon atoms. GPC: Mn = 98,800; Mw / Mn = 1.81. EXAMPLE 68 Copolymerization of ethylene and ethyl undecenoate with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane in the presence of MMAO (23% iso-butylaminoxane) . A flaked Schlenk flask equipped with a stir bar and a rubber septum was charged with 50 mL of toluene and 6 mg of nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dioxane. The flask was cooled to 0 ° C in a bath with ice and filled with ethylene (1 atmosphere). To the flask was added, 2.0 mL of MMAO in heptane (6.42% by weight of aluminum). Within 15 seconds, 2.5 mL of ethyl undecenoate was added to give a purple solution. The mixture was allowed to stir for 16 hours. Acetone, methanol and 6M HCl were added to quench the reaction and precipitate the polymer.The polymer was collected by suction filtration and washed with copious amounts of acetone to ensure that all of the ethyl undecenoate comonomer is removed resulting in 510 mg of a white powder polymer The NMR spectroscopic analysis is consistent with the preparation of a copolymer-containing ester group In addition, the ethylene homopolymer, which resulted from the short reaction time before the addition of the undecenoate of ethyl, was presented IR: CO elastic to 1742 cm-1. 1 H NMR: 1.0 wt.% Of ethyl undecenoate incorporated. GPC: Mn = 61,000, Mw / Mn = 6.4 DSC: Tm = 125 ° C. Example 69 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) -4-methylmorpholine in the presence of MAO. A 1 L Fischer-Porter bottle was assembled in a pressure heat equipped with a mechanical stirrer and liquid feeder duct ports, then pressurized to 75 psig of ethylene and relieved at ambient pressure seven times. The bottle was immersed at 54 ° C. The water bath, then 100 mL of dry deoxygenated toluene was added by means of a syringe. The mixture was re-pressurized with ethylene at 75 psig and stirred at 300 rpm for 5 minutes to saturate the solution with ethylene, then the pressure was relieved again, and 4.0 mL of 10% by weight solution of MAO in toluene were added. quickly. The apparatus was re-pressurized again at 75 psig in ethylene and stirred at 300 rpm for another 5 minutes to ensure saturation with ethylene. The pressure was again relieved at ambient pressure and 0.5 mL of a prepared stored solution of 10.0 mg of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) -4-methylmorphdin and 10 mL of dichloromethane were added. quickly and the system was rapidly pressurized once with ethylene at 75 psig. After 7 minutes, the pressure was relieved at atmospheric pressure and the reaction was quenched by the addition of 5 mL of methanol. After the apparatus was disassembled, in 50 additional mL of methanol, 50 mL of 6 N aqueous HCl and 20 mL of acetone were added. The resulting organic layer was separated, washed with 6 N aqueous HCl (1 x 25 mL), and water (2 x 50 mL), then concentrated by rotary evaporation under reduced pressure (10 Torr) at 40 ° C. The residue was then treated with toluene (50 mL) and re-concentrated to yield 134 mg of a very elastic clear polyethylene (55,000 TO / h). XH NMR: 134 branches / 1000 carbon atoms. GPC: Mn = 169,000; Mw / Mn = 1.4. Example 70 Polymerization of ethylene with nickel dibromide complex of 2,3-bis (2,6-dimethyl-phenylimino) -4-methylmorpholine in the presence of MMAO.

A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 1 mL of stored solution (10 mg in 20 mL of CH2Cl2) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -4-methylmorpholine. The autoclave was heated to 45 ° C and 3 mL of MMAO in heptane (6.42% by weight of aluminum) was added. The reactor was rapidly pressurized to 100 psig and the temperature was raised to 50 ° C. After 10 minutes at 50 ° C, the reaction was quenched by the addition of acetone and methanol. The swollen polyethylene which was separated was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C resulting in 0.87 g of a white elastic solid that was isolated (138,000 TO / h). XH NMR: 97 branches / 1000 carbon atoms. EXAMPLE 71 Polymerization of ethylene with the nickel dibromide complex of 1,3-bis (4-methoxy-2,6-dimethylphenyl) -4,5-bis (4-methoxy-2,6-dimethylphenylimino) imidazolidin-2 ona was the presence of MAO. A 500 mL round bottom flask fitted with a Schlenk adapter and equipped with a magnetic stir bar and capped with a septum was evacuated, dried in flame, then filled with ethylene. The flask is proportional to an ambient temperature (approximately 23 ° C) of bath in water, then charged with 100 mL of dry deoxygenated toluene and allowed to equilibrate with 1 atmosphere of ethylene for 30 minutes while stirring at 1000 rpm. The reaction mixture was then treated with 4.0 mL of 10% by weight of MAO solution in toluene and stirred under 1 atmosphere of ethylene, then 0.10 mL of stored solution prepared from 6.0 mg of nickel dibromide complex of 1 , 3-bis (4-methoxy-2,6-dimethylphenyl) -4,5-bis (4-methoxy-2,6-dimethylphenylimino) imidazo-lidin-2-one and 6.0 mL of dichloromethane were added. After approximately 7 minutes and 20 seconds an additional 0.25 mL of a stored solution was added. After a further 15 minutes, the reaction mixture was quenched by the addition of acetone, methanol and aqueous 6 N HCl. The polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried on the filter for 2 hours, then further dried 13 days in a vacuum oven at 80 ° C to obtain 172 mg of white polyethylene. DSC: (2nd heat) fusion with an endothermic maximum at 124 ° C. 1H NMR showed this material to contain about 18 branches / 1000 carbon atoms. GPC: Mn = 56,500; Mw / Mn = 3.55. Example 72 Polymerization of ethylene with the reaction product of 1,3-bis (2,6-dimethyl-phenyl) -4,5-bis- (2,6-dimethyl-phenylimino) -imidazolidin-2-one, dibromide of (1, 2-dimethoxyethane) nickel- (II), and silver tetrafluoroborate in the presence of MAO. A 500 mL round bottom flask fitted with a Schlenk adapter, capped with a septum, and equipped with a magnetic stir bar, was charged with 100 mL of dry deoxygenated toluene. The flask was placed in a water bath and allowed to equilibrate with 1 atmosphere of ethylene for 10 minutes, then 0.10 mL of a stored solution (freshly prepared from 240 mg of the reaction product of 1,3-bis) was added. (2,6-dimethylphenyl) -4,5-bis- (2,6-dimethylphenylimino) -imidazolidin-2-one, (1,2-dimethoxyethane) nickel (II) dibromide, and silver tetrafluoroborate at 10. mL of dry deoxygenated dichloromethane). The reaction mixture was then treated with 4.0 mL of 10% by weight of MAO solution in toluene and stirred under 1 atmosphere of ethylene. The ethylene was incorporated and the formation of a polyethylene precipitate was observed. After 6.33 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which was separated was isolated by vacuum filtration, then dried at 80 ° C in vacuo for several hours. 860 mg of a white polyethylene powder was isolated (87,000 TO / h). XH NMR: 15 branches / 1000 carbon atoms. GPC: Mn = 76,000; Mw / Mn = 2.6. Example 73 Polymerization of ethylene using a catalyst generated in situ from tetrakis (2,6-dimethylphenyl) oxalamidine, bis (1,5-cyclooctadienp) nickel (0) and HB (Ar) 4 (Ar = 3,5-bis) (trifluoromethyl) phenyl). A 250 mL pear shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 8.0 mg of bis (1,5-cyclooctadiene) nickel (0), 19 mg of N1, N2, N3, iV4-tetrakis (2,6-dimethylphenyl) oxalamidine, and 33 mg of the ether solvate of HB (Ar) The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The yellow solution which resulted was stirred under ethylene at 0 ° C for 30 minutes, then warmed to 25 ° C and stirred for another 30 minutes under ethylene before being quenched by the addition of acetone (50 mL) and methanol (50 mL). The polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.5 mm Hg) for 14 hours to give 0.70 g of a white elastic polyethylene (860 average TO / h). 1E NMR: 83 branches / 1000 carbon atoms. GPC: Mn = 173,000; Mw / Mn = 2.8. Example 74 Polymerization of ethylene with the nickel dibromide complex of _ 1 L 4 -dimethyl-2,3-bis (2,6-dimethylphenylimino) -piperazine in the presence of MAO.

A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 10.4 mg of the nickel dibromide complex of 1,4-dimethyl-2,3-bis (2,6- dimethylphenylimino) piperazine. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension was cooled to 0 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 15 minutes, then treated with 4.0 mL of 10% by weight of a solution of MAO in toluene. The yellow solution which resulted was stirred under ethylene at 0 ° C for 1 hour, and then quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.5 mm Hg) for 14 hours to give 1.3 g of a clear elastic polyethylene (2531 TO / h). XH NMR: 91 branches / 1000 carbon atoms. GPC: Mn = 127,000; Mw / Mn = 1.3. Example 75 Polymerization of ethylene using XXXV complex. A flaked Schlenk flask equipped with a stir bar and a rubber septum was charged with 50 mL of methylene chloride and 50 mg of the palladium complex XXXV. The flask was placed under an ethylene atmosphere (1 atmosphere). The mixture was allowed to stir for 20 hours. Acetone and methanol were added to quench the reaction and precipitate the polymer. The polymer was collected and dried in vacuo resulting in 2.6 g of the sticky polymer. The NMR spectroscopic analysis is consistent with the preparation of an ethylene homopolymer. 1H NMR: highly branched polyethylene. GPC: Mn = 34,000, Mw / Mn = 2.5 DSC: Tm = -39 ° C. Tg = -69 ° C. Example 76 Polymerization of propylene using complex XXXV. A flaked Schlenk flask equipped with a stir bar and a rubber septum was charged with 50 ml of methylene chloride and 50 mg of the palladium complex XXXV. The flask was placed under a propylene atmosphere (1 atmosphere). The mixture was allowed to stir for 20 hours. Acetone and methanol were added to quench the reaction and precipitate the polymer. The polymer was collected and dried in va cuo resulting in 580 mg of the sticky polymer. XH NMR: 192 branched points / 1000 carbon atoms. GPC: Mn = 17, 000, Mw / Mn = 2.08. DSC: Tg = -53 ° C. Example 77 Copolymerization of ethylene / vinyl ethylene carbonate using complex XXXV. A 200 ml dried flaked pear Schlenk flask equipped with a stir bar and capped with a septum was loaded with catalyst XXXV (2,6-diisopropylphenylimino) - [1,4] dithia Pd (II) (100 mg ) in a glove box filled with argon. Until the removal of the glove box, the flask was evacuated and subsequently filled with ethylene. The catalyst was dissolved in CH2C12 (25 mL) and treated immediately with vinylethylene carbonate (5 mL). The resulting orange solution was stirred at 23 ° C under an atmosphere of ethylene (1 atm) for 20 hours. A small amount of polymer precipitated out of the solution. The polymerization was quenched with MeOH and acetone leaving gray oil adhering to the walls of the flask. The polymer was washed several times with acetone and MeOH to remove any permanent monomer. The polymer was dissolved in CH2C12 and transferred to a storage jar. The solvent was allowed to evaporate and the resulting oily polymer was dried in vacuo at ~ 80 ° C for 3 days to produce a sticky solid (2.15 g, 1100 TO). 1 H NMR was consistent with a copolymer containing about 96.5% by weight of ethylene and 3.5% by weight of vinylethylene carbonate monomer units; Mn 40,200 moles; Mw 92,100 '/ moles / DSC Tg -68 ° C, Tm -38 ° C. Example 78 Copolymerization of ethylene / vinyl ethylene carbonate using complex XXXV. A 200 ml dried flaked pear Schlenk flask, equipped with a magnetic stir bar and capped with a septum, was charged with catalyst XXXV (2,6-diisapropylaminimino) - [1,4] -ditiano Pd (II ) (100 mg), in a glove box filled with argon. Until the removal of the glove box, the flask was evacuated and subsequently filled with ethylene. The catalyst was dissolved in CH2Cl2 (20 mL) and immediately treated with vinylethylene carbonate (10 mL). The resulting orange solution was stirred at 23 ° C under an ethylene atmosphere (1 atm) for 28 hours. A small amount of polymer precipitated out of the solution. The polymerization was quenched with MeOH and the acetone leaving gray oil adhering to the walls of the flask. The polymer was dissolved in CH2C12 and transferred to a stored jar. The solvent was allowed to evaporate and the resulting oily polymer was washed several times with acetone and MeOH to remove any permanent monomer and dry in vacuo at ~80 ° C for 1 day to produce a sticky solid (1.15 g, 613 TO). 1H NMR was consistent with a copolymer containing about 95.5% by weight of ethylene and 4.5% by weight of vinylethylene carbonate monomer units; Mn 15,400 g / mo? Es; Mw 96,000 g / mo? Es; DSC Tg -64 ° C, Tm -31 ° C. Example 79 Preparation of the nickel dibromide complex of 2,3-bis (2,6-diisopropylphenylimino) - [1,4] dioxane. A Schlenk flask equipped with a magnetic stir bar was charged with 100 mg of 2,3-bis (2,6-diisopropylimino) - [1,4] dioxane (0.25 mmol) and 71 mg of dibromide (1, 2). -dimethoxyethane) nickel (II) (0.23 mmole) under an argon atmosphere. Dry deoxygenated dichloromethane (15 mL) was added and the mixture was stirred under an argon atmosphere, becoming red-brown within about 10 minutes. After 2 hours, the red / orange solution was transferred through a filter cannula to a new flame dried Schlenk flask to remove non-reactive trace amounts of (1,2-dimethoxyethane) nickel (II) dibromide. The CH2Cl2 was removed in vacuo. The resulting red-brown solid was washed with 2x10 mL of hexane and the solid was dried in vacuo for several hours yielding 80 mg of a brown solid. Example 80 Preparation of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo [2, 1-jbjthiazole. A 50 mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser capped by a nitrogen inlet was charged with 752 mg of N-NXbis (2,6-dimethylphenyl) oxalodiimidoyl dichloride, 200 mg of hydride of sodium (60% dispersion of mineral oil), 5.0 mL of dry tetrahydrofuran, and 250 mg of 2-merpcatoimidazole. The mixture was heated to reflux for 120 minutes. After cooling, the mixture was diluted with water and dichloromethane, and the organic layer was separated and concentrated to produce a yellow-orange oil. Column chromatography (Si02, 230-400 Merck Grade 9385 mesh, 60 A, 12 vol% ethyl acetate in hexane) yielded 487 mg of a yellow-orange solid. Recrystallization from heptane gave 366 mg of yellow-orange prisms. Field desorption mass spectrometry showed a parent ion peak at 360 m / z. Example 81 Preparation of the diphenylester of N ^ N ^ -bis (2,6-dimethyl-phenyl) -ethanediimidoselenoic acid. A 50 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by a nitrogen inlet was charged with 961 mg of N1, N2-bis (2,6-dimethylphenyl) oxalodiimidoyl dichloride, 287 mg of sodium hydride (60% dispersion in mineral oil), 8.2 mL of dry tetrahydrofuran, and .068 mL of benzeneslenol. The mixture was heated to reflux for 45 minutes. After cooling, the mixture was diluted. with water and diethyl ether. The ether layer was separated and washed again with water, then concentrated in vacuo to yield a crystalline yellow-orange solid. The solid was dissolved in hot hexane, then filtered, and then reconcentrated. Recrystallization from heptane produced 745 mg of orange prisms. The grains. Field desorption mass spectrometry showed a cluster or parent ion peaks of 570-578 m / z. XH NMR (300 MHz, CDC13, chemical changes in ppm relative to TMS at 0 ppm): 1.95 (12p, s), 6.75 (6p, apparent s), 7.02-7.20 (6p, m), 7.39-7.48 (4p, m). EXAMPLE 82 Polymerization of ethylene using a catalyst generated in situ from the diphenylester of N ^ N ^ - is (2,6-dimethylphenyl) ethanediimidoselenoic acid, bis (1,5-cyclooctadiene) -nickel (0) and HB (Ar) 4 (Ar = 3,5-bis (trifluoromethyl) phenyl). A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 5 mg of bis (1,5-cycloatadiene) nickel (0), 10 mg of diphenylester of N ^ NXbis acid (2,6-dimethylphenyl) ethanediimidoselenoic acid and 25 mg of the ether solvate of HB (Ar) 4. The flask was evacuated and filled with ethylene, then charged with 45 mL of dry deoxygenated toluene. The yellow solution which resulted was stirred under ethylene at 21 ° C for 10 minutes, then quenched by the addition of methanol (50 mL). The polyethylene was separated, isolated by vacuum filtration and washed with methanol, then dried under reduced pressure (0.5 mm Hg) for 14 hours to give 0.060 g of an elastic blue-green polyethylene. 1H? MR: 24 branches / 1000 carbon atoms. GPC: Mn = 181,000; Mw / Mn = 3.5. Example 83 Preparation of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo [2, 1-Jb] thiazole. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 141 mg of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo [2, 1-jb] thiazole and 110 mg of (1,2-dimethoxyethane) nickel (II) dibromide under an inert atmosphere. Dry deoxygenated dichloromethane (5 mL) was added and the mixture was stirred under an argon atmosphere. After 1 hour, another 5 mL of dichloromethane was added. The mixture was stirred another 16 hours at 21 ° C, then diluted with 10 mL of dry deoxygenated hexane and stirred for another 3 hours. The supernatant was removed through a filter paper cannula, and the residue was dried in vacuo at 1 mm Hg to yield 66 mg of a brown microcrystalline solid. Example 84 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo- [2, 1-jb] -thiazole in the presence of MAO. A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was loaded with 2.5 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2, 3 -dihydroimidazo [2,1-jbjtiazol. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension was allowed to equilibrate with 1 atmosphere of ethylene at 21 ° C for 15 minutes, then treated with 200 μl of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. After 21 minutes, the reaction was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL). The swollen polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 24 hours to give 198 mg of a white polyethylene. ? NMR: 13 branches / 1000 carbon atoms. GPC: bimodal, with Mn = 23,000; Mp = 366,000; Mw / Mn = 13.5. Example 85 Preparation of the nickel dibromide complex of N1, N2, N3, N4-tetrak 'xs (2,6-dimethylphenyl) oxalamidine. A 50 mL Schlenk flask equipped with a magnetic stir bar and capped with a septum was loaded with 100 mg of N1, N2, N3, N-tetratrax (2,6-dimethylphenyl) oxalamidine and 55 mg of dibromide (1). , 2-dimethoxyethane) nickel (II) under an inert atmosphere. Dry deoxygenated dichloromethane (5 mL) was added and the mixture was stirred under an argon atmosphere. After 1 hour another 5 mL of dichloromethane were added. The mixture was stirred another 16 hours at 21 ° C, then diluted with 10 mL of dry deoxygenated hexane and stirred for another 3 hours. The supernatant was removed through a filter paper cannula, and the residue was dried in vacuo at 1 mm Hg to yield 95 mg of light green crystals. Example 86 Polymerization of ethylene with the nickel dibromide complex of N ^ N ^ N ^ i ^ -tetrakis (2,6-dimethylphenyl) oxalamidine in the presence of MAO. A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 2.4 mg of the nickel dibromide complex of Nx N'X N'N'-tetrakis (2,6-dimethylphenyl) ) oxalamidine. The flask was evacuated and filled with ethylene, then charged with 75 mL of dry deoxygenated toluene. The resulting suspension allowed to equilibrate with 1 atmosphere of ethylene at 21 ° C for 15 minutes, then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. After 30 minutes, the reaction was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous HCl 6? (100 mL). The swollen polyethylene which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg) for 24 hours to give 743 mg of a white polyethylene. 1H? MR: 112 branches / 1000 carbon atoms. GPC: Mn = 330,000; Mw / Mn = 1.4. EXAMPLE 87 Copolymerization of ethylene and 1-pentene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4-dithiane in the presence of MAO.] A pear-shaped Schlenk flask of 200 mL equipped with a magnetic stir bar and capped with a septum was loaded with 0.5 mL of a stored solution of 12.4 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane in 10.0 mL of dichloromethane The flask was evacuated and filled with ethylene, then charged with 100 mL of dry deoxygenated toluene, and 5.0 mL of 1-pentene The resulting suspension was cooled to 0 ° C and allowed equilibrate with 1 atmosphere of ethylene for 15 minutes, then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene.After 45 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6 N HCl (100 mL) The swollen copolymer which is eparo was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (255 mm Hg) at 100 ° C for 24 hours to obtain 2.0 g of the white copolymer. XH NMR: 24 branches / 1000 carbon atoms. 13C NMR: 7.6 branches of methyl / 1000 carbons, 1.2 branches of ethyl / 1000 carbons, 9.1 branches of propyl / 1000 carbons, 2.1 branches of butyl / 1000 carbons, 3.4 branches of pentyl and higher alkyl / 1000 carbons. GPC: Mn = 274,000; Mw / Mn = 2.3. Example 88 Copolymerization of ethylene and 1-heptene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MAO. A 200 mL pear shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was loaded with 0.5 mL of a stored solution of 12.4 mg of the 2,3-bis nickel dibromide complex (2.6 -dimethylphenylimino) - [1,4] dithiano in 10. Q mL dichloromethane. The flask was evacuated and filled with ethylene, then charged with 100 mL of dry deoxygenated toluene, and 5.0 mL of 1-heptene. The resulting suspension was cooled to 0 ° C and allowed to equilibrate with 1 atmosphere of ethylene for 15 minutes, then treated with 4.0 mL of a 10% by weight solution of MAO in toluene and stirred under 1 atmosphere of ethylene. After 33 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and aqueous 6N HCl (100 mL). The swollen copolymer which was separated was isolated by vacuum filtration and washed with water, methanol and acetone, then dried under reduced pressure (255 mm Hg) at 100 ° C for 24 hours to obtain 1.25 g of a white copolymer . 1H NMR: 19 branches / 1000 carbon atoms. 13C NMR: 5.9 methyl branches / 1000 carbons, less than 1 ethyl branch / 1000 carbons, less than 1 propyl branch / 1000 carbons, 1.8 butyl branches / 1000 carbons, 11.5 pentyl and higher alkyl branches / 1000 carbons. GPC: Mn = 223,000; Mw / Mn = 2.3. Example 89 Polymerization of 1-hexene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of MAO A 22 mL flask equipped with a stir bar magnetic and capped by a septum was sequentially loaded with 1.8 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane, 4.0 mL of 1-hexene, and 2.0 mL of a solution at 10% by weight of MAO in toluene, under Ar. The resulting violet mixture markedly thickened in minutes. After 34 minutes, the reaction was quenched with acetone, methanol and aqueous 6 N HCl, and the polyhexene which was separated, filtered and dried in vacuo (0.4 mm Hg) to obtain 428 mg of an elastic polyhexene. 1E NMR: 173 branches / 1000 carbon atoms. GPC: Mn = 92,000; Mw / Mn = 2.0. Example 90 Polymerization of 1-hexene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo- [2, 1-J "lthiazole in the presence of MAO.

A 22 mL bottle equipped with a magnetic stir bar and covered by a septum was loaded sequentially with 2.1 mg of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) -2,3-dihydroimidazo [2]. , l-Jb] thiazole, 4.0 mL of 1-hexene, and 2.0 mL of a 10% by weight solution of MAO in toluene, under Ar. The resulting dark purple-brown blend remarkably thickened within 10-20 minutes. After 53 minutes, the reaction was quenched with acetone, methanol and aqueous 6N HCl, and the polyhexene which was separated was filtered and dried in vacuo (0.4 mm Hg) to obtain 283 mg of an elastic polyhexene. XH NMR: 110 branches / 1000 carbon atoms GPC: Mn = 91,000; Mw / Mn = 1.9. Example 91 Polymerization of 1-hexene with the nickel dibromide complex of 1,4-dimethyl-2,3-bis (2,6-dimethylphenylimino) -piperazine in the presence of MAO. A 22 mL bottle equipped with a magnetic stir bar and capped by a septum was loaded sequentially with 2.1 mg of the nickel dibromide complex of 1,4-dimethyl-2,3-bis (2,6-dimethylphenylimino) -piperazine. , 4.0 mL of 1-hexene, and 2.0 mL of a 10% by weight solution of MAO in toluene, under Ar. The resulting light yellow solution was stirred at 23 ° C for 400 minutes, then the reaction was quenched with acetone, methanol and aqueous 6N HCl, and the polyhexene which separated was filtered and dried in vacuo (0.4 mm Hg). to obtain 408 mg of an elastic polyhexene. 1 H NMR: 90 branches / 1000 carbon atoms GPC: Mn = 47,000; Mw / Mn = 1.7. Example 92 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) [1,4] dithiane. A flake-dried pear-shaped flask equipped with a stir bar and a septum was charged with 30 mg (52 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane and 1 g of MAO was treated with silica (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 25 mL of CH2C12 was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour the solvent was removed in va cuo. The resulting purple solid was washed with CH2C12 using a filter cannula and dried under dynamic vacuum. Example 93 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A flake-dried pear-shaped flask equipped with a stir bar and a septum was charged with 15 mg (26 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane and 1 g of MAO was treated with silica (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of toluene was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour the solid was fixed and the solvent was removed by means of a filter cannula. The resulting purple solid was washed with toluene using a filter cannula. The resulting purple silica support material was dried under dynamic vacuum yielding 916 mg of the supported catalyst material. Example 94 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A flake-dried pear-shaped flask equipped with a stir bar and a septum was charged with 30 mg (52 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane and 1 g of MAO was treated with silica (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of toluene was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour the solid was allowed to settle and the solvent was removed through a filter cannula. The resulting purple solid was washed with toluene using a filter cannula and dried under dynamic vacuum to give 900 mg of the supported catalyst material. Example 95 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylamino) - [1,4] dithiane. A flake-dried pear-shaped flask equipped with a stir bar and a septum was charged with 34 mg (50 μmol) of the nickel dibromide complex., 3-bis (2,6-diisopropylphenylimino) - [1,4] dithiano and 1 g of MAO was treated with silica (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of CH2C12 was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour the solvent was removed in vacuo. The resulting brown red solid was washed with CH2C12 using a filter cannula and dried under dynamic vacuum to give 780 mg of the supported catalyst. Example 96 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A flake-dried pear-shaped flask equipped with a stir bar and a septum was charged with 15 mg (26 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dithiane and 1 g of MAO was treated with silica (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of CH2C12 was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour the solvent was removed in vacuo resulting in 940 mg of a purple solid.

Example 97 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in example 92. A pear-shaped flask, flame dried, equipped with a stir bar and a septum was charged with 100 mg of the nickel / MAO treated in supported catalyst system of silica prepared in example 92. The flask was placed under an ethylene atmosphere and 50 mL of toluene was added giving a red suspension. coffee. The polymerization was allowed to stir for 1 hour at 23 ° C. After 60 minutes at 23 ° C, the reaction was quenched by the addition of acetone, 6M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 1.6 g of a white elastic solid (11,000 TO / h based on 100% active catalyst). DSC: (2nd heat) fusion with an endothermic maximum at 118 ° C. XH NMR: 30 branches / 1000 carbon atoms. GPC: Mn = 208,000; Mw / Mn = 2.45. Example 98 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in Example 92. A Parr® autoclave of 600 mL was first heated to about 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded in the glove box with 200 mg of the supported catalyst prepared in Example 92. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 60 °. C. The reactor was rapidly pressurized to 90 psig of ethylene. After 60 minutes at 60 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 22.5 g of a white elastic solid £ 80,000 TO / h) 1 H NMR: 31 branches / 1000 carbon atoms. GPC: Mn = 128,000; Mw / Mn = 2.58. Example 99 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in Example 92. A Parr® autoclave of 600 mL was first heated to about 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 100 mg of the supported catalyst prepared in Example 92. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 100 °. C. The reactor was rapidly pressurized to 90 psig of ethylene and the temperature was raised to 140 ° C. After 60 minutes at 140 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C. GPC: Mn = 56,000; Mw / Mn = 7.19. Example 100 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4-dithiane prepared in Example 95. A Parr® autoclave of 600 mL was first heated to approximately 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 100 mg of the supported catalyst prepared in Example 95. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 50 °. C. The reactor was rapidly pressurized to 90 psig of ethylene. After 30 minutes at 50 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 1.25 g of a white elastic solid (18,000 TO / h) XH NMR: 62 branches / 1000 carbon atoms. GPC: Mn = 336,000; Mw / Mn = 2.22. Example 101 Polymerization of ethylene using the supported nickel complex of 2, 3-bis (2, 6-dimethylphenylimino) - [1,4] dithiane prepared in Example 93. A Parr® 600 mL autoclave was first heated to about 100 ° C under dynamic vacuum to make sure the reactor dried. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 200 mg of the supported catalyst prepared in Example 93. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 50 °. C. The reactor was rapidly pressurized to 90 psig of ethylene. After 60 minutes at 50 ° C, the reaction was quenched by the addition of acetone, 6M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 2.13 g of a white elastic solid (30,000 TO / h) DSC: 2ds heat showed an endothermic maximum at 120 ° C. 1 H NMR: 17 branches / 1000 carbon atoms. GPC: Mn = 119,000; Mw / Mn = 2.93. Example 102 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in Example 94. A Parr® autoclave of 600 mL was first heated to about 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 100 mg of the supported catalyst prepared in Example 94. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 50 °. C. The reactor was rapidly pressurized to 90 psig of ethylene. After 60 minutes at 50 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and metansl. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 5.97 g of a white elastic solid (41,000 TO / h) DSC: 2nd heat showed an endothermic maximum at 120 ° C. GPC: Mn = 138,000; Mw / Mn = 2.95. 1R NMR: 17 branches / 1000 carbon atoms. Example 103 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared according to the procedure described in example 92. A Parr® autoclave of 600 L heated first at approximately 100 ° C under dynamic vacuum to make sure the reactor dried. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 100 mg of the supported catalyst. Until the autoclave was removed from the box, 150 mL of toluene was added and the reactor was heated to 65 ° C. The reactor was rapidly pressurized to 100 psig of ethylene. After 60 minutes at 65 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 9.0 g of a white elastic solid (62,000 TO / h). DSC: 2nd heat showed an endothermic maximum at 116 ° C. GPC: Mn = 83,500; Mw / Mn = 4.71. XH NMR: 35 branches / 1000 carbon atoms. Example 104 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in Example 96. A Parr® autoclave of 600 mL was first heated to approximately 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded in the glove box with 100 mg of the supported catalyst prepared in Example 96. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 50 °. C. The reactor was rapidly pressurized to 100 psig of ethylene. After 60 minutes at 50 ° C, the reaction was quenched by the addition of acetone, 6M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 6.5 g of a white elastic solid (88,000 TO / h) DSC: 2nd heat showed a wide melting transition with endothermic maximum at 119 ° C. GPC: Mn = 182,600; Mw / Mn = 3.01. XH NMR: 19 branches / 1000 carbon atoms. EXAMPLE 105 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4T-dithiane prepared in example 96. A Parr® autoclave of 600 mL was first heated to about 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded in the glove box with 100 mg of the supported catalyst prepared in Example 96. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 50 °. C. The reactor was rapidly pressurized to 100 psig of ethylene. After 60 minutes at 50 ° C, the reaction was quenched by the addition of acetone, 6M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 5.4 g of a white elastic solid (74,000 TO / h) DSC. 2nd heat showed wide fusion transition with endothermic maximum at 120 ° C. GPC: Mn = 186,500; Mw / Mn = 2.66. XH NMR: 18 branches / 1000 carbon atoms. Example 106 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared in Example 96. A Parr® autoclave of 600 mL was first heated to about 100 ° C under dynamic vacuum to ensure that the reactor dries. The reactor was then purged with argon. The Parr® autoclave of 600 mL was loaded into the glove box with 100 mg of the supported catalyst prepared in Example 96. Until the autoclave was removed from the box, 150 mL of the toluene was added and the reactor was heated to 30 °. C. The reactor was rapidly pressurized to 100 psig of ethylene. After 60 minutes at 30 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 100 ° C resulting in 11.5 g of a white elastic solid (160,000 TO / h). DSC: 2nd heat showed an endothermic maximum at 127 ° C. GPC: Mn = 279,000; Mw / Mn = 2.73. XH NMR: 7 branches / 1000 carbon atoms. Example 107 Synthesis of the supported nickel complex of 2,3-bis (phenylimino) - [1,4] dithiane.

A 500 ml flamed pear-shaped flask equipped with a magnetic stir bar and capped by a septum was loaded with 27 mg (52 μmol) of the nickel dibromide complex of 2,3-bis (phenylimino) - [1, 4] dithiane and 1.0 g MAO was treated with silica (Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 25 mL of dry deoxygenated CH2C12 was added. The reaction was stirred at 0 ° C for 50 minutes, then the volatiles were removed by evaporation under reduced pressure (0.2 torr) at 0 ° C for 40 minutes to produce the supported catalyst as a light gray-green powder which was stored under nitrogen at -25 ° C. EXAMPLE 108 Synthesis of the supported nickel complex of 2,3-bis (2-tert-butylphenylimino- [1,4] "dithiane. A pear-shaped flask, flame dried at 500 mL, equipped with a magnetic stir bar and capped by a septum was loaded with 34 mg (56 μmoles) of the nickel dibromide complex of 2, 3-bis (2-tert-butylphenylamino) - [1,4] dithiane and 1.0 g of silica treated with MAO (Witco TA 02794 / HL / 04) .The solid mixture was cooled to 0 ° C in an ice bath and 25 mL of dry deoxygenated CH2C12 was added in. The reaction was stirred at 0 ° C for 50 minutes, then the volatiles were removed. by evaporation under reduced pressure (0.2 torr) at 0 ° C for 40 minutes to produce the supported catalyst as a light brown powder which was stored under nitrogen at -25 ° C. Example 109 Synthesis of supported nickel complex of 2, 3 -bis (2,6-dimethylphenylimino) - [1,4] dioxane A pear-shaped flask, dried in a 500 mL flame, equipped with a bar magnetic stirring capped by a septum was loaded with 30 mg (55 μmol) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane and 1.01 g of silica treated with MAO (Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in a bath with ice and 25 mL of dry deoxygenated CH2C12 was added. The reaction was stirred at 0 ° C for 65 minutes, then the volatiles were removed by evaporation under reduced pressure (0.2 torr).; 20 minutes at 0 ° C, 75 minutes at 25 ° C) to produce the supported catalyst as a brown powder, which was stored under nitrogen at -25 ° C. Example 110 Polymerization of ethylene using the supported nickel complex of 2,3-bis (phenylimino) - [1,4] dithiane. A pear shaped flask, dried in a 500 mL flame, equipped with a magnetic stir bar and capped by a septum was charged with 100 mg of the supported nickel complex of 2,3-bis (phenylimino) - [1, 4 ] ditian prepared in Example 107. The flask was evacuated and filled with ethylene, then treated with 50 mL of dry deoxygenated toluene and stirred under 1 atmosphere of ethylene at 23 ° C for 14 hours. The reaction was quenched by the addition of methanol, acetone and 6 N HCl. The polymer which separated, was isolated by filtration and dried in vacuo to yield 0.177 g of a white powder polyethylene. DSC: (2nd heat) maximum endothermic fusion at approximately 100, 106 and 127 ° C. GPC: Mn = 1,100 g / moles; Mw / Mn = 15.5. Example 111 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2-tert-butylphenylimino) - [1,4] dithiane. A pear shaped flask, dried in a 500 mL flame, equipped with a magnetic stir bar and capped by a septum was charged with 100 mg of the supported nickel complex of 2,3-bis (2-er-butylphenylimino) - [1,4] dithiane prepared in Example 108. The flask was evacuated and filled with ethylene, then treated with 50 mL of dry deoxygenated toluene, and stirred under 1 atmosphere of ethylene at 23 ° C for 125 minutes. The reaction was quenched by the addition of methanol, acetone and 6 N HCl. The polymer which separated was isolated by filtration and dried in vacuo to yield 0.529 g of the white powder polyethylene. DSC: (2nd heat) maximum endothermic fusion at 96 and 110 ° C. XH NMR (o-dichlorobenzene): 36 branches / 1000 carbon atoms GPC: Mn = 120,000; Mw / Mn = 2.46.

Example 112 Polymerization of ethylene using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dioxane. A 500 ml flaked, pear-shaped flask equipped with a magnetic stir bar and capped with a septum was loaded with 106 mg of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1, 4] dioxane prepared in Example 109. The flask was evacuated and filled with ethylene, then treated with 50 mL of dry deoxygenated toluene, and stirred under 1 atmosphere of ethylene at 23 ° C for 255 minutes. The reaction was quenched by the addition of methanol, acetone and 6 N HCl. The polymer which was separated was isolated by filtration and dried in vacuo to yield 3.2 g of the white powder polyethylene. XH NMR (o-dichlorobenzene). 20 branches / 1000 carbon atoms. DSC: (2nd heat) maximum endothermic fusion at 118 ° C. CPG: Mn = 150, 000; Mw / Mn = 3.10. EXAMPLE 113 Copolymerization of ethylene and ethyl undecenoate using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared as described in example 92. A flask in the form of Pear, dried in flame, equipped with a stir bar and a septum was charged with 100 mg of nickel / MAO treated with a supported catalyst system of silica. The flask was placed under an atmosphere of ethylene and 45 mL of toluene and 2.5 mL of ethyl undecenoate was added, giving a purple suspension. The polymerization was allowed to stir for 5 hours at 0 ° C. After 5 hours at 0 ° C, the reaction was quenched by the addition of acetone, 6 M HCl and methanol. The white copolymer was isolated by filtration, washed with copious amounts of acetone and dried for several hours in a vacuum oven at 100 ° C resulting in 1.3 g of a white powdery solid (1800 TO / h based on 100% of the active catalyst). XH NMR indicated 1% by weight of the ethyl undecenoate incorporated in the copolymer. EXAMPLE 114 Copolymerization of ethylene and ethyl undecenoate using the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane prepared as described in example 92. A pear-shaped flask , dried in flame, equipped with a stir bar and a septum was charged with 100 mg of nickel / MAO treated with the supported catalyst system of silica. The flask was placed under an atmosphere of ethylene, 45 mL of toluene and 2.5 mL of ethyl undecenoate was added giving a purple suspension. The polymerization was allowed to stir for 3.5 hours at 23 ° C.

After 3.5 hours at 23 ° C, the reaction was quenched by the addition of acetone, 6M HCl and methanol. The white copolymer was isolated by filtration, washed with copious amounts of acetone and dried for several hours in a vacuum oven at 100 ° C resulting in 1.4 g of a white powder solid (2700 TO / h based on 100% of the active catalyst). H NMR indicates 1% by weight of ethyl undecenoate incorporated in the copolymer. Obviously, numerous modifications and variations of the present invention are possible in light of the prior art. It will therefore be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. Example 115 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano. A flame-dried, pear-shaped flask equipped with a stir bar and a septum was charged with 9 mg (16 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1 , 4] dithiane and 3 g of silica was treated with MAO (purchased by Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 25 mL of toluene was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour, the solvent was removed in vacuo giving 2.8 g of the supported catalytic material. Example 116 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A pear-shaped, flame-dried flask equipped with a stir bar and a septum was charged with 6 mg (10 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1 , 4] ditian and 1 g of silica treated with MAO (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of CH2Cl2 was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour, the solvent was removed in vacuo, yielding a supported coffee catalytic material. The supported catalyst was then suspended in 20 mL of hexane followed by the addition of 2 mL (4 mmol) of trimethylaluminium (TMA). The mixture was stirred at 0 ° C for one hour. The solvent was removed in vacuo together with the excess TMA leaving the catalyst system supported. Example 117 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano. A pear-shaped flask, dried in flame, equipped with a stir bar and a septum was charged with 15 mg (26 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [ 1, 4] dithiano and 1 g of silica (Grace Davison XPO-2402). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of toluene and 7 mL of a MAO solution in toluene was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour, the solvent was removed in vacuo to give 1.3 g of the supported catalyst. Example 118 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano. A pear-shaped flask, dried in flame, equipped with a stir bar and a septum was charged with 18 mg (31 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [ 1, 4] ditian and 3 g of silica treated with MAO (purchased from Witco TA 02794 / HL / 04). The solid mixture was cooled to 0 ° C in an ice bath and 25 mL of CH2C12 was added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour, the solvent was stirred in vacuo yielding a coffee supported catalytic material. The supported catalysts were then suspended in 20 mL of hexane followed by the addition of 0.5 mL of MAO. The mixture was stirred at 0 ° C for one hour. The solvent was removed in vacuo leaving 2.9 g of the supported catalyst. Example 119 Synthesis of the supported nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4-dithiane A pear-shaped flask, dried in flame, equipped with a stir bar and a septum charged with 6 mg (10 μmoles) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,] dithiane and 1 g of silica (Grace Davison XPO-2402). The solid mixture was cooled to 0 ° C in an ice bath and 20 mL of hexane and 2 mL of TMA solution in toluene were added. The reaction was stirred rapidly at 0 ° C for 1 hour. After 1 hour, the solvent was removed in vacuo giving 0.94 g of the supported catalyst. Gas Phase Polymerization XXVII Preparation of A-XXVII / MAO Catalysts in Silica (Witco) /O.3 mg of XXVII per gram of silica. See example 115 as a representative example. B- XXVII / MAO in Silica (Witco) / 3 mg of XXVII per gram of silica. See example 92 as a representative example.

C- XXVII / MAO in Silica (Witco) /O.3 mg of XXVII per gram of silica / extra added MAO. See example 118 as a representative example. D- XXVII / Silica (Grace Davison XPO-2402) / MAO solution / 1.5 mg of XXVII per gram of silica. See example 117 as a representative example. E- XXVII / MAO in Silica (Witco) /O.6 mg of XXVII per gram of silica / extra added MAO. See example 118 as a representative example. F- XXVII / MAO on silica (Witco) /O.6 mg of XXVII per gram of silica / extra added TMA. See example 116 as a representative example. G- XXVII / Silica (Grace Davison XPO-2402) / TMA solution / 0.6 mg of XXVII per gram of silica. See example 117 as a representative example. H- XXVII / MAO in Silica (Witco) /O.6 mg of XXVII per gram of silica. See example 115 as a representative example. Gas Phase Polymerization Procedure The basic procedure involves supporting a stirred Parr ® 600 mL autoclave with 300 g of NaCl (drying in a vacuum oven at 100 ° C for 24 hours) and a known quantity of supported XXVII catalyst. The ethylene homopolymerization reactions summarized below were continued between 50 ° C and 80 ° C and 100 and 1000 psig of ethylene.

The resulting polyethylene was isolated by dissolving the NaCl in a mixer and collecting the remaining polymer by filtration. The polyethylene was washed with 6 M HCl, water and acetone. The polymer was then dried in a vacuum oven at 100 ° C. A- 80 ° C / 800 psig ethylene / 20 minutes reaction time / 200 mg of supported catalyst. B- 65 ° C / 400 psig of ethylene / 60 minutes of reaction time / 200 mg of supported catalyst. C- 65 ° C / 200 psig ethylene / 60 minutes reaction time / 200 mg of supported catalyst. D- 65 ° C / 100 psig ethylene / 60 minutes reaction time / 200 mg of supported catalyst. E- 80 ° C / 100 psig ethylene / 60 minutes reaction time / 200 mg supported catalyst. F- 80 ° C / 200 psig of ethylene / 60 minutes reaction time / 200 mg of supported catalyst. G- 80 ° C / 400 psig ethylene / 60 minutes reaction time / 200 mg of supported catalyst. H- 80 ° C / 400 psig ethylene / 60 minutes reaction time / 100 mg of supported catalyst. I- 80 ° C / 100 psig ethylene / 60 minutes reaction time / 50 mg supported catalyst. J- 80 ° C / 100 psig ethylene / 60 minutes reaction time / 100 mg supported catalyst.

K- 100 ° C / 100 psig ethylene / 60 minutes reaction time / 100 mg supported catalyst. L- 80 ° C / 200 psig ethylene / 60 minutes reaction time / 100 mg supported catalyst. M- 100 ° C / 200 psig ethylene / 60 minutes reaction time / 100 mg supported catalyst. N- 100 ° C / 400 psig ethylene / 60 minutes reaction time / 100 mg supported catalyst. O- 80 ° C / 200 psig ethylene / 15 minutes reaction time / 100 mg supported catalyst. P- 80 ° C / 200 psig ethylene / 0 minutes reaction time / 100 mg supported catalyst. Gas Phase Polymerization (Part 1). Polymerization er i Gas Phase f Part 1) Ex. Catalyst Procedure Mass of Total M "PDI Branches / tm Polymer TO 1000C (" O (g) (*? NIVIR) 120 AA 11.5 395K 164 3.21 8 128 121 AB 8.5 293K 174K 3.59 9 124 122 A c 6.5 224K 124K 4.14 14 120 123 AD 4.7 160K 126K 4.01 21 1 17 124 AE 3.5 121K 91K 3.67 28 119 125 AF 4.3 110K 94 3.33 27 1 1 B 126 AG 9.8 336K 121 K 3.51 13 121 127 HB 13.5 231 K 133K 3.22 10 122 128 HG 12 206K 117K 3.39 13 121 129 HE 9.4 161 K 106K 3.57 26 115 130 HH 7.8 267K 195K 3.16 9 123 131 BE 14 48K 60K 4.42 48 1 14 132 B l 3 41 K 94K 3.2 36 1 14 133 BJ 6.8 47K 88K 3.49 36 119 134 CJ 9 61K 89K 3.94 34 119 135 BK 4.4 30K 48K 4.14 53 1 13 136 c K 5.6 38K 63K 3.63 45 116 137 BL 8 55K 93K 3.57 28 118 138 c L 12 82K 91K 3.79 30 1 19 Gas Phase Polymerization (Part 2) Ex-Catalyst Procedure Mass of Total Mn PDI Branches / tm Polymer TO 1000C (° C) (g) (1HNMR) 139 BM 7 48K 57K 4.61 43 115 140 C M 7 48K 79K 3.77 48 116 141 B H 13.8 94K 106K 3.84 24 120 142 B H 12.7 87K 99K 3.63 26 120 143 D J 4 54K 69K 5.53 35 112 144 D K 3 41K 45K 4.11 56 112 145 D L 5 68K 117K 3.48 28 115 146 D M 3.6 50K 70K 3.74 37 115 147 D H 5 68K 107K 3.24 18 118 148 D N 5.9 80K 76K 4.2 25 116 149 E J 3.8 129K 65K 4.86 36 113 150 E K 1.5 51K 43K '4.4 47 114 151 E L 4 137K 74K '4.6 28 119 152 F H 4.7 161K 106K 3.77 14 120 153 G H 0.35 12K 81K 4.32 23 119 154 G H 0.25 9K 57 K 5.64 27 118 155 F H 3.8 130K 94K 3.46 18 120 156 A O 1.8 123K 71K 4.70 29 117 157 A P 2.1 145K 80K 4.09 33 117 158 A L 2.3 157K 78K 4.72 30 117 159 B O 4.9 34K 58K 4.50 38 117 The polymer made in the gas phase in Example 31 (10.57 grams) was fractionated using supercritical propane by isothermy increasing pressure profiles and fractionation of elution by raising the critical, isobaric temperature, to give the following data. (See B. Folie, et al., "Fractionation of Poly (ethylene-co-vinyl acetate) in Supercritical Propylene: Towards a Molecular Understanding of a Macromolecule Complex", J. Appl. Polym, Sci., 64, 2015-2030 , 1997, and publicly available literature from Phasex Corporation, 360 Merrimack St., Lawrence, MA 01843, and www.Phasex.com).

Fraction Temperature Weight of the Mn PDI Branching tm Collected Fraction (HIMMR) (° C) (° C) (g) 1 40 1.43 29,500 2.76 72.2 50 2 40-60 0.43 28,600 3.02 62.3 55 3 60-65 0.74 49,400 2.37 57.5 79 4 65-75 0.52 83,100 2.14 45.9 92 5 75-85 0.80 80,900 2.22 36.5 99 6 85-95 0.50 77,400 2.40 34.3 102 7 95-100 0.61 93,200 2.26 26.3 108 8 100-110 0.47 116,000 2.15 19.3 1 17 9 110-140 0.41 125,000 2.23 16.7 122 10 140-150 0.15 184,000 2.96 14.3 124 residue - 3.85 - - < 5 - Volume - - 59,900 4.42 48 1 14 Sample The polymer made in the gas phase in the example 138 (12 grams) was fractionated using supercritical propane by isothermy increasing pressure profiles and fractionation of elution by raising the critical, isobaric temperature to give the following data. (See, B. Folie, et al., "Fractionation of Poly / ethylene-co-vinyl acetate) in Supercritical Propylene: Towards a Molecular Understanding of a Macromolecule Complex" J. Appl. Polym. Sci., 64, 2015-2030, 1997, and publicly available literature from Phasex Corporation, 360 Merrimack St., Lawrence, MA 01843, and to www.Phasex.com): Fraction Temperature Weight of the Mn PDI Branching tm Collected Fraction (1HNMR) (° C) (° C) (g) 1 40 0.38 20,500 3.12 7? 64 2 40-65 0.60 30,200 3.10 57 70 3 65-75 0.73 43,600 2.73 47 87 4 75-85 0.82 49,900 3.16 35 98 5 85-90 0.54 63,200 2.58 30 106 6 90-95 0.62 81,200 2.42 25 109 7 95-100 0.60 79,700 2.51 22 114 8 100-105 0.89 77,900 3.04 18 118 9 105-1 10 0.81 117,600 2.30 16 121 10 110-115 0.65 115,000 2.59 13 124 11 115-120 0.39 116,500 2.61 1 1 126 12 120-125 0.16 139,500 2.43 1 1 125 13 125-150 0.25 151, 300 2.43 - 123 waste - 2.2 141, 000 5.29 - - Volume - 12 90,700 3.79 30 1 19 Sample Polymerization of Phase Solution XXVII Phase Solution Polymerization Procedure A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to ensure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and a stored solution (CH2Cl2) of the 2,3-bis (2,6-dimethyl-phenylimino) [1,] -ditiane nickel dibrsmide complex. The autoclave was heated to the desired temperature and a cocatalyst was added. The reactor was rapidly pressurized to the desired pressure. After the desired reaction time, the polymerization was quenched by the addition of acetone and methanol. The separated swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. As used herein, Et2AlCl refers to diethylaluminum chloride.

A- cocatalyst = Et2AlCl; mol cat. = 8.7 x 10"; solvent = mineral volatiles; temperature = 80 ° C; ethylene pressure = 60D psig; reaction time 20 minutes. B- cocatalyst = Et2AlCl; mol cat. = 8.7 x 10 ~ 7; solvent = mineral volatiles; temperature = 65 ° C; ethylene pressure = 600 psig; reaction time 20 minutes. C- cocatalyst = Et2AlCl; mol cat. = 8.7 x 10-7; solvent = mineral volatiles; temperature = 65 ° C; ethylene pressure = 800 psig; reaction time 20 minutes. D- cocatalyst = Et2AlCl; mol cat. = 17.5 x 10"7; solvent = toluene, temperature = 80 ° C, ethylene pressure = 600 psig, reaction time 20 minutes, E- cocatalyst = Et2AlCl, mol cat = 17.5 x 10-7, solvent = toluene; temperature = 75 ° C, ethylene pressure = 600 psig, reaction time 20 minutes, F- cocatalyst = Et2AlCl, mol cat = 17.5 x 10-7, solvent = toluene, temperature = 75 ° C, ethylene pressure = 800 psig, reaction time 20 minutes, G- cocatalyst = Et2AlCl, mol cat = 17.5 x 10-7, solvent = toluene, temperature = 80 ° C, ethylene pressure = 400 psig, reaction time 20 minutes. = Et2AlCl; mol cat. = 17.5 x 10-7; solvent = toluene; temperature = 65 ° C; ethylene pressure = 400 psig; reaction time 20 minutes.

I- cocatalyst = Et2AlCl; mol cat. = 17 5 x 10 ~ 7; solvent = toluene; temperature = 100 ° C; ethylene pressure = 800 psig; reaction time 20 minutes. Phase Polymerization of Solution Ej-i Catalyst Procedure Mass of Total Mn PDI Branches / Tm Polymer TO 1000C (° C) (g) (1HNMR) 160 XXVI! A 6 247K 83K 2.42 33 94 161 XXVII B 9 370K 135K 2.61 26 1 13 162 xxvu C 6 245K 144K 2.30 24 1 13 163 XXVÍI D 5.7 116K 66K 1.85 47 80 164 XXVII E 6.3 129K 58K 2.18 44 75 165 XXVII F 7.8 159K 63K 2.43 37 95 166 XXVII G 3.8 78K 52K 1.85 - 55 167 XXVII H 5.5 112K 78K 1.93 45 78 168 XXVÜ I 1.5 31K 32K 1.85 63 55 Example 169 Preparation of MAO supported on silica (Grace Davison XPO-2402) MAO / 2402. A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison XPO-2402, 3.08 g) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum layer. Until stirring, anhydrous toluene (80 mL) was then added, followed by 19.0 mL of 10% by weight of MAO in toluene. The suspension was heated at 80 ° C for 4 hours, cooled to room temperature and then transferred by means of a cannula into a filter funnel. The solid was washed with toluene (3 x 50 mL) and dried in vacuo to give 3.64 g of the solid. The BET surface area: 300.9 m2 g "1. Pore volume: 1.19 cm3 g ~ x Average Pore Diameter 157.3 A. Obsd% by weight Al: 6.8 Example 170 Preparation of diethylaluminum chloride (DEAC) supported on silica ( Grace Davison XPO-2402), DEAC / 2402. A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison XPO-2402; 3.87 g) under an inert nitrogen atmosphere The flask was equipped with a magnetic stir bar and a septum cap.Ant stirring, anhydrous toluene (80 mL) was then added, followed by 20.0 mL of 1.8 M DEAC. in toluene The suspension was heated at 80 ° C for 4 hours, cooled to room temperature and then transferred through a cannula into a filter funnel The solid was washed with toluene (5 x 50 mL) and dried in vacuo to give 4.21 g of solid The BET surface area: 280 m2 g "1. Pore volume: 1.0 cm3 g_1. Average Pore Diameter: 132 Á .: Obsd% by weight Al: 2.7. Example 171 Preparation of triethylaluminium (TEAL) supported on silica (Grace Davison XPO-2402). TEAL / 2402 A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison XPO-2402; 6.15 g) under an atmosphere of inert nitrogen. The flask was equipped with a magnetic stir bar and a septum cap. To the stirring anhydrous toluene (50 mL) was added, followed by 100 mL of 1.9 mL of TEAL in toluene. The suspension was heated at 80 ° C for 4 hours, cooled to room temperature and then transferred by means of a cannula into a filter funnel. The solid was washed with toluene (1 x 50 mL + 4 x 25 mL) and dried in vacuo to give 6.34 g of the solid. Example 172 Preparation of DEAC supported on silica (Grace Davison Sylopol 2212). DEAC / 2212 A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison Sylopol 2212, 3.8 g) under an atmosphere of inert nitrogen. The flask was equipped with a magnetic stir bar and a septum cap. To the stirring anhydrous toluene (80 mL) was added, followed by 16 mL of a 10% by weight solution of MAO in toluene. The suspension was heated at 80 ° C for 4 hours, cooled to room temperature and then transferred by means of a cannula into a filter funnel. The solid was washed with toluene (1 x 50 mL + 6 x 25 mL + 1 x 50 mL) and dried in vacuo to give 3.35 g of the solid. Obsd _ in weight Al: 2.6. Example 173 Preparation of MAO supported on silica (Grace Davison Sylopol 2212). MAO / 2212 A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison Sylopol 2212; 6.27 g) under an atmosphere of inert nitrogen. The flask was equipped with a magnetic stir bar and a septum cap. To the stirring anhydrous toluene (50 mL) was added, followed by 54 mL of 10% by weight of a MAO solution in toluene. The suspension was heated at 80 ° C for 5 hours, cooled to room temperature and then transferred by means of a cannula into a filter funnel. The solid was washed with toluene (1- x SO mL + 4 x 25 mL) and dried in vacuo to give 6.88 g of the solid.

Example 174 Preparation of the 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane nickel complex supported on MAO / 2402, XXVI / MAO / 2402. A 500 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with MAO / 2402 (1.62 mg) and the nickel complex of 2, 3-bis ( 2,6-dimethylphenylimino) - [1,4] dithiane (46.7 mg, 81.2 μmol) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. The solid was cooled to 0 ° C and dichloromethane (20 mL) was added under vigorous stirring. The volatiles were removed in vacuo. The residual solid was dried in vacuo to give 1.40 g. Example 175 Preparation of the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano supported on DEAC / 2402, XXVII / DEAC / 2402. A 50 mL pear-shaped flask, previously heated at 2 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with DEAC / 2402 (637 mg) and the nickel complex of 2, 3-bis ( 2,6-dimethylphenylimino) - [1,4] -dithiano (18.0 mg, 31.3 μmol) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. The solid was cooled to 0 ° C and dichloromethane (25 mL) was added under vigorous stirring. After 1 hour, the mixture was filtered through a cannula. The residual solid was then rinsed with 10 mL of dichloromethane and filtered through a cannula a second time. The solid was dried in vacuo and stored at -30 ° C. Producing: 213.4 mg. Ni / support complex loading g: 43 μmoles (based on Ni analysis) and 37 μmoles (based on S analysis). Ni complex: Al relation: 22 (based on Ni analysis) and 26 (based on S analysis). Example 176 Preparation of the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [lf 4] -dithiano supported on DEAC / 2212, XXVII / DEAC / 2212. A 100 mL pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with DEAC / 2212 (758 mg) and the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano (22.1 mg, 38.4 μmol) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. The solid was cooled to 0 ° C and dichloromethane (25 mL) was added under vigorous stirring. After 1 hour, the mixture was filtered through a cannula. The residual solid was then rinsed with 10 mL of dichloromethane and filtered through a cannula a second time. The solid was dried in vacuo and stored at -30 ° C. Producing: 718 mg. Ni / support complex loading g: 49 μmoles (based on Ni analysis) and 34 μmoles (based on S analysis). Ni complex: Al ratio: 20 (based on Ni analysis) and 28 (based on S analysis). Example 177 Treatment of the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano supported on DEAC / 2212 with trimethylaluminum (TMAL), TMAL / XXVII / DEAC / 2212. A 200 ml pear shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1 , 4] -ditiana supported on DEAC / 2212, XXVII / DEAC / 2212 (81.5 mg, 3.4 μmol of Ni) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. The solid was cooled to 0 ° C and toluene (25 mL) was added under vigorous stirring. After 15 minutes, the volatile materials were removed in vacuo at 0 ° C. The resulting solid was further used to evaluate the activity toward d-ethylene polymerization. Example 178 Treatment of the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano supported on DEAC / 2212 with MAO, MAO / XXVII / DEAC / 2212.

A 50 mL pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [ 1, 4) -ditiano supported in DEAC / 2212, XXVII / DEAC / 2212 (113.6 mg; 4.8 μmol Ni) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. The solid was cooled to 0 ° C and toluene (25 mL) was added under vigorous stirring. After 2 minutes, the suspension was transferred by means of a cannula into a filter funnel. The resulting solid was dried in vacuo (89 mg) and used to evaluate the polymerization activity of ethylene. Example 179 Polymerization of ethylene using XXVII / MAO / 2402 A 50 mL pear-shaped flask was charged with 152. 2 mg of XXVII / MAO / 2402 (38 μmol of Ni / g, 5.8 μmol) under an inert nitrogen atmosphere. The inert atmosphere was replaced by 1 atmosphere of ethylene and toluene was added (25 mL). The suspension was stirred for 2 hours at room temperature. The reaction was then quenched with acetone and 6 M HCl. The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 626.5 mg (where 152.5 mg of XXVII / MAO / 2402 were used): Mn = 95.5K, Mw = 467.7K, M "/ Mn = 4.9; 27 ramifications / 1000 C (per XH NMR): Tm = 118 ° C.

Example 180 Polymerization of ethylene using XXVII / MAO / 2402 A Parr® stirred 1000 mL reactor was charged with 169.3 mg (38 μmol) Ni / g; 6.4 μmoles of Ni) under a nitrogen atmosphere. Toluene (250 mL) was added and the reactor was pressurized with ethylene (800 psig). The mixture was stirred at 40 ° C for 60 minutes. The vessel was vented and the catalyst was quenched with methanol and 6M HCl. The mixture was filtered and the collected solid was dried in vacuo at 100 ° C to give 18.60 g of the polymer. Example 181 Polymerization of ethylene using XXVII / MAO / 2402 A 200 ml pear-shaped flask was charged with 79.3 mg of XXVII / MAO / 2402 (38 μmol Ni / g, 3.0 μmol) under a nitrogen atmosphere. The inert atmosphere was replaced with 1 atmosphere of ethylene and toluene (50 mL) was added, followed by 2.0 mL of MAO (10% by weight of toluene). The suspension was stirred for 11 minutes at room temperature and then quenched with methanol and 6M HCl. The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 643 mg. Mn = 100.5 K, Mw = 325.3K, Mw / Mn = 3.2; 41 branches / 1000 C (by XH NMR); Tm = 83 ° C (by DSC). Example 182 Polymerization of ethylene using XXVII / MAO / 2402 A stirred 600 mL Parr® reactor was charged with 72.1 mg of XXVII / MAO / 2402 (38 μmol Ni / g, 2.7 μmol Ni) under an inert nitrogen atmosphere. The reactor was then charged with 150 mL of anhydrous toluene and heated to 50 ° C. Then 2.0 mL of a 10% by weight solution of MAO in toluene was added. The vessel was pressurized with 100 psig of ethylene and further heated to 69 ° C. The suspension was stirred for 45 minutes. The mixture was quenched at elevated pressure by the addition of methanol through an injection loop. The vessel was depressurized and the mixture was treated with 6 M HCl. The polymer was isolated by filtration and dried in vacuo at 100 ° C to give 4.21 g of the polymer Mn = 55.7 K, Mw = 651.5K, Mw / Mn = 11.7; 32 ramifications / 1000 C (per XH NMR); Tm = 113 ° C (by DSC). Example 183 Polymerization of ethylene using XXVII / MAO / 2402 A 200 ml pear-shaped flask was charged with 57.5 mg of XXVII / MAO / 2402 (38 μmoles Ni / g, 2.2 μmoles) and 645 mg of MAO treated with silica (purchased from Witco TA 02794 / HL / 04). The atmosphere of inert nitrogen was replaced by 1 atmosphere of ethylene, and 50 mL of anhydrous toluene was then added. The suspension was stirred for 1 hour at room temperature before being quenched with acetone and 6M HCl. The mixture was filtered and the collected solid was dried in vacuo at 10 ° C to give 478 mg Mn = 195.5K, Mw = 840.5K, Mw / Mn = 4.3; 16 branches / 1000 C; Tm = 116 ° C (by DSC). EXAMPLE 184 Polymerization of ethylene using XXVII / MAO / 2402 A 600 mL Parr® stirred reactor was charged with 65. 0 mg of XXVII / MAO / 2402 (38 μmoles of Ni / g, 2.5 μmoles of Ni), 170 mg of solid MAO and 214 g of sodium chloride under an inert nitrogen atmosphere. The reactor was heated to 60 ° C and subsequently pressurized with 100 psig of ethylene. The mixture was further heated to 65 ° C and stirred an additional 45 minutes. The vessel was vented and the solid mixed with water. The mixture was filtered and the solid was washed with water, 6M HCl and methanol. The collected polymer was dried in vacuo at 100 ° C to give 2.38 g of the polymer. Mn = 65.7K, Mw = 487.0K, Mw / Mn = 7.4; 29 ramifications / 1000 C (per XH NMR); Tm = 118 ° C (by DSC). Example 185 Polymerization of ethylene using XXVII / DEAC / 2402 A 200 mL pear-shaped flask was charged with 82 mg of XXVII / DEAC / 2402 (40 μmol Ni / g; 3.3 μmol) under an inert nitrogen atmosphere. Toluene (30 mL) was added. The inert atmosphere was then replaced by 1 atmosphere of ethylene. The suspension was stirred for 2 hours at room temperature. The reaction was then quenched with acetone and 6M HCl. The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 418 mg. Mn = 114. OK, M "= 264.7K, Mw / Mn = 2.3; 65 branches / 1000 C (by XH NMR); Tm = 110 ° C (by DSC). Example 186 Polymerization of ethylene using XXVII / DEAC / 2402 A stirred 600 mL Parr® reactor was charged with 80.2 mg (40 μmol Ni / g, 3.2 μmol Ni) under an inert nitrogen atmosphere. Toluene (150 mL) was added and the reactor was pressurized with ethylene (800 psig). The mixture was stirred at 40 ° C for 58 minutes. The vessel was vented and the catalyst was quenched with methanol and 6 M HCl. The mixture was filtered and the solid was dried in vacuo at 100 ° C to give 0.56 g of the polymer. Mn = 246.5K, M? = 524.4K, Mw / Mn = 2.1; 9 branches / 1000 C (per XH NMR); Tm = 127 ° C (by DSC). Example 187 Polymerization of ethylene using XXVII / DEAC / 2212 A 200 ml pear-shaped flask was charged with 89.1 mg of XXVII / DEAC / 2212 (42 μmol Ni / g, 3.7 μmol) under an inert nitrogen atmosphere. The inert atmosphere was replaced by 1 atmosphere of ethylene and toluene (50 mL) was added followed by 2.0 mL of MAO (10% by weight in toluene). The suspension was stirred for 10 minutes at room temperature. The temperature was controlled with a water bath. The reaction was then quenched with acetone and 6M HCl.

The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 1.80 g. Mn = 132.8K, Mw = 272.1K, Mw / Mn = 2.0; 52 ramifications / 1000 C (per XH NMR); Tm = 57 ° C (by DSC). Example 188 Polymerization of ethylene using XXVII / DEAC / 2212 A 200 mL pear-shaped flask was charged with 81.2 mg of XXVII / DEAC / 2212 (42 μmol Ni / g, 3.4 μmol) under an atmosphere of inert nitrogen. The inert atmosphere was replaced by 1 atmosphere of ethylene and toluene (50 mL) was added, followed by 2.0 mL of DEAC (1.8 M in toluene). The suspension was stirred for 6 minutes at room temperature. The temperature was controlled with a water bath. The reaction was then quenched with acetone and 6M HCl. The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 857 mg. Mn = 179.2K, Mw = 444.7K, Mw / Mn = 2.5; 32 ramifications / 1000 C (per XH NMR); Tm = 110 ° C (by DSC). Example 189 Polymerization of ethylene using TMAL / XXVII / DEAC / 2212 A suspension of TMAL / XXVII / DEAC / 2212 (3.4 μmol of Ni) in toluene (50 mL) was then prepared at 0 ° C. The reaction flask was evacuated and subsequently filled with 1 atmosphere of ethylene. The mixture was stirred at room temperature for 2 hours and then quenched with methanol and 6M HCl. The mixture was filtered. The resulting solid was collected and dried in vacuo at 100 ° C to give 212 mg. Mn = 215.9K, Mw = 910.6K, Mw / Mn = 4.2; 15 ramifications / 1000 C (per 1 H NMR); Tm = 117 ° C (by DSC). Example 190 Polymerization of ethylene using MAO / XXVII / DEAC / 2212 A 200 mL pear-shaped flask was charged with MAO / XXVII / DEAC / 2212 (2.9 μmol) and toluene (50 mL) under an inert nitrogen atmosphere. The flask was evacuated and subsequently filled with 1 atmosphere of ethylene. The suspension was stirred for 2.5 hours before, this was quenched with methanol and 6M HCl. The column was filtered and the collected solid was dried at 100 ° C to give 304 mg. Mn = 59.9K, Mw = 487.3K, Mw / Mn = 8.1; Tm = 125 ° C (by DSC). Example 191 Preparation of MAO supported in silica (Grace Davison XPO-2402) using incipient moisture, MAOIW / 2402. A 50 ml pear-shaped flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with silica (Grace Davison XPO-2402; 3.33 g) under an inert nitrogen atmosphere. The flask was equipped with a magnetic stir bar and a septum cap. While stirring the contents of the flask, 4 mL of MAO (Aldrich, 10% by weight of toluene) were added in drops. The flask was then placed in vacuo for 2 hours, then stored at room temperature under nitrogen for two days. The flask was then heated at 80 ° C for 1 hour and evacuated. The MAO was also added in 4 mL of fractions until a total of 24 mL of MAO had been added. The volatile materials were removed at room temperature under vacuum between each addition. After the additions were complete, the solid was further dried in vacuo for 90 minutes, yielding 4.80 g of the solid. Example 192 Preparation of the nickel complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano supported in MAOI / 2402 by incipient wetness impregnation XXVIIIW / MAOIW2402 A pear-shaped flask 50 L, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with MAOIW / 2402 (784.9 mg) and cooled to 0 ° C. A solution of the nickel complex of 2, 3-bis (2,6-dimethylphenylimino) - [1,4] -dithiano in dichloromethane (10.4 mg in 1.2 mL) was then added dropwise under an inert nitrogen atmosphere.The solid readily turned purple.The solid was dried in vacuo 0 ° C and stored at -30 ° C Producing: 615 mg The calculated Ni / support complex loading g: 23 μmoles / g Example 193 Polymerization of ethylene using XXVIII / MAOI / 2402 A stirred Parr® reactor 1000 mL was loaded with 75.2 mg of XXVIII / MAOI / 2402 (5 μmoles of Ni / g; 0.38 μmol of Ni) under an inert nitrogen atmosphere. Toluene (300 mL) was added and the reactor was pressurized with ethylene (300 psig). The mixture was stirred at 30 ° C for 60 minutes. The vessel was vented and the catalyst was quenched with methanol and 6M HCl. The mixture was filtered and the collected solid was dried in vacuo at 100 ° C to give 470.3 mg of the polymer. Mn = 268.1K, Mw = 832.1K, Mw / Mn = 3.1; 3 branches / 1000 C (per XH NMR); Tm = 132 ° C. Example 194 Treatment of XXVIIIW / MAOI / 2402 with 1-Hexene by incipient humidity, HexenoIW / XXVIII / MAOI / 2402. A 20 ml flask, previously heated at 200 ° C for several hours and allowed to cool to room temperature under vacuum, was charged with XXVIII / MAOI / 2402 (410.6 mg) and cooled to -30 ° C. 1-Hexene (0.5 mL) was then added in drops with vigorous stirring. A fraction of the resulting solid was stored at -30 ° C and another at room temperature. Example 195: Polymerization of ethylene using Hexeno IWXXVIII / MAQI / 2402 Under an atmosphere of inert nitrogen, a Parr® stirred reactor of 1000 mL was charged with 55.3 mg Hexeno IW / XXVIII / MAOIW / 2402 (12 μmol Ni / g; 0.66 μmol Ni) that has been stored at room temperature for 28 days. Toluene (300 mL) was added and the reactor was pressurized with ethylene (300 psig). The mixture was stirred at 30 ° C for 55 minutes. The vessel was vented and the catalyst was quenched with methanol and 6M HCl. The mixture was filtered and the collected solid was dried in vacuo at 100 ° C to give 1.41 g of the polymer. Mn = 347.0, M "= 1077.0, Mw / Mn = 3.1; 5 branches / 1000 C (per XH NMR); Tm = 134 ° C. Example 196 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane in the presence of Et 2 AlCl. A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 ml of mineral volatiles and 1 ml of Et2AlCl. The autoclave was heated to 80sC and 2.0 mL of a stored solution (0.25 mg in 1 mL of CH2C12) of the nickel dibromide complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane was added through a high pressure sample loop. The reactor was rapidly pressurized to 600 psig of ethylene. After 20 minutes at 80 ° C, the reaction was quenched by the addition of methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. 3.3 g of a white elastic solid was isolated 405,000 TO / h). DSC: (2d0 heat) fusion with an endothermic maximum at 51 ° C. XH NMR: 45 branches / 1000 carbon atoms. CPG: Mn = 60,900; Mw / Mn = 1.90. Example 197 Polymerization of ethylene with 2,3-bis (2,6-dimethylphenylimino) [1,4] dithiane nickel dibromide complex in the presence of Et 2 AlCl. A Parr® 600 mL autoclave was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon. Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 2 mL of Et2AlCl. The autoclave was heated to 75 ° C and pressurized to 500 psig of ethylene and 2.0 mL of a stored solution (0.25 mg in 1 mL of CH2C12) of the 2,3-bis (2,6-dimethylphenylimino) nickel dibromide complex. ) - [l, 4] dithian was added through a high pressure sample loop. The reactor was rapidly pressurized to 600 psig of ethylene and the temperature was raised to 80 ° C. After 20 minutes at 80 ° C, the reaction was quenched by the addition of methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. 3.0 g of a white elastic solid was isolated (368,000 TO / h). DSC: (2nd heat) fusion with an endothermic maximum at 77 ° C. H NMR: 45 branches / 1000 carbon atoms. GPC: Mn = 52,300; Mw / Mn = 2.18. Example 198 Synthesis of the Ni [? 3- (H2CC (CQ2Me) CH2) 1 complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. A flame-dried Schlenk flask equipped with a stir bar and a rubber septum was loaded with 75 mg of [3- (H2CC (C02Me) CH2) Ni (μ-Br)] 2 (0.159 mmol), 293 mg (0.318 mmol) of sodium tetra [3,5 (trifluoromethylphenyl)] borate and 113 mg (0.318 mmol) of 2, 3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. The solid mixture was dissolved in 10 mL of Et2 ?.

The solution was stirred for 3 hours at room temperature although under an argon atmosphere. After 2 hours, the reaction mixture was filtered and the solvent was removed in vacuo to give the desired product (328 mg, 75% yield). [? 3- (H2CC (C02Me) CH2) Ni (μ-Br)] 2 was synthesized according to the procedure described in Wilke, G. et al. Angew. Chem. Int. , ed. Engl. 1966, 5, 151. EXAMPLE 199 Polymerization of Ethylene using Ni [? 3- (H2CC (CQ2Me) CH2) 1 complex of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithiane. An autoclave The 600 mL Parr® was first heated to approximately 100 ° C under high vacuum to make sure the reactor dried. The reactor was cooled and purged with argon.

Under an argon atmosphere, the autoclave was charged with 200 mL of toluene and 2 mL of MAO (10% by weight of solution in toluene). The autoclave was heated to 25 ° C and pressurized to 100 psiq of ethylene and 2.0 mL of a stock solution (1 mg in 1 mL of toluene) of the Ni [γ3- (H2CC (C02Me) CH2)] 2 complex. , 3-bis (2,6-dimethylphenylimino) - [1,4] dithiane was added through a high pressure sample loop. The reactor was rapidly pressurized to 400 psig of ethylene. After 60 minutes at 25 ° C, the reaction was quenched by the addition of methanol. The swollen polyethylene was isolated by filtration and dried for several hours in a vacuum oven at 80 ° C. 1.1 g of a white solid powder was isolated. DSC: (2nd heat) fusion with an endothermic maximum at 133 ° C. XH NMR: 2 branches / 1000 carbon atoms. EXAMPLE 200 Synthesis of the Ni [γ3- (H2CC (CO ?Me) CH2)] complex supported on silica from 2, 3-bis (2,6-dimethylphenylimino) -i [1,4] dithiane. A flame-dried Schlenk flask equipped with a stir bar and a rubber septum was loaded with 30 mg (22 μmoles) of Ni [3- (H2CC (C02Me) CH2)] complex of 2,3-bis (2 , 6-dimethylphenylimino) - [1,4] dithiane and 1 g of MAO treated with silica (Witco TA02794 / HL / 04). The solid mixture was cooled to 0 ° C and 20 mL of CHC12 was added to the flask and stirred for 45 minutes. After 45 minutes, the solvent was removed in vacuo to give the supported catalyst.

EXAMPLE 201 Polymerization of ethylene using the Ni [3- (H2CC (C02Me) CH2) 1 complex supported on silica of 2,3-bis (2,6-dimethylphenylimino) - [1,4] dithia A Parr® stirred autoclave of 600 mL with 300 g of NaCl (dried in a vacuum oven at 100 ° C for 24 hours) and 100 mg of the supported catalyst prepared in Example 200 was heated to 50 ° C and rapidly pressurized to 400 psig of ethylene. The temperature was raised to 60 ° C and the gas phase polymerization was stirred for 1 hour. After 1 hour, the reactor was vented and the contents emptied into a cup. The resulting polyethylene was isolated by dissolving the NaCl in a mixer and collecting the resulting polymer by filtration. The polyethylene was washed with 6M HCl, water and acetone. The polymer was then dried in a vacuum oven at 100 ° C yielding 4.7 grams of free flowing polyethylene. DSC. (2nd heat) fusion with an endothermic maximum at 122 ° C. XH NMR: 22 branches / 1000 carbon atoms.

Claims

CLAIMS 1. A catalyst for the polymerization of olefins characterized in that it comprises a complex comprising (a) a ligand of the formula X, (b) a transition metal of the group 8-10, and optionally (c) a Bronsted or Lewis acid , R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl; N represents nitrogen; and A and B are each, independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is attached to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order to form the catalyst.
2. The catalyst according to claim 1, characterized in that the solid support is pre-treated with a Bronsted or Lewis acid.
3. A catalyst for the polymerization of olefins characterized by the reaction of the product of a compound of the formula XII, a compound Y and a solid support. XII Rx and R6 each independently represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q ~ or W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
4. The catalyst according to claim 3, characterized in that the compound of the formula XII is selected from the group consisting of XXVII wherein Rx and R6 are 2,6-dimethylphenyl; XXVIII wherein Rx and R6 are 2,6-diisopropylphenyl; XXXII wherein R1 and R6 are 2,6-dimethylphenyl; XXXIII wherein R1 and R6 are 2,6-diisopropylphenyl; XXXVIII wherein Rx and R6 are 2,6-dimethylphenyl; and XXXIX wherein Rx and R6 are 2,6-diisopropylphenyl.
5. A process for the preparation of supported catalysts characterized in that they comprise contacting a group of the transition metal complex of the group 8-10 of a ligand of the formula X, a solid support, and optionally a Bronsted or Lewis acid. wherein R x and R 6 are each, independently hydrocarbyl, substituted hydrocarbyl, or silyl; N represents nitrogen; and A and B are each, independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is bound to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order to form such a supported catalyst.
6. The process according to claim 5, characterized in that the solid support is pre-treated with a Bronsted or Lewis acid.
7. A process for the preparation of supported catalysts characterized in that it comprises the reaction product of a compound of the formula XII, a compound Y and a solid support: XII Rx and R6 each independently represents hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q ~ or W "to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
8. The process according to claim 7, characterized in that the compound of the formula XII is selected from the group consisting of XXVII wherein R and R are 2,6-dimethylphenyl; XXVIII wherein Rx and R6 are 2,6-diisopropylphenyl; XXXII wherein R1 and R6 are 2,6-dimethylphenyl; XXXIII wherein Rx and R6 are 2,6-diisopropylphenyl; XXXVIII wherein Rx and R6 are 2, 6-aimethylphenyl; and XXXIX wherein R1 and R6 are 2,6-diisopropylphenyl.
9. A process for the polymerization of olefins, characterized in that it comprises contacting one or more monomers of the formula RCH = CHR8 with a catalyst comprising a transition metal complex of the group 8-10 of a ligand of the formula X and optionally a Bronsted or Lewis acid. wherein R and R each, independently, represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin; R1 and R6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl; N represents nitrogen; and A and B are each, independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; wherein the complex is attached to a solid support, and wherein the solid support, the Bronsted or Lewis acid, and the complex are combined in any order.
10. A process for the polymerization of olefins, characterized in that it comprises contacting one or more monomers of the formula RCH = CHR with the reaction product of a compound of the formula XII, a compound Y and a solid support: XII wherein R and R8 each independently represent a hydrogen, a hydrocarbyl, or fluoroalkyl, and may be linked to form a cyclic olefin; R1 and R6 each independently represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; "N represents nitrogen, and M represents Ni (II), Pd (II), Co (II), or Fe (II), and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q ~ o. W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion 11. The process according to claim 10, characterized because the compound of formula XII is selected from the group consisting of XXVII wherein R1 and R6 are 2,6-dimethylphenyl; XXVIII wherein Rx and R6 are 2,6-diisopropylphenyl; XXXII wherein R1 and R6 are 2,6-dimethylphenyl; XXXIII wherein R1 and R6 are 2,6-diisopropylphenyl; XXXVIII wherein R1 and R6 are 2,6-dimethylphenyl; and XXXIX wherein R1 and R6 are 2,6-diisopropylphenyl. 12. A process for the polymerization of olefins, characterized in that it comprises contacting one or more monomers of the formula RCH = CHR8 with a supported catalyst formed by combining a compound of the formula XII: XII with a solid support which has been pre-treated with a compound Y, wherein R and R each independently represent hydrogen, a hydrocarbyl, or fluoroalkyl, and may be linked to form a cyclic olefin; Rx and R6 each independently represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q ~ or W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion. 13. A process for the copolymerization of ethylene and a comonomer of the formula CH2 = CH (CH2) nC02Rx characterized in that it comprises contacting ethylene and a comonomer of the formula CH2 = CH (CH2) nC02Rx with a supported catalyst formed by combining silica with a compound of the formula XII and optionally a compound Y; XII wherein R1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl; n is an integer greater than 3; Rx and R6 each independently represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each, independently, a mono-radical connected heteroatom wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II), or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting Q ~ or W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion. The process according to claim 13, characterized in that the compound of formula XII is represented by formula XXIV. XXIV wherein R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, or can collectively form a bridging hydrocarbyl, substituted bridging hydrocarbyl, or a substituted silicon atom; Q is alkyl, chloride, iodide or bromide; W is alkyl, chloride, iodide or bromide; N is nitrogen; Z is sulfur or oxygen; and M is Ni (II). 15. A polyethylene composition characterized in that it comprises a mixture of polyethylene polymers, wherein the mixture has an average degree of branching of about 5 to 120 branches of alkyl per 1000 carbon atoms, wherein any individual component of the mixture has a branching degree from 0 to 150 alkyl branches per 1000 carbon atoms, wherein the polymers are prepared in a reaction vessel, solely from ethylene, and wherein the polymers are prepared using a Group 8 transition metal catalyst 10 supported on a solid support which has been pre-treated with a compound Y selected from the group consisting of methylaluminoxane and other aluminum sesquioxides having the formulas R73A1, R72A1C1 and R7A1C12, wherein R7 is alkyl. 16. The composition according to claim 15, characterized in that the compound Y is methylaluminoxane. 17. A polyethylene composition characterized in that it comprises a mixture of polyethylene polymers, wherein the mixture has an average degree of branching of from 5 to 120 alkyl branches per 1000 atoms, wherein any individual component of the mixture has a degree of branching of 0. at 150 alkyl branches per 1000 carbon atoms, wherein the polymers are prepared in a reaction vessel, solely from ethylene, and wherein the polymers are prepared using a Group 8-10 transition metal catalyst which Y is reacted with a solid support and optionally a compound Y, in any order, wherein Y is selected from the group consisting of methylaluminoxane and other aluminum sesquioxides having the formulas R73A1, R72A1C1, and R7A1C12, wherein R7 is alkyl. 18. A polyolefin which when fractionated is based on solubility using supercritical propane by isothermy increasing profiles and elution fractionation raising critical, isobaric temperature, in ten fractions between about 40 and about 140 ° C, characterized in that a first fraction taken at about 40 ° C has between about 40 and about 100 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are branching of propyl, about 0 to about 15% are butyl branches, and between about 5 and about 15% are pentyl or longer branches; a second fraction taken between about 40-60 ° C has between about 30 and about 90 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 and about 15% are pentyl or longer branches; a third fraction taken between about 60-65 ° C has between about 30 and about 80 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a fourth fraction taken between about 65-70 ° C between about 20 and about 60 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 1 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a fifth fraction taken between about 75-85 ° C has between about 10 and about 50 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a sixth fraction taken between about 85-95 ° C has about 10 to about 40 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; a seventh fraction taken between about 95-100 ° C has between about 5 and about 35 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 5 to about 15% are pentyl or longer branches; an eighth fraction taken between about 100-110 ° C has between about 0 and about 25 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 0 to about 15% are pentyl or longer branches; a ninth fraction taken between about 110-140 ° C has between about 0 and about 30 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 0 to about 15% are pentyl or longer branches; a tenth fraction taken between about 140-150 ° C has between about 0 and about 20 branches per 1000 carbon atoms, wherein between about 50 to about 90% are methyl branches, about 5 to about 15% are ethyl branches, about 0 to about 10% are propyl branches, about 0 to about 15% are butyl branches, and between about 0 to about 15% are pentyl or longer branches; and a tenth fraction has between about 0 and about 20 branches per 1000 carbon atoms. 19. A polymer derived from ethylene essentially only characterized by having more than 30 branches per 1000 carbon atoms and a melting transition (maximum endothermic) in the DSC of more than about 110 ° C. 20. The polymer according to claim 19, characterized in that it is a free-flowing polymer. 21. A polymer derived from ethylene alone, characterized in that it has a broad composition distribution and a molecular weight distribution of less than 6 and more than 2.5, wherein the polymer has an average branching degree of from 5 to 120 alkyl branches per 1000 atoms of carbon, and wherein any individual component of the polymer has a degree of branching of 0 to 150 branches of alkyl per 1000 carbon atoms. 22. The polymer according to claim 19, characterized in that an individual component of the polymer has between about 40 and 100 branches per 1000 carbon atoms, another component has between about 30 and 90 branches per 1000 carbon atoms, another component has between about 30 and 80 branches per 1000 carbon atoms, another component has between 20 and 60 branches per 1000 carbon atoms, another component has between about 10 and 50 branches per 1000 carbon atoms, another component has between about 10 and 40 branches per 1000 carbon atoms, another component has between about 5 and 35 branches per 1000 carbon atoms, another component has between about 0 and 25 branches per 1000 carbon atoms, another component has between about 0 and 30 branches per 1000 carbon atoms , another component has between approximately 0 and 20 branches per 1000 carbon atoms. 23. A transition metal catalyst of Group 8-10 characterized in that it has an improved ratio for the copolymerization of one or more olefin monomers of the RCH = CHR8 type with one or more functional olefin monomers of the formula CH2 = CH (CH2 ) nJ, in an olefin polymerization reaction comprising combining the catalyst with a solid support, and optionally a Bronsted or Lewis acid in any order, prior to the use of the catalyst in the olefin polymerization reaction, wherein R and R8 each, independently represents a hydrogen, a hydrocarbyl, or a fluoroalkyl, and can be linked to form a cyclic olefin; n is an integer between 1-20; J is a group selected from the ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, arylamine, alkylamido, arylamido, alkylimido, arylimido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxythiol, thioalkoxy , acid, urea, sulfonamido and sulfoester. The method as described in claim 23, characterized in that the catalyst is the catalyst of claim 1. 25. A homopolymer of ethylene with a CDBl of less than 50%. 26. A polyalkene with a CDBl of less than 50%, which is characterized in that it contains about 80 to about 150 branches per 1000 methylene groups, and which contains for each ICO branches that are methyl, about 30 to about 90 branches of ethyl, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl branches or longer. 27. The polyalkene according to claim 26, which is characterized in that it contains about 200 to about 130 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 50 to about 75 branches of ethyl, about 5 to about 15 propyl branches, about 24 to about 40 butyl branches, about 5 to about 10 amyl branches, and about 65 to about 120 hexyl branches or longer. 28. The polyalkene according to claim 27, which is a homopolymer of ethylene. 29. A polyalkene with a CDBl of less than 50% which contains about 20 to about 150 branches per 1000 methylene groups, which contains for every 100 branches that are methyl, about 4 to about 20 branches of ethyl, 1 to about 12 branches of propyl, 1 to about 12 branches of butyl, 1 to about 10 branches of amyl, and 0 to about 20 Hexila branches or longer. 30. The polyalkene according to claim 29, characterized in that it contains about 40 to about 100 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 6 to about 15 branches of ethyl, about 2 to about 10 ramifications of propyl, about 2 to about 10 ramifications of butyl, about 2 to about 8 ramifications of amyl, and about 2 to about 15 ramifications of hexyl or longer. 31. The polyalkene according to claim 30, is characterized in that it is an ethylene homopolymer. 32. A process for the copolymerization of one or more olefin monomers of the RCH = CHR8 type with one or more functional olefin monomers of the formula CH2 = CH (CH2) nJ characterized in that it comprises a catalyst, in an olefin polymerization reaction which comprises combining a complex of the formula XII, a solid support, and optionally a compound Y, before the use of the catalyst in the olefin polymerization reaction. wherein R and R8 each independently represent a hydrogen, a hydrocarbyl or a fluoroalkyl, and may be linked to form a cyclic olefin; n is an integer between 1-20; J is a group selected from ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, arylamine, alkylamido, arylamido, alkylimido, arylimido, ether, nitrile, alcohol, keto, amino, amido, imido, alkoxythiol, thioalkoxy , acid, urea, sulfonamido and sulphoester; B R, 11 - Nxx yyiNNT-- Rc M M Q 't XII Rx and R6 each independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl; A and B are each independently, a mono-radical connected heteroatom wherein the connected hetero atom is selected from Group 15 or 16; in addition, A and B may be linked by a bridge group; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide; N represents nitrogen; and M represents Ni (II), Pd (II), Co (II) or Fe (II); and Y is selected from the group consisting of neutral Lewis acid capable of abstracting QX or W ~ to form a weakly coordinating anion, a cationic Lewis acid whose counter ion is a weakly coordinating anion, and a Bronsted acid whose base conjugate is a weakly coordinating anion.