WO1998040374A2 - Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes - Google Patents

Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes Download PDF

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WO1998040374A2
WO1998040374A2 PCT/US1998/003593 US9803593W WO9840374A2 WO 1998040374 A2 WO1998040374 A2 WO 1998040374A2 US 9803593 W US9803593 W US 9803593W WO 9840374 A2 WO9840374 A2 WO 9840374A2
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hydrocarbyl
formula
independently
represent
compound
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PCT/US1998/003593
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WO1998040374A3 (fr
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Peter Borden Mackenzie
Leslie Shane Moody
Christopher Moore Killian
James Allen Ponasik, Jr.
Jason Patrick Mcdevitt
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Eastman Chemical Company
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Priority to JP53958698A priority Critical patent/JP2002514252A/ja
Priority to EP98907610A priority patent/EP0973762A2/fr
Priority to CA002283223A priority patent/CA2283223A1/fr
Publication of WO1998040374A2 publication Critical patent/WO1998040374A2/fr
Publication of WO1998040374A3 publication Critical patent/WO1998040374A3/fr

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    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
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    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • Provisional Application Serial No. 60/039945 filed March 10, 1997; Provisional Application Serial No. 60/041542, filed March 25, 1997; Provisional Application Serial No. 60/042925, filed April 4, 1997; Provisional Application Serial No. 60/043406, filed April 4, 1997; Provisional Application Serial No. 60/044691 , filed April 18, 1997, and Provisional Application Serial No. 60/059372, filed September 18, 1997.
  • the present invention is directed to Group 8-10 transition metal- containing complexes, their use in olefin polymerizations, and to novel olefin polymers produced thereby.
  • Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes, and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, 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.
  • novel catalysts are constantly being sought in attempts to obtain a catalytic process for polymerizing olefins which permits more efficient and better controlled polymerization of olefins.
  • Conventional polyolefins are prepared by a variety of polymerization techniques, including homogeneous liquid phase, gas phase, and slurry polymerization.
  • Certain transition metal catalysts such as those based on titanium compounds (e.g. TiCI 3 or TiCU) in combination with organoaluminum cocatalysts, are used to make linear and linear low density polyethylenes as well as poly- ⁇ -olefins such as polypropylene.
  • TiCI 3 or TiCU titanium compounds
  • organoaluminum cocatalysts are used to make linear and linear low density polyethylenes as well as poly- ⁇ -olefins such as polypropylene.
  • European Patent Application Serial No. 381 ,495 describes the polymerization of olefins using palladium and nickel catalysts which contain selected bidentate phosphorous containing ligands.
  • These catalysts have been described to polymerize ethylene to high molecular weight branched polyethylene.
  • Pd complexes act as catalysts for the polymerization and copolymerization of olefins and methyl acrylate.
  • WO Patent Application 97/02298 discloses the polymerization of olefins using a variety of neutral N, O, P, or S donor ligands, in combination with a nickel(O) compound and an acid.
  • the present invention is directed to novel Group 8-10 transition metal catalysts, to batch or continuous olefin polymerizations using these catalysts, and to the polymers produced thereby.
  • the process of the present invention comprises contacting one or more olefin monomers of the formula LI:
  • R and R 8 each, independently, represent a hydrogen, a hydrocarbyl or a fluoroalkyl, and may be linked to form a cyclic olefin; with a Group 8-10 transition metal having coordinated thereto a bidentate ligand having the formula X:
  • R 1 and R 6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16, preferably N, O, S, and wherein A and B may be linked by a bridging group; and, optionally, a Bronsted or Lewis acid; and polymerization is carried out to obtain a polymer comprising units of the aforementioned olefin monomer.
  • the process of the present invention comprises contacting one or more monomers of the aforementioned formula LI with a catalyst of the present invention having the following formula XI:
  • R 1 , R 6 , A, and B are as in formula (X) above;
  • T represents a hydrogen or a hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll) or Fe(ll), more preferably Ni(ll) or Pd(ll); and X ' is a weakly coordinating anion; and polymerization is carried out to obtain a polymer comprising units of the aforementioned olefin monomer.
  • the process of the present invention comprises contacting an olefin monomer of formula LI with a catalyst of the present invention, formed by combining a compound of formula (XII):
  • a compound Y 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 counterion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is a weakly coordinating anion; and wherein R 1 , R 6 , A, and B are as in formula X above; Q represents an alkyl, chloride, iodide or bromide; W represents an alkyl, chloride, iodide or bromide;
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(ll); and polymerization is carried out to obtain a polymer comprising units of the aforementioned olefin monomer.
  • the catalysts used in the processes of the present invention readily convert ethylene and ⁇ -olefins to high molecular weight polymers, and allow for olefin polymerizations under various conditions, including ambient temperature and pressure, and in solution.
  • the polymers of the present invention include homopolymers of olefins, such as polyethylene, polypropylene, and the like, and to olefin copolymers, including functional-group containing copolymers.
  • ethylene homopolymers can be prepared with strictly linear to highly branched structures by variation of the catalyst structure, cocatalyst composition, and reaction conditions, including pressure and temperature. The effect these parameters have on polymer structure is described herein.
  • These polymers and copolymers have a wide variety of applications, including use as packaging material and in adhesives. Accordingly, it is an object of the present invention to provide novel catalysts capable of polymerizing olefins, including functional group- containing olefins.
  • N, O, S, P, and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon, respectively.
  • Examples of neutral Lewis acids include, but are not limited to, methylalumoxane (hereinafter MAO) and other aluminum sesquioxides, R 7 3 AI, R 7 2 AICI, R 7 AICI 2 (where R 7 is alkyl), organoboron compounds, boron halides, B(C 6 F 5 )3, BPh 3 , and B(3,5-(CF3)C 6 H 3 )3.
  • Examples of ionic compounds comprising a cationic Lewis acid include: R 9 3Sn[BF 4 ], (where R 9 is hydrocarbyl), MgCI 2 , and H + X " , where X ' is a weakly coordinating anion.
  • neutral Lewis bases include, but are not limited to, (i) ethers, for example, diethyl ether or tetrahydrofuran, (ii) organic nitriles, for example acetonitrile, (iii) organic sulfides, for example dimethylsulfide, or (iv) monoolefins, for example, ethylene, hexene or cyclopentene.
  • hydrocarbyl group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms.
  • monovalent hydrocarbyls include the following: C1-C 2 0 alkyl;
  • divalent (bridging) hydrocarbyls include: -CH 2 - -CH 2 CH 2 - -CH 2 CH 2 CH 2 -, and 1,2-phenylene.
  • sil group refers to a SiR3 group wherein Si is silicon and R is hydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR 3 ) 3 .
  • 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.
  • monovalent substituted hydrocarbyls 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-trimethylammoniumphenyl (associated with a weakly coordinated anion), 2,6-dimethyl-4- hydroxyphenyl
  • divalent (bridging) substituted hydrocarbyls examples include: 4-methoxy-1 ,2-phenylene, 1-methoxymethyl-1 ,2-ethanediyl, 1 ,2- bis(benzyloxymethyl)-1 ,2-ethanediyl, or 1-(4-methoxyphenyl)-1,2- ethanediyl.
  • a "sterically hindered aryl” means (i) a phenyl ring with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br or silyl substituents at both the 2- and 6- positions, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO 2 Me, CO 2 H, C(O)CH 3 , CF 3 , or fluoroalkyl substituents, (ii) a 2-substituted napth-1-yl ring, optionally substituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO 2 Me, CO 2 H, C(O)CH 3 , CF 3 , or fluoroalkyl substituents, (iii) an 9
  • heteroatom connected mono-radical 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 -SiR 9 2 - group, wherein R 9 is a hydrocarbyl or substituted hydrocarbyl.
  • a “substituted phosphorous atom” refers to a -P(O)(OR 9 )- group, wherein R 9 is a hydrocarbyl or substituted hydrocarbyl.
  • a “substituted sulfur atom” refers to a -S(O)-, -SO 2 -, or -S(NR 9 ) 2 - group, wherein R 9 is a hydrocarbyl or substituted hydrocarbyl.
  • a “bridging group” refers to a divalent hydrocarbyl, divalent substituted hydrocarbyl, -C(O)-, -C(S)-, substituted silicon atom, substituted sulfur atom, substituted phosphorous atom, -CH 2 C(O)-, -C(O)C(O)-, or 3,4,5,6-tetrafluoro-1 ,2-phenylene.
  • the bridging group, together with groups A and B, may collectively form a divalent heteroatom substituted heterocyde; examples include:
  • a "mono-olefm” refers to a hydrocarbon containing one carbon- carbon double bond.
  • a “suitable metal precursor” refers to a Group 8-10 metal compound, preferably Ni, Co, Pd, and Fe compounds, which may be combined with compound X (preferably, compound III, VI, IX, XVII or XVIII, described below), and optionally a Lewis or Bronsted acid, to form an active olefin polymerization catalyst.
  • Examples include: (1 ,2- dimethoxyethane)nickel(ll) dibromide, bis[( ⁇ -chloro)(1 , 2, 3- ⁇ 3 -2- propenyl)nickel(ll)], bis[( ⁇ -chloro)(1 , 2, 3- ⁇ 3 -2-propenyl)palladium(ll)], bis[( ⁇ - chloro)(1 , 2, 3- ⁇ 3 -1-trimethylsilyloxy-2-propenyl)nickel(ll)], CoBr 2 , FeBr 2 , bis(acetylacetonate)Ni(ll), and [tetrakis(acetonitrile)Pd(ll)][BF 4 ].
  • a “suitable nickel precursor” refers to a suitable metal precursor wherein the metal is nickel.
  • a “suitable nickel(O) precursor” refers to a suitable metal precursor which is a zerovalent nickel compound.
  • fluoroalkyl refers to a C 1 -C 20 alkyl group substituted by one or more fluorine atoms.
  • polymer as used herein is meant a species comprised of monomer units and having a degree of polymerization (DP) of ten or higher.
  • DP degree of polymerization
  • ⁇ -olefin as used herein is a 1 -alkene with from 3 to 40 carbon atoms.
  • a " ⁇ -allyl” group refers to a monoanionic group with three sp 2 carbon atoms bound to a metal center in a ⁇ 3 -fashion. Any of the three sp 2 carbon atoms may be substituted with a hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or O-silyl group. Examples of ⁇ -allyl groups include: -C 6 H 5
  • ⁇ -benzyl group denotes an ⁇ -allyl group where two of the sp 2 carbon atoms are part of an aromatic ring.
  • ⁇ -benzyl groups include:
  • weakly coordinating anion is well-known in the art perse and generally refers to a large bulky anion capable of delocalization of the negative charge of the anion.
  • the coordinating ability of such anions is known and described in the literature (Strauss, S. et al., Chem. Rev. 1993, 93, 927).
  • the terms “monomer” or “olefin monomer” refer to the olefin or other monomer compound before it has been polymerized; the term “monomer units” refers to the moieties of a polymer that correspond to the monomers after they have been polymerized.
  • a compound Y is required as a cocatalyst.
  • Suitable compounds Y include a neutral Lewis acid capable of abstracting Q " or W " to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is a weakly coordinating anion.
  • Preferred compounds Y include: methylalumoxane (hereinafter MAO) and other aluminum sesquioxides, R 7 3 AI, R 7 2 AICI, R 7 AICI 2 (wherein R 7 is alkyl), organoboron compounds, boron halides, B(C 6 F 5 )3, R 9 3Sn[BF 4 ] (wherein R 9 hydrocarbyl), MgCI 2 , and H + X " , wherein X " is a weakly coordinating anion.
  • MAO methylalumoxane
  • R 7 3 AI R 7 2 AICI
  • R 7 AICI 2 wherein R 7 is alkyl
  • organoboron compounds boron halides
  • B(C 6 F 5 )3, R 9 3Sn[BF 4 ] wherein R 9 hydrocarbyl
  • MgCI 2 and H + X "
  • X " is a weakly coordinating anion.
  • solid support examples include inorganic oxide support materials, such as: talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, silica co- gels.
  • inorganic oxide support materials such as: talcs, silicas, titania, silica/chromia, silica/chromia/titania, silica/alumina, zirconia, aluminum phosphate gels, silanized silica, silica hydrogels, silica xerogels, silica aerogels, silica co- gels.
  • R and R 8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
  • R 1 and R 6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
  • N represents nitrogen;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group.
  • composition comprising (a) a Group 8-10 transition metal M, (b) one or more Lewis acids, and (c) a binucleating or multinucleating compound of the formula X:
  • Lewis acid or acids are bound to one or more heteroatoms which are ⁇ -conjugated to the donor atom or atoms bound to the transition metal M;
  • R 1 and R 6 are each, independently, hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl; N represents nitrogen;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group.
  • Preferred Group 8-10 transition metals are Ni, Pd, Fe, and Co, more preferably Ni and Pd.
  • Preferred ligands X are those given below:
  • R 1 and R 6 are as defined above;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , or R 5 may collectively form a bridging group, provided that when the ligand is of formula VI or IX, the bridging group is not a substituted sulfur atom or a substituted phosphorous atom; Synthesis of ligands of the formula X in general is based on a modification of methods previously described, and is detailed in the examples given below.
  • the Group 8-10 transition metal complex having coordinated thereto the bidentate ligand of X, above, may also have coordinated to it one or more additional ligands depending, for example, on whether the complex is the active catalyst, a precursor thereto, or the complex is the resting state of the catalyst.
  • one or more olefin monomers of the aforementioned formula LI is contacted with
  • nickel(O) precursor preferably bis(1 ,5- cyclooctadiene)nickel(0)compound
  • R and R each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group;
  • T represents a hydrogen or a hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents Ni(ll), Pd(ll), Co(ll), or Fe(ll), preferably Ni(ll) or Pd(ll);
  • N nitrogen
  • X ' is a weakly coordinating anion.
  • compound XI is selected from compounds having the following formulas:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , T, L, and M are as defined above.
  • T represents the growing polymer chain
  • L is a mono-olefin
  • the formulas represent the chain propagating species.
  • T and L may collectively represent a ⁇ -allyl or ⁇ -benzyl complex, represented by the symbol G in the formula below, which is coordinated to M.
  • G in the formula below
  • R 1 -R 6 , and X " are as defined above;
  • G is a ⁇ -allyl or ⁇ -benzyl group
  • M is a Group 8-10 transition metal, preferably Pd(ll), Ni(ll), Fe(ll), or
  • R and R 8 each, independently, represent a hydrogen, a hydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclic olefin;
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group; Q represents an alkyl, chloride, iodide or bromide;
  • W represents an alkyl, chloride, iodide or bromide
  • N represents nitrogen
  • M represents Ni(ll), Pd(ll), Co(ll), or Fe(ll), preferably Ni(ll) or Pd(ll); 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 counterion is a weakly coordinating anion, and a Bronsted acid whose conjugate base is a weakly coordinating anion.
  • compounds of formula XII are those selected from the following formulas:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl
  • any two of R 2 , R 3 , R 4 , and R 5 may be linked by a bridging group, provided that when the compound is of formula V or VIII, the bridging group is not a substituted sulfur atom or a substituted phosphorous atom
  • Q represents an alkyl, chloride, iodide or bromide
  • W represents an alkyl, chloride, iodide or bromide
  • X " is a weakly coordinating anion.
  • the catalysts of the present invention may be used in polymerization processes that incorporate functional group- containing olefin units within the resultant polymer.
  • Functionalized olefin polymers and copolymers, and processes for obtaining the same, are described in copending Provisional Patent Application Serial No. 60- 062609, incorporated herein by reference.
  • the present invention also provides a process for the production of linear ⁇ -olefins, comprising contacting ethylene with (a) a suitable nickel precursor, (b) a compound of the formula:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl or 4-methoxyphenyl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form a bridging group;
  • N nitrogen
  • O oxygen
  • S sulfur
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl or 4-methoxyphenyl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form a bridging group, provided that when the compound is of formula IV or VII, the bridging group is not a substituted sulfur atom or a substituted phosphorous atom;
  • T represents a hydrogen or hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • X " is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl or 4-methoxyphenyl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form bridging group, provided that when the complex is of formula V or VIII, the bridging group is not a substituted sulfur atom or a substituted phosphorous atom;
  • Q represents a hydrocarbyl, chloride, iodide or bromide
  • W represents a hydrocarbyl, chloride, iodide or bromide
  • M represents Ni(ll);
  • N nitrogen
  • O oxygen
  • S sulfur
  • 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 counterion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is a weakly coordinating anion.
  • R 1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl; n is an integer greater than 3, preferably greater than 5 and less than 25;
  • R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, or may collectively form a bridging hydrocarbyl, bridging substituted 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(ll).
  • R 1 is hydrogen, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl
  • n is an integer greater than 3, preferably greater than 5 and less than 25
  • R 2 and R 3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, or may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, -C(O)-, or a substituted silicon atom;
  • N is nitrogen;and Z is sulfur or oxygen.
  • the catalysts of the present invention comprise a Group 8-10 transition metal coordinated by the bidentate ligand X; these include, but are not limited to, the preferred compounds I, II, IV, V, VII, VIII, XI-XVI, XIX- XXVIII, and XXX-XLII, set forth in detail herein.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form a bridging group;
  • T represents a hydrogen or hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll),
  • N nitrogen
  • X " is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form a bridging group;
  • Q represents a hydrocarbyl, chloride, iodide or bromide
  • W represents a hydrocarbyl, chloride, iodide or bromide
  • N represents nitrogen
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(II), more preferably Ni(ll) or Pd(ll).
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom;
  • T represents a hydrogen or hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or
  • N represents nitrogen; and X ' is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, or 4-methoxyphenyl or sterically hindered aryl
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom;
  • Q represents a hydrocarbyl, chloride, iodide or bromide
  • W represents a hydrocarbyl, chloride, iodide or bromide
  • N nitrogen
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or Pd(ll);
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl; and R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom.
  • Described herein is a catalyst comprising a compound of the formula VII:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom;
  • T represents a hydrogen or hydrocarbyl;
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or
  • N nitrogen
  • X " is a weakly coordinating anion. Also described herein is a catalyst comprising a compound of formula VIII:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted 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
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or Pd(ll);
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , and R 4 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging group;
  • T represents a hydrogen or hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or Pd(ll);
  • N represents nitrogen; and X " is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; T represents a hydrogen or hydrocarbyl;
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or Pd(ll);
  • N represents nitrogen;
  • X ' is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , and R 4 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging group;
  • Q represents a hydrocarbyl, chloride, iodide or bromide
  • W represents a hydrocarbyl, chloride, iodide or bromide
  • N represents nitrogen
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(il), or Fe(ll), preferably Ni(ll) or Pd(ll).
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl; and R 2 , R 3 , and R 4 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , or R 4 may collectively form a bridging group.
  • a catalyst comprising a compound of formula XVI:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, preferably sterically hindered aryl;
  • Q represents a hydrocarbyl, chloride, iodide or bromide;
  • W represents a hydrocarbyl, chloride, iodide or bromide;
  • N represents nitrogen;
  • M represents a Group 8-10 transition metal, preferably Ni(ll), Pd(ll), Co(ll), or Fe(ll), more preferably Ni(ll) or Pd(ll);
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl.
  • a catalyst comprising a compound of the formula XIX:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , R 4 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , R 4 , and R 5 may collectively form a bridging group; G is a ⁇ -allyl or ⁇ -benzyl group; M represents Ni(ll) or Pd(ll); N represents nitrogen; and
  • X " is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom;
  • G is a ⁇ -allyl or ⁇ -benzyl
  • X " is a weakly coordinating anion.
  • a catalyst comprising a compound of the formula XXI:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 3 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl, and, in addition, may collectively form a bridging hydrocarbyl, bridging substituted hydrocarbyl, or a substituted silicon atom;
  • G is a ⁇ -allyl or ⁇ -benzyl
  • M represents Ni(ll) or Pd(ll);
  • N nitrogen
  • X ' is a weakly coordinating anion.
  • a catalyst comprising a compound of the formula XXII:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 , R 3 , and R 4 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl; in addition, any two of R 2 , R 3 , and R 4 may collectively form a bridging group;
  • G is a ⁇ -allyl or ⁇ -benzyl
  • M represents Ni(ll) or Pd(ll);
  • N nitrogen
  • X " is a weakly coordinating anion.
  • a catalyst comprising a compound of the formula XXIII:
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • R 2 and R 5 each, independently, represent a hydrogen, hydrocarbyl, substituted hydrocarbyl, or silyl;
  • G is a ⁇ -allyl or ⁇ -benzyl
  • M represents Ni(ll) or Pd(ll);
  • N nitrogen
  • X " is a weakly coordinating anion.
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group;
  • T represents a hydrogen or a hydrocarbyl
  • L represents a mono-olefin or a neutral Lewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;
  • M represents Ni(ll) or Pd(ll);
  • N nitrogen
  • X " is a weakly coordinating anion.
  • a catalyst for the polymerization of olefins comprising a compound of formula XXV,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXVI,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXVII,
  • XXVII wherein R 1 and R 6 are 2,6-dimethylphenyl.
  • a catalyst for the polymerization of olefins comprising a compound of formula XXVIII,
  • XXVIII wherein R 1 and R 6 are 2,6-diisopropylphenyl. Also provided herein is a catalyst comprising a compound of formula XXIX,
  • R 1 and R 6 each, independently, represent hydrocarbyl, substituted hydrocarbyl, or silyl, preferably phenyl, 4-methoxyphenyl, or sterically hindered aryl;
  • a and B are each, independently, a heteroatom connected mono- radical wherein the connected heteroatom is selected from Group 15 or 16; in addition, A and B may be linked by a bridging group;
  • Q represents a hydrocarbyl, chloride, iodide or bromide
  • W represents a hydrocarbyl, chloride, iodide or bromide
  • M represents Ni(ll) or Pd(ll); and N represents nitrogen.
  • a catalyst for the polymerization of olefins comprising a compound of formula XXX,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXI,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXII, XXXII wherein R 1 and R 6 are 2,6-dimethylphenyl. Also provided herein is a catalyst for the polymerization of olefins, comprising a compound of formula XXXIII,
  • XXXIII wherein R 1 and R 6 are 2,6-diisopropylphenyl.
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXIV,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXV,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXVI,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXVII,
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXVIII,
  • XXXVIII wherein R 1 and R 6 are 2,6-dimethylphenyl.
  • a catalyst for the polymerization of olefins comprising a compound of formula XXXIX, XXXIX wherein R 1 and R 6 are 2,6-diisopropylphenyl.
  • a catalyst for the polymerization of olefins comprising a compound of formula XL,
  • a catalyst for the polymerization of olefins comprising a compound of formula XLI,
  • composition comprising an ester containing semicrystalline copolyethylene with 5 to 30 alkyl branches/1000 carbon atoms, wherein the majority of alkyl branches are methyl branches, and an average of from about 1 to 50 ester terminated branches per chain resulting from ester comonomer incorporation.
  • composition comprising an olefin containing semicrystalline copolyethylene with 5 to 30 alkyl branches/1000 carbon atoms, wherein the majority of alkyl branches are methyl branches, and an average of from about 1 to 50 olefin terminated branches per chain resulting from linear diene comonomer incorporation.
  • a polymer composition comprising an ethylene homopolymer with greater than 125 alkyl branches per 1000 carbon atoms, useful as an adhesive or tackifying agent.
  • Preferred olefins useful in the practice of the processes of the present invention include ethylene and ⁇ -olefins such as propylene, 1- butene, 1-hexene, 1-octene, ethyl undecenoate and cyclic olefins such as cyclopentene.
  • said liquid phase may include solvent or neat monomer.
  • the molar ratio of neutral Lewis acid to transition metal complex can be from 1 to 10000, preferably 10 to 1000.
  • the pressure at which the ethylene polymerizations and copolymerizations take place can be from 1 atmosphere to 1000 atmospheres, preferably 1 to 100 atmospheres.
  • Lewis acid may be acting to further activate the catalysts provided herein via coordination to one or more of those heteroatoms which are not directly bound to the transition metal M, but which are ⁇ -conjugated to the nitrogens which are bound to the transition metal M.
  • Substituents which contain additional Lewis basic groups, including, but not limited to, methoxy groups, positioned so as to further promote the binding of the Lewis acid at such ⁇ -conjugated heteroatoms, are also included in this invention.
  • a nonlimiting example of secondary Lewis acid binding would include the following:
  • R 1 , R 2 , R 5 , and R 6 are 2,6-dimethylphenyl; and X ' is a weakly coordinating anion.
  • the polymerizations may be conducted as solution polymerizations, as non-solvent slurry type polymerizations, as slurry polymerizations using one or more of the olefins or other solvent as the polymerization medium, or in the gas phase.
  • 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, may be used.
  • Propylene and 1-butene are excellent monomers for use in slurry-type copolymerizations and unused monomer can be flashed off and reused.
  • Suitable polymerization temperatures are preferably from about -100 °C to about 200 °C, more preferably in the 20 °C to 150 °C range.
  • the polymers of the present invention are useful as components of thermoset materials, as elastomers, as packaging 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 readily processed using conventional extrusion, injection molding, compression molding, and vacuum forming techniques well known in the art.
  • Useful articles made from them include films, fibers, bottles and other containers, sheeting, molded objects and the like.
  • Low molecular weight resins are useful, for example, as synthetic waxes and they may be used in various wax coatings or in emulsion form. They are also particularly useful in blends with ethylene/vinyl acetate or ethylene/methyl acrylate-type copolymers in paper coating or in adhesive applications.
  • typical additives used in olefin or vinyl polymers may be used in the new homopolymers and copolymers of this invention.
  • Typical additives include pigments, colorants, titanium dioxide, carbon black, antioxidants, stabilizers, slip agents, flame retarding agents, and the like. These additives and their use in polymer systems are known per se in the art.
  • 2,6-dimethylaniline, triethylamine, and dichloromethane were dried by passage through basic alumina.
  • a solution of 25.34 g of oxalyl chloride in 80 mL of dichloromethane was added dropwise under nitrogen with stirring and ice-bath cooling over 1.2 hours to give a thick paste which had to be occasionally swirled by hand to effect mixing.
  • 2,6-Diisopropylaniline, triethylamine, and dichloromethane were dried by passage through basic alumina.
  • Example 3 Preparation of N, ⁇ /'-bis (4-methoxy-2,6-dimethylphenv0oxalamide.
  • Triethylamine and dichloromethane were dried by passage through basic alumina.
  • a solution of 0.39 of oxalyl chloride in 2 mL of dichloromethane was added dropwise under a nitrogen atmosphere with stirring and ice-bath cooling over 35 min.
  • a 1 L round bottom flask was charged with 30.0 g of N,N -bis(2,6- dimethylphenyl)oxalamide, 58.8 g of phosphorous 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 heated to reflux over 30 minutes, then maintained at reflux under nitrogen for another 95 minutes to give a yellow solution. Heating was discontinued and the mixture was allowed to cool to room temperature (about 23° C).
  • Example 5 Preparation of ⁇ / 1 ./V 2 -bis(2,6-diisopropylphenv ⁇ oxalodiimidoyl dichloride.
  • 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 ⁇ / ⁇ /V 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 136 mg of sodium hydride (60% mineral oil dispersion), 4.0 mL of dry tetrahydrofuran and 0.140 mL of 1 ,2-ethanedithiol.
  • the mixture was heated at reflux for 2 hours, after which another 66 mg of sodium hydride dispersion was added and the mixture was refluxed for an additional hour.
  • a 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was sequentially charged with 0.69 g of a 60% dispersion of sodium hydride in mineral oil, 3.34 g of ⁇ / 1 , ⁇ / 2 -bis(2,6-diisopropylphenyl)oxalodiimidoyl dichloride, 20 mL of dry tetrahydrofuran, and 0.70 mL of 1,2-ethanedithiol.
  • the mixture was heated under argon at reflux for 3 hours, after which another 0.25 g of sodium hydride dispersion was added and the mixture was refluxed for an additional 2.5 hours.
  • a 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was sequentially charged with 0.69 g of a 60% dispersion of sodium hydride in mineral oil, a freshly prepared solution of 2.08 g N N 2 - diphenyloxalodiimidoyl dichloride in 20 mL of dry tetrahydrofuran, and 0.70 mL of 1 ,2-ethanedithiol.
  • the mixture was heated under argon at reflux for 2 hours, after which another 0.30 g of sodium hydride dispersion was added and the mixture refluxed for an additional 3 hours. After cooling, the mixture was diluted with water and diethyl ether, and the ether layer was separated, washed with water, and dried with magnesium sulfate to afford a yellow-orange gummy solid.
  • a 100 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was sequentially charged with 0.294 g of a 60% dispersion of sodium hydride in mineral oil, 4 mL of dry tetrahydrofuran, and 0.253 g of 1,2-benzenedithiol. After the bubbling had subsided, 0.600 g of ⁇ / 1 , ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride was added. The mixture was stirred at 25° C. for 45 minutes, then heated to reflux over 15 minutes and held at reflux for 1 hour.
  • the resulting mixture was syringed into the ⁇ / 1 , ⁇ / 2 -bis(4- methoxy-2,6-dimethylphenyl)oxalodiimidoyl dichloride solution using 5 mL dry THF to complete the transfer.
  • the reaction flask was heated at reflux for 3 hours, after which another 45 mg of sodium hydride dispersion and another 20 ⁇ L ethane dithiol was 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 afford a yellow-orange solid.
  • 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 ⁇ / 1 , ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 66 mg of sodium hydride (60% mineral oil dispersion), 5.0 mL of dry tetrahydrofuran, 0.230 mL of triethylamine (dried by passage through alumina) and 0.093 mL of dry ethylene glycol. The mixture was heated at reflux for 105 minutes, after which another 66 mg of sodium hydride dispersion was added and the mixture was refluxed for an additional hour.
  • 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 ⁇ / 1 , ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 155 mg of sodium hydride (60% mineral oil dispersion), 3.5 mL of dry tetrahydrofuran and 188 mg of 3-methoxy-1 ,2-propanediol.
  • the mixture was heated to reflux over 10 min and held at reflux for 2 hours.
  • a 100 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser capped by an argon inlet was charged with 265 mg of sodium hydride (60% mineral oil dispersion), 7.5 mL of dry tetrahydrofuran, 1.0 g of 3-methoxy-1 ,2-propanediol and 1.0 g of ⁇ / 1 , ⁇ / -bis(2,6- dimethylphenyl)oxalodiimidoyl dichloride.
  • the yellow mixture was heated to reflux over 15 min and became very viscous. More tetrahydrofuran (5 mL) was added and the mixture was stirred with a glass rod, then heated for another 30 min.
  • 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 /V 1 , ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 346 mg triethylamine, 4 mL dry, deoxygenated toluene, and 0.135 mL 2- (methylamino)ethanol.
  • the mixture was heated to reflux under nitrogen over 30 minutes and maintained at reflux for another 4.25 hours. After cooling, the mixture was diluted with 45 mL diethyl ether and washed three times with water (110 mL total).
  • 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 725 mg of ⁇ / 1 , ⁇ / 2 -bis(2,6-diisopropylphenyl)oxalodiimidoyl dichloride, 143 mg of sodium hydride (60% mineral oil dispersion), 4 mL dry tetrahydrofuran, and 0.144 mL 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 water.
  • a 100 mL round bottom was equipped with a magnetic stirrer and charged with 0.75 mL dry triethylamine, 6 mL dry and deoxygenated dichloromethane, and 0.335 g ⁇ / 1 , ⁇ / 2 , ⁇ / 3 , ⁇ / 4 -tetrakis(4-methoxy-2,6- dimethylphenyl)oxalamidine.
  • 178 mg triphosgene was added, and the flask was quickly capped with a septum. A precipitate formed and the color shifted from yellow to orange.
  • After 2.5 days another 78 mg triphosgene was added, and the reaction left to stir another 2 hours. 150 mg more triphosgene was added, and the reaction left to stir for another 16 hrs.
  • reaction mixture was diluted with 50 mL diethyl ether and washed with water (2 x 50 mL). The aqueous washings were back-extracted with dichloromethane. The organic layers were combined and dried over magnesium sulfate, and concentrated in vacuo to afford an orange oil.
  • 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 A/ 1 ,/ ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 43 mL of dry toluene and 32.7 g of 2,6-dimethylaniline (dried by passage through alumina).
  • the mixture was heated to reflux under nitrogen over 30 minutes, then maintained at reflux 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 precipitate.
  • 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 ⁇ / 1 , ⁇ / 2 -bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 1.1 mL of ⁇ /, ⁇ /'-dimethylethylenediamine and 4.0 mL of dry toluene.
  • the mixture was heated to reflux under nitrogen over 15 minutes and maintained at reflux for another 30 minutes. After cooling, the mixture was diluted with diethyl ether and washed three times with water.
  • 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 via a filter paper-tipped cannula, and the residue dried in vacuo at 1 mm Hg to afford 116 mg of red-brown crystals.
  • a flame-dried Schlenk flask equipped with a magnetic stir bar was charged with 159.6 mg of 1 ,3-bis-(2,6-dimethyl- phenyI)-4,5-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-one and 92.7 mg of (1,2-dimethoxyethane)nickel(ll) dibromide and 59.4 mg silver tetrafluoroborate.
  • the flask was wrapped in aluminum foil, and on the
  • a 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 5.3 mg of the nickel dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1 ,4]dithiane.
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • the resultant suspension was cooled to 0 °C and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene.
  • a 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 20 mg of bis(1 ,5- cyclooctadiene)nickel(O), 33 mg of 2,3-bis(2,6-dimethylphenylimino)- [1 ,4]dithiane, and 83 mg of the ether solvate HB(Ar) 4 .
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • Example 38 Polymerization of ethylene with the nickel dibromide complex of 2.3-bis(2.6- dimethylphenyliminoW1.41dithiane 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 a stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane.
  • the flask was evacuated and refilled 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 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. A white polyethylene precipitate was observed within seconds.
  • the autoclave Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.3 mL of a stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 40° C and 2 mL of MMAO in heptane (6.42 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig with ethylene and the temperature ramped up to 50° C. After 10 minutes at 50° C, the reaction was quenched by the addition of acetone, and methanol.
  • a 600 mL Parr ® autoclave was first heated to about 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 1.0 mL of a stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 55° C and 2 mL of MMAO in heptane (6.42 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig with ethylene and the temperature ramped up to 65° C. After 10 minutes at 65° 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 a vacuum oven at 80° C. 5.3 g of a white rubbery solid was isolated (640,000 TO/h).
  • DSC (2nd heat) melt with an endothermic maximum at 78° C.
  • 1 H NMR 47 branches/1000 carbon atoms.
  • Example 43 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis(2,6- dimethylphenyliminoH1 ,4ldithiane in the presence of MMAO (23 % iso- butylaluminoxane).
  • a 600 mL Parr ® autoclave was first heated to about 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 1.0 mL of a stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 70° C and 2 mL of MMAO in heptane (6.42 wt% aluminum) was added.
  • the autoclave Under an argon atmosphere, the autoclave was charged with 150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mL CH2CI2) of the nickel dibromide complex of 2,3-bis(2,6-di-iso- propylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 40° C and 2 mL of MMAO in heptane (6.42 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig with ethylene and the temperature ramped up to 50° C. After 10 minutes at 50° C, the reaction was quenched by the addition of acetone, and methanol.
  • a 1 L Fischer-Porter bottle was assembled onto a pressure head equipped with a mechanical stirrer and gas and liquid feed-through ports, then pressurized to 75 psig of ethylene and relieved to ambient pressure seven times.
  • the bottle was immersed in a 21.5° C. water bath, then 50 mL of dry, deoxygenated toluene was added via syringe, followed by 100 ⁇ L of a stock solution of 15.3 mg of the 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 ethylene for 5 minutes to saturate the solution with ethylene, then the pressure was relieved, and 4.0 mL of a 10 wt% solution of MAO in toluene was quickly added.
  • the flask was immediately re-pressurized to 75 psig ethylene and stirred at 300 rpm. After 30 minutes, the pressure was relieved and the reaction quenched by 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 acetone were added and the mixture was stirred to complete hydrolysis of the MAO.
  • the flask was placed in a water bath and allowed to equilibrate with 1 atmosphere ethylene for 10 minutes, then 0.25 mL of a stock solution prepared from 10.2 mg of the nickel dibromide complex of 2,3-bis-(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1 ,4]dithiine in 13.11 g dry, deoxygentated dichloromethane was added.
  • the reaction mixture was then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. Ethylene uptake and formation of a polyethylene precipitate were observed.
  • reaction mixture was then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene, then 0.10 mL of a stock solution (prepared from 6.3 mg of the nickel dibromide complex of 2,3- bis(4-methoxy-2,6-dimethylphenylimino)- [1 ,4]dithiane and 6.5 mL dichloromethane) was added. After 10 minutes, the reaction mixture was quenched by the addition of acetone, methanol and 6 N aqueous HCl.
  • a 600 mL Parr ® autoclave was first heated to about 100 °C under high vacuum to ensure 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 stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- diisopropylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 45 °C and 0.2 mL of (CH 3 CH 2 ) 2 AICI (500 equiv.) in toluene was added.
  • the reactor was rapidly pressurized to 100 psig and the temperature ramped up to 50 °C. After 10 minutes at 50 °C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which separated was isolated by filtration and dried for several hours in a vacuum oven at 80 °C resulting in 2 g of a white rubbery solid (590,000 TO/h).
  • a 600 mL Parr ® autoclave was first heated to about 100 °C under high vacuum to ensure 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 stock solution (10 mg in 10 mL CH 2 CI 2 ) of the nickel dibromide complex of 2,3-bis(2,6- diisopropylphenylimino)-[1 ,4]dithiane.
  • the autoclave was heated to 45 °C and 0.04 mL of (CH 3 CH 2 ) 2 AICI (100 equiv.) in toluene was added.
  • the reactor was rapidly pressurized to 100 psig and the temperature ramped up to 50 °C. After 10 minutes at 50 °C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which 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 rubbery solid (440,000 TO/h).
  • DSC (2nd heat) broad melt with an endothermic maximum at 29 °C.
  • 1 H NMR 80 branches/1000 carbon atoms.
  • a flame dried 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]dithiane.
  • the flask was cooled to 0 °C in an ice-water bath and filled with ethylene (1 atmosphere).
  • the flask was placed in a 23° C water bath and allowed to equilibrate with 1 atmosphere of ethylene for 5 minutes, then 4.0 mL of a 10 wt% solution of MAO in toluene was added and the mixture was stirred under 1 atmosphere of ethylene. Ethylene uptake 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 6 N aqueous HCl (100 mL).
  • the resultant suspension was cooled to 0° C and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. A white polyethylene precipitate (with a faint yellow-orange tinge) was observed within minutes. After 38 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL).
  • Example 58 Polymerization of ethylene with the nickel dibromide complex of 2,3- bis(benzyloxymethvO-5,6-bis(2,6-dimethylphenyliminoH1 ,41dioxane in the presence of MAO.
  • a 500 mL round bottom flask was fitted with a Schlenk adapter and 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 with 1 atmosphere ethylene for 19 minutes, then 0.25 mL of a stock solution prepared from 10.0 mg of the nickel dibromide complex of 2,3-bis(benzyloxymethyl)-5,6-bis(2,6- dimethylphenylimino)-[1 ,4]dioxane and 10.0 mL dichloromethane was added.
  • the reaction mixture was then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. Ethylene uptake and formation of a polyethylene precipitate were observed.
  • a 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 3.8 mg of the nickel dibromide complex of 5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)- [1 ,4]dioxane.
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • the resultant suspension was cooled to 0 °C. and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene.
  • a 600 mL Parr ® autoclave was first heated to about 100 °C under high vacuum to ensure 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 stock solution (10 mg in 10 mL CH 2 CI 2 ) 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 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig and the temperature ramped up to 65 °C. After 10 minutes at 65 °C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which separated was isolated by filtration and dried for several hours in a vacuum oven at 80° C. 1.3 g of a white rubbery solid was isolated (480,000 TO/h).
  • DSC (2nd heat) melt with an endothermic maximum at 76 °C.
  • 1 H NMR 33 branches/1000 carbon atoms.
  • Example 61 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis(2,6- dimethylphenyliminoWI ,41dioxane in the presence of MMAO (23 % iso- butylaluminoxane).
  • Example 62 Polymerization of ethylene with the nickel dibromide complex of 2,3-bis(2,6- dimethylphenyliminoH1 ,41dioxane in the presence of MMAO (23 % iso- butylaluminoxane).
  • a 600 mL Parr ® autoclave was first heated to about 100 °C under high vacuum to ensure 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 stock solution (10 mg in 10 mL CH CI 2 ) 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 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig and the temperature ramped up to 65 °C. After 10 minutes at 65 °C, the reaction was quenched by the addition of acetone, and methanol. The swollen polyethylene which separated was isolated by filtration and dried for several hours in a vacuum oven at 80 °C. 2.5 g of a white rubbery solid was isolated (660,000 TO/h).
  • DSC (2nd heat) broad melt with an endothermic maximum at 30 °C.
  • 1 H NMR 82 branches/1000 carbon atoms.
  • Example 68 Copolvmerization of ethylene and ethyl undecenoate with the nickel dibromide complex of 2,3-bis(2,6-dimethylphenyliminoH1 ,41dioxane in the presence of MMAO (23 % iso-butylaluminoxane).
  • a flame dried Schlenk flask equipped with a stir bar and a rubber septum was charged with 50 ml of toluene and 6 mg of the nickel dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1 ,4]dioxane.
  • the flask was cooled to 0 °C in an ice-water bath and filled with ethylene (1 atmosphere).
  • To the flask was added, 2.0 ml of MMAO in heptane (6.42 wt% aluminum). Within 15 seconds 2.5 ml of ethyl undecenoate was added to give a purple solution. The mixture was left to stir for 16 hours.
  • 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 onto a pressure head equipped with a mechanical stirrer and gas and liquid feed-through ports, then pressurized to 75 psig of ethylene and relieved to ambient pressure seven times.
  • the bottle was immersed in a 54° C. water bath, then 100 mL of dry, deoxygenated toluene was added via 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 again relieved, and 4.0 mL of a 10 wt% solution of MAO in toluene was quickly added.
  • the apparatus was again re-pressured to 75 psig ethylene and stirred at 300 rpm for another 5 min to ensure saturation with ethylene.
  • the pressure was once again relieved to ambient pressure and 0.5 mL of a stock solution prepared from 10.0 mg of the nickel dibromide complex of 2,3-bis(2,6- diisopropylphenylimino)-4-methylmorpholine and 10 mL dichloromethane was quickly added and the system quickly pressurized once again with ethylene to 75 psig. After 7 min the pressure was relieved to atmospheric and the reaction was quenched by addition of 5 mL methanol. After the apparatus was disassembled, an additional 50 mL methanol, 50 ml aqueous 6N HCl and 20 mL acetone was added.
  • Example 70 Polymerization of ethylene with the nickel dibromide complex of 2.3-bis(2.6- dimethyl-phenylimino)-4-methylmorpholine in the presence of MMAO.
  • a 600 mL Parr ® autoclave was first heated to about 100 °C under high vacuum to ensure 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 1 mL of a stock solution (10 mg in 20 mL CH2CI2) of the nickel dibromide complex of 2,3-bis(2,6-dimethyl- phenylimino)-4-methylmorpholine.
  • the autoclave was heated to 45 °C and 3 mL of MMAO in heptane (6.42 wt% aluminum) was added.
  • the reactor was rapidly pressurized to 100 psig and the temperature ramped up to 50 °C.
  • Example 71 Polymerization of ethylene with the nickel dibromide complex of 1 ,3-bis(4- methoxy-2,6-dimethylphenv0-4,5-bis(4-methoxy-2,6- dimethylphenylimino)imidazolidin-2-one 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, flame-dried, then refilled with ethylene.
  • the flask was provided with a room temperature (ca. 23°C) water bath, then charged with 100 mL of dry, deoxygenated toluene and allowed to equilibrate with 1 atmosphere ethylene for 30 minutes while stirring at 1000 rpm.
  • reaction mixture was then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene, then 0.10 mL of a stock solution prepared from 6.0 mg of the nickel dibromide complex of 1 ,3-bis(4- methoxy-2,6-dimethylphenyl)-4,5-bis (4-methoxy-2,6- dimethylphenylimino)imidazolidin-2-one and 6.0 mL dichloromethane was added. After about 7 min and 20 seconds an additional 0.25 mL of the stock solution was added. After 15 more minutes, the reaction mixture was quenched by the addition of acetone, methanol and 6 N aqueous HCl.
  • Example 72 Polymerization of ethylene with the reaction product of 1 ,3-bis-(2,6- dimethyl-phenv ⁇ -4,5-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-one, (1.2-dimethoxyethane)nickel(ll) dibromide, 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 ethylene for 10 minutes, then 0.10 mL of a stock solution (freshly prepared from 240 mg of the reaction product of 1 ,3-bis-(2,6dimethylphenyl)-4,5-bis-(2,6-dimethylphenylimino)- imidazolidin-2-one, (1,2-dimethoxyefhane)nickel(ll) dibromide, and silver tetrafluoroborate in 10 mL dry, deoxygentated dichloromethane) was added.
  • 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(O), 19 mg of ⁇ / 1 , ⁇ / 2 , ⁇ / 3 , ⁇ 4 -tetrakis(2,6- dimethylphenyl)oxalamidine, and 33 mg of the ether solvate of HB(Ar) 4 .
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • Example 75 Ethylene polymerization using complex XXXV.
  • H NMR was consistent with a copolymer containing approximately 96.5 weight % ethylene and 3.5 weight % vinyl ethylene carbonate monomer units.; M n 40,200 9 / m0 ⁇ ; M w 92,100 g / m0 ⁇ ; DSC T fl -68 °C, T m -38 °C.
  • Example 78 Ethylene/vinyl ethylene carbonate copolymerization using complex XXXV.
  • a 200 mL flame dried pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with (2,6-di- isopropylphenylimino)-[1 ,4]dithiane Pd(ll) catalyst XXXV (100 mg) in an argon filled glove box. Upon removal from the glove box, the flask was evacuated and backfilled with ethylene.
  • the catalyst was dissolved in CH 2 CI 2 (20 mL) and immediately treated with vinyl ethylene carbonate (10mL). The resulting orange solution was stirred at 23 °C under an ethylene atmosphere (1 atm) for 28 hours.
  • a Schlenk flask equipped with a magnetic stir bar was charged with 100 mg of 2,3-bis(2,6-diisopropylphenylimino)-[1 ,4]dioxane (0.25 mmol) and 71 mg of (1 ,2-dimethoxyethane)nickel(ll) dibromide (0.23 mmol) under an argon atmosphere. Dry, deoxygenated dichloromethane (15 mL) was added and the mixture was stirred under an argon atmosphere, turning red-brown within about 10 minutes.
  • Example 83 Preparation of the nickel dibromide complex of 2.3-bis(2,6- dimethylphenylimino)-2,3-dihvdroimidazor2,1- ⁇ 1thiazole.
  • Example 84 Polymerization of ethylene with the nickel dibromide complex 2,3-bis(2,6- dimethylphenylimino)-2,3-dihvdroimidazor2.1-blthiazole 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 2.5 mg of the nickel dibromide complex of 2,3-bis(2,6-dimethylphenylimino)-2,3- dihydroimidazo[2,1-ib]thiazole.
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • the mixture was stirred another 16 hours at 21 ° C, then diluted with 10 mL of dry, deoxygenated hexane and stirred another 3 hours.
  • the supernatant was removed via a filter paper-tipped cannula, and the residue dried in vacuo at 1 mm Hg to afford 95 mg of light green crystals.
  • 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 nickel dibromide complex of ⁇ / 1 , ⁇ / 2 , ⁇ / 3 , ⁇ / 4 -tetrakis(2,6-dimethylphenyl)oxalamidine.
  • the flask was evacuated and refilled with ethylene, then charged with 75 mL of dry, deoxygenated toluene.
  • the resultant suspension allowed to equilibrate with 1 atmosphere ethylene at 21 °C for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene.
  • Example 87 Copolvmerization of ethylene and 1-pentene with the nickel dibromide complex of 2,3-bis(2,6-dimethylphenyliminoH1.41dithiane 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 0.5 mL of a stock solution of 12.4 mg of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane in 10.0 mL dichloromethane.
  • the flask was evacuated and refilled with ethylene, then charged with 100 mL of dry, deoxygenated toluene, and 5.0 mL 1-pentene.
  • the resultant suspension was cooled to 0 °C and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. After 45 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen copolymer which 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 2.0 g of white coploymer.
  • 1 H NMR 24 branches/1000 carbon atoms.
  • a 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with 0.5 mL of a stock solution of 12.4 mg of the nickel dibromide complex of 2,3-bis(2,6- dimethylphenylimino)-[1 ,4]dithiane in 10.0 mL dichloromethane.
  • the flask was evacuated and refilled with ethylene, then charged with 100 mL of dry, deoxygenated toluene, and 5.0 mL 1-heptene.
  • the resultant suspension was cooled to 0 °C and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes, then treated with 4.0 mL of a 10 wt% solution of MAO in toluene and stirred under 1 atmosphere ethylene. After 33 minutes, the mixture was quenched by the addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen copolymer which 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 white coploymer.
  • 1 H NMR 19 branches/1000 carbon atoms.
  • a 22 mL vial equipped with a magnetic stir bar and capped by a septum was sequentially charged with 2.1 mg of the nickel dibromide complex 2, 3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1- jb]thiazole, 4.0 mL 1 -hexene, and 2.0 mL of a 10 wt% solution of MAO in toluene, under Ar.
  • the resultant dark purple-brown mixture thickened noticably within 10-20 minutes.

Abstract

L'invention concerne des procédés permettant de préparer des polymères d'oléfines, ou des catalyseurs à base d'oligomères permettant de préparer des polymères d'oléfines, et des ligands bidentés utilisés pour la préparation de ces catalyseurs. Les polymères peuvent être préparés en mettant en contact les monomères correspondants et un catalyseur contenant un métal de transition des groupes 8-10. Les polymères conviennent au traitement réalisé lors de processus d'extrusion classiques. Ils peuvent être formés à partir de feuilles ou films haute barrière ou de résines de faible poids moléculaire qui sont destinées à être utilisées dans des paraffines synthétiques d'enrobages à la paraffine ou en tant qu'émulsions.
PCT/US1998/003593 1997-03-10 1998-02-24 Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes WO1998040374A2 (fr)

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JP53958698A JP2002514252A (ja) 1997-03-10 1998-02-24 第８〜１０族遷移金属を含むオレフィン重合触媒、二座配位子、このような触媒の使用方法及びそれから得られるポリマー
EP98907610A EP0973762A2 (fr) 1997-03-10 1998-02-24 Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes
CA002283223A CA2283223A1 (fr) 1997-03-10 1998-02-24 Catalyseurs de polymerisation d'olefines contenant des metaux de transition des groupes 8-10, ligands bidentes, procedes utilisant de tels catalyseurs et polymeres obtenus a partir de ces procedes

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US4292597P 1997-04-04 1997-04-04
US60/043,406 1997-04-04
US60/042,925 1997-04-04
US4469197P 1997-04-18 1997-04-18
US60/044,691 1997-05-02
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999062968A1 (fr) * 1998-06-01 1999-12-09 Eastman Chemical Company Catalyseurs sur supports de polymerisation olefinique utilisant des metaux de transition des groupes 8-10
WO2000006620A2 (fr) * 1998-07-29 2000-02-10 E.I. Du Pont De Nemours And Company Polymerisation d'olefines
WO2000022007A1 (fr) * 1998-10-14 2000-04-20 E.I. Du Pont De Nemours And Company Polymerisation d'olefines
EP1026179A1 (fr) * 1999-02-01 2000-08-09 Elenac GmbH Procédé de préparation de polyoléfines présentant une large distribution de poids moléculaire
EP1026180A1 (fr) * 1999-02-01 2000-08-09 Elenac GmbH Procédé de préparation de polyoléfines présentant une large distribution de poids moléculaire
WO2000050475A1 (fr) * 1999-02-23 2000-08-31 Eastman Chemical Company Catalyseurs mixtes de polymerisation d'olefine, procedes faisant intervenir de tels catalyseurs et polymeres ainsi obtenus
WO2000053646A1 (fr) * 1999-03-09 2000-09-14 Basell Technology Company B.V. Procede multi-etape pour la (co) polymerisation des olefines
US6245871B1 (en) 1997-04-18 2001-06-12 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
DE19963589A1 (de) * 1999-12-23 2001-06-28 Univ Schiller Jena Verfahren zur Herstellung von katalytisch aktiven Metallkomplexen
US6281303B1 (en) 1999-07-27 2001-08-28 Eastman Chemical Company Olefin oligomerization and polymerization catalysts
US6303710B1 (en) 1999-01-27 2001-10-16 E. I. Du Pont De Nemours And Company Control of olefin polymerization using hydrogen
WO2001077193A1 (fr) * 2000-04-10 2001-10-18 Bp Chemicals Limited Procede de polymerisation
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US6350837B1 (en) 2000-06-09 2002-02-26 Eastman Chemical Company Copolymerization of norbornene and functional norbornene monomers
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WO2002036585A2 (fr) * 2000-11-06 2002-05-10 Eastman Chemical Company Procede de preparation de ligands pour catalyseurs de polymerisation des olefines
US6395668B1 (en) 1998-12-15 2002-05-28 Basell Technology Company Bv Catalyst system for olefin polymerization
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US6605677B2 (en) 2000-02-18 2003-08-12 Eastman Chemical Company Olefin polymerization processes using supported catalysts
US6608224B2 (en) 2000-02-24 2003-08-19 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
US6660677B1 (en) 1997-03-10 2003-12-09 Eastman Chemical Company Supported group 8-10 transition metal olefin polymerization catalysts
US6706891B2 (en) 2000-11-06 2004-03-16 Eastman Chemical Company Process for the preparation of ligands for olefin polymerization catalysts
EP1471079A2 (fr) * 1998-10-14 2004-10-27 E.I.Du pont de nemours and company Polymérisation d'éthylène
US6822062B2 (en) 1997-03-10 2004-11-23 Eastman Chemical Company Supported group 8-10 transition metal olefin polymerization catalysts
US7056996B2 (en) 2000-02-18 2006-06-06 E. I. Du Pont De Nemours And Company Productivity catalysts and microstructure control
US7183332B2 (en) 2000-12-22 2007-02-27 Basell Poliolefine Italia S.P.A. Process for the preparation of porous polymers and polymers obtainable thereof
US7220801B2 (en) 2001-06-22 2007-05-22 Exxonmobil Chemical Patents Inc. Metallocene-produced very low density polyethylenes or linear low density polyethylenes as impact modifiers
US7314903B2 (en) 2002-07-09 2008-01-01 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
DE112006001733T5 (de) 2005-07-01 2008-07-31 Albemarle Corporation Aluminoxanatsalzzusammensetzungen mit verbesserter Stabilität in aromatischen und aliphatischen Lösungsmitteln
US7417006B2 (en) 2001-05-21 2008-08-26 Basell Polyolefine Gmbh Catalyst system for the polymerization of olefins
EP2308815A1 (fr) 2001-08-06 2011-04-13 Ineos Europe Limited Procede de reaction de croissance de chaine
WO2012071205A2 (fr) 2010-11-22 2012-05-31 Albemarle Corporation Compositions d'activateurs, leur préparation et leur utilisation en catalyse
WO2013162745A1 (fr) 2012-04-27 2013-10-31 Albemarle Corporation Compositions d'activateur, leur préparation et leur utilisation dans des catalyseurs
US9315755B2 (en) 2011-05-16 2016-04-19 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalytic system for preparation of high branched alkane from olefins
WO2018164798A1 (fr) 2017-03-09 2018-09-13 Exxonmobil Chemical Patents Inc. Procédé de production de polymères de polyéthylène
WO2021083350A1 (fr) 2019-10-31 2021-05-06 中国石油化工股份有限公司 Complexe métallique de diimine, son procédé de préparation et son application
WO2021083330A1 (fr) 2019-10-31 2021-05-06 中国石油化工股份有限公司 Complexe métallique amino-imine ainsi que son procédé de préparation et son application

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4857475B2 (ja) * 2001-03-12 2012-01-18 東ソー株式会社 遷移金属化合物、オレフィン重合用触媒およびオレフィンの重合方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997002298A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Procede de polymerisation d'olefines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997002298A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Procede de polymerisation d'olefines

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DOERING M.: "Nitrogen derivatives of oxylic acid as new complexing agent" ZEITSCHRIFT F]R ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 620, no. 3, 1994, pages 551-560, XP002067882 *
GOK YASAR: "Axial-ligation and macrocyclization of nval (E,E)-dioximes of Ni(II), Pd(II), Pt(II) and Co(II)" TRANSITION METAL CHEMISTRY, vol. 20, no. 3, June 1909, pages 225-319, XP002067883 *
JOHNSON L K ET AL: "COPOLYMERIZATION OF ETHYLENE AND PROPYLENE WITH FUNCTIONALIZED VINYL MONOMERS BY PALLADIUM(II)-CATALYSTS" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 118, 10 October 1996, page 267/268 XP000644783 *
JOHNSON L K ET AL: "MEW PD(II)- AND NI(II)-BASED CATALYSTS FOR POLYMERIZATION OF ETHYLENE AND ALPHA-OLEFINS" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 117, no. 23, 14 June 1995, page 6414/6415 XP000644782 cited in the application *
LINDAUER, DIRK ET AL: "Aminolysis of bisimidoyl chlorides of oxalic acid. Part I. Reaction with aromatic and aliphatic amines" J. PRAKT. CHEM./CHEM.-ZTG. (1995), 337(2), 143-52 CODEN: JPCCEM;ISSN: 0941-1216, XP002067907 *
MARINGGELE W.: "Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molek}len." ZEITSCHRIFT F]R NATURFORSCHUNG, vol. 40b, no. 2, February 1985, pages 277-281, XP002067881 *
See also references of EP0973762A2 *

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