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US 5,714,556 AGranted
Olefin polymerization process
AssigneeE. I. DuPont de Nemours and Company
InventorsLynda Kaye Johnson, Jerald Feldman, Kristina Ann Kreutzer, Stephan James McLain, Alison Margaret Anne Bennett, Edward Bryan Coughlin, Dennis Scott Donald, Lissa Taka Jennings Nelson, Anju Parthasarathy, Xing Shen, Wilson Tam, Yueli Wang
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Abstract
Disclosed herein is a process for the polymerization of ethylene, norbornenes and styrenes, by contacting in solution a selected nickel compound and a selected compound which is or can coordinated to the nickel with the olefin(s). The polymers produced are useful for films and molding resins.
Claims59
A process for the polymerization of a polymerizable monomer, comprising,
- (a) contacting ethylene, a norbornene or a styrene, and a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group consisting of:
- ##STR150## and wherein:
- X is a noncoordinating anion;
- Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl;
- each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl;
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.9 is independently hydrogen or hydrocarbyl;
- and
- each R.sup.3 is independently a monovalent aromatic moiety;
- m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.44 is aryl;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
- and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
30 more elements
A process for the polymerization of a polymerizable monomers, comprising, contacting ethylene, a norbornene, or a styrene with a nickel II! complex of a first compound selected from the group consisting of:
- ##STR151## and wherein:
- X is a noncoordinating anion;
- Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl;
- each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.3 is independently a monovalent aromatic moiety;
- each R.sup.9 is independently hydrogen or hydrocarbyl;
- m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarby;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety, --CO.sub.2 R.sup.25, or Ar.sup.7 and Ar.sup.8 taken together are a divalent aromatic moiety and wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.44 is aryl;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms, and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
27 more elements
A process for the polymerization of polymerizable monomers, comprising, contacting ethylene, a norbornene or a styrene with a nickel containing first compound of the formula L.sup.1.sub.q L.sup.2.sub.r L.sup.3.sub.s L.sup.4.sub.t Ni!.sup.+ X.sup.- (XXXIII), wherein:
- L.sup.1 is a first monodentate neutral ligand coordinated to said nickel, L.sup.2 is a second monodentate neutral ligand coordinated to said nickel which may be said first monodentate neutral ligand and r is 0 or 1, or L.sup.1 and L.sup.2 taken together are a first bidentate neutral ligand coordinated to said nickel and r is 1;
- L.sup.3 and L.sup.4 taken together are a .pi.-allyl ligand coordinated to said nickel, L.sup.3 and L.sup.4 taken together are ##STR152## coordinated to said nickel, or L.sup.3 is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can be displaced by an olefin, and L.sup.4 is R.sup.38 ;
- q, s and t are each 1;
- X is a relatively non-coordinating anion;
- said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of ##STR153## Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl;
- each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.9 is independently hydrogen or hydrocarbyl;
- and
- each R.sup.3 is independently a monovalent aromatic moiety;
- m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms;
- and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
- R.sup.35 is hydrocarbylene;
- R.sup.36 is hydrogen, alkyl, or --C(O)R.sup.39 ;
- each R.sup.37 is hydrocarbyl or both of R.sup.37 taken together are hydrocarbylene to form a carbocyclic ring;
- R.sup.38 is hydride, alkyl or --C(O)R.sup.39 ;
- R.sup.39 is hydrocarbyl;
- and
- R.sup.44 is aryl.
37 more elements
Dependencies are inferred from the claim text.