Metal catalyzed synthesis of hyperbranched ethylene and/or α-olefin polymers

A method of synthesizing polymers from propylene, which comprises:

• contacting under polymerization conditions and optionally, in the presence of a halogenated solvent (a) propylene and (b) a catalyst system consisting essentially of (i) a transition metal component, (ii) an excess of a Lewis acid component having the formula AlXxR3−x, where X is a halogen, R is a lower alkyl and x is 0 to 3, and, optionally, (iii) a nitrogen, oxygen, phosphorus or mixed nitrogen and/or oxygen and/or phosphorus based monodentate, bidentate or tridentate ligand, so as to form branched propylene polymers that are liquid, viscous oils at about room temperature, said polymers having a molecular weight in excess of about 300 and having a ratio of methyl hydrogens centered around 0.85 ppm in the 1H-NMR spectra of the polymers relative to the total aliphatic hydrogens in the polymers of greater than 0.50;
• said Lewis acid component being present during the propylene polymer synthesis in an amount of from about 2 to 50 moles per mole of transition metal component, wherein the transition metal component is selected from the group consisting of {(π-(meth)allyl)Ni(Br)}2, (1,5-cyclooctadiene)Pd(CH3)(Cl), {Ni((meth)allyl)(trifluoroacetate)}2, Ni(1,5-cyclooctadiene)2, PdCl2, Pd(1,5-cyclooctadiene)Cl2, Co(acetylacetonate)3, Mn(acetylacetonate)2, {(1,5-cyclooctadiene)Rh(Cl)}2, complexes of Ni that consist of Ni and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, complexes of Pd that consist of Pd and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, and mixtures thereof.

A method of synthesizing polymers from butene, which comprises:

• contacting under polymerization conditions and optionally, in the presence of a halogenated solvent (a) butene and (b) a catalyst system consisting essentially of (i) a transition metal component, (ii) an excess of a Lewis acid component having the formula AlXxR3−x, where X is a halogen, R is a lower alkyl and x is 0 to 3, and, optionally, (iii) a nitrogen, oxygen, phosphorus or mixed nitrogen and/or oxygen and/or phosphorus based monodentate, bidentate or tridentate ligand, so as to form branched butene polymers that are liquid, viscous oils at about room temperature, said polymers having a molecular weight in excess of about 300 and having a ratio of methyl hydrogens centered around 0.85 ppm in the 1H-NMR spectra of the polymers relative to the total aliphatic hydrogens in the polymers of at least about 0.40, wherein the transition metal component is selected from the group consisting of {(π-(meth)allyl)Ni(Br)}2, (1,5-cyclooctadiene)Pd(CH3)(Cl), {Ni((meth)allyl)(trifluoroacetate)}2, Ni(1,5-cyclooctadiene)2, PdCl2, Pd(1,5-cyclooctadiene)Cl2, Co(acetylacetonate)3, Mn(acetylacetonate)2, {(1,5-cyclooctadiene)Rh(Cl)}2, complexes of Ni that consist of Ni and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, complexes of Pd that consist of Pd and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, and mixtures thereof.

A method of synthesizing polymers from ethylene, which comprises:

• contacting under polymerization conditions and optionally, in the presence of a halogenated solvent (a) ethylene and (b) a catalyst system consisting essentially of (i) a transition metal component, (ii) an excess of a Lewis acid component having the formula AlXxR3−x, where X is a halogen, R is a lower alkyl and x is 0 to 3, and (iii) a nitrogen, oxygen, phosphorus or mixed nitrogen and/or oxygen and/or phosphorus based monodentate, bidentate or tridentate ligand, so as to form branched ethylene polymers that are liquid, viscous oils at about room temperature, said polymers having a molecular weight in excess of about 300 and having a ratio of methyl hydrogens centered around 0.85 ppm in the 1H-NMR spectra of the polymers relative to the total aliphatic hydrogens in the polymers of at least about 0.40, wherein the transition metal component is selected from the group consisting of {(π-(meth)allyl)Ni(Br)}2, (1,5-cyclooctadiene)Pd(CH3)(Cl), {Ni((meth)allyl)(trifluoroacetate)}2, Ni(1,5-cyclooctadiene)2, PdCl2, Pd(1,5-cyclooctadiene)Cl2, Co(acetylacetonate)3, Mn(acetylacetonate)2, {(1,5-cyclooctadiene)Rh(Cl)}2, complexes of Ni that consist of Ni and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, complexes of Pd that consist of Pd and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, and mixtures thereof.

A method of synthesizing polymers from propylene, which comprises:

• contacting under polymerization conditions and optionally, in the presence of a halogenated solvent (a) propylene and (b) a catalyst system consisting essentially of (i) a transition metal component, (ii) an excess of a Lewis acid component having the formula AlXxR3−x, where X is a halogen, R is a lower alkyl and x is 0 to 3, and (iii) a nitrogen, oxygen, phosphorus or mixed nitrogen and/or oxygen and/or phosphorus based monodentate, bidentate or tridentate ligand, so as to form branched propylene polymers that are liquids viscous oils at about room temperature, said polymers having a molecular weight in excess of about 300 and having a ratio of methyl hydrogens centered around 0.85 ppm in the 1H-NMR spectra of the polymers relative to the total aliphatic hydrogens in the polymers of greater than 0.50, wherein the transition metal component is selected from the group consisting of {(π-(meth)allyl)Ni(Br)}2, (1,5-cyclooctadiene)Pd(CH3)(Cl), {Ni((meth)allyl)(trifluoroacetate)}2, Ni(1,5 -cyclooctadiene)2, PdCl2, Pd(1,5-cyclooctadiene)Cl2, Co(acetylacetonate)3, Mn(acetylacetonate)2, {(1,5-cyclooctadiene)Rh(Cl)}2, complexes of Ni that consist of Ni and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, complexes of Pd that consist of Pd and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, and mixtures thereof.

A method of synthesizing polymers from butene, which comprises:

• contacting under polymerization conditions and optionally, in the presence of a halogenated solvent (a) butene and (b) a catalyst system consisting essentially of (i) a transition metal component, (ii) an excess of a Lewis acid component having the formula AlXxR3−x, where X is a halogen, R is a lower alkyl and x is 0 to 3, and (iii) a nitrogen, oxygen, phosphorus or mixed nitrogen and/or oxygen and/or phosphorus based monodentate, bidentate or tridentate ligand, so as to form branched butene polymers that are liquid, viscous oils at about room temperature, said polymers having a molecular weight in excess of about 300 and having a ratio of methyl hydrogens centered around 0.85 ppm in the 1H-NMR spectra of the polymers relative to the total aliphatic hydrogens in the polymers of at least about 0.40, wherein the transition metal component is selected from the group consisting of {(π-(meth)allyl)Ni(Br)}2, (1,5-cyclooctadiene)Pd(CH3)(Cl), {Ni((meth)allyl)(trifluoroacetate)}2, Ni(1,5-cyclooctadiene)2, PdCl2, Pd(1,5-cyclooctadiene)Cl2, Co(acetylacetonate)3, Mn(acetylacetonate)2, {(1,5-cyclooctadiene)Rh(Cl)}2, complexes of Ni that consist of Ni and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, complexes of Pd that consist of Pd and at least one moiety selected from the group consisting of alkyl, aryl and halide moieties, and mixtures thereof.