Transition Metal Catalysts. I. Ethylene Polymerization with a Soluble Catalyst Formed from an Aluminum Halide, Tetraphenyltin and a Vanadium Halide¹

Isoprene polymerization mediated by vanadium-[ONNO] complexes

“…7 These classical Ziegler-type vanadium catalyst systems typically consist of a vanadium compound (VOCl 3 , VCl 4 , VCl 3 , V(acac) 3 with acac = acetylacetonate, etc.) 8 Indeed, such vanadiumbased catalyst systems are known to produce: (i) high molecular weight linear polyethylene (compared with Ti-based Ziegler catalysts) with narrow molecular weight distribution, 1,9,10 (ii) high molecular weight amorphous polymers applied to the synthesis of ethylene/propylene/diene copolymers used for the manufacture of synthetic rubber and elastomers (EPDM)) as well as ethylene/α-olefin and ethylene/cyclic olefin copolymers with high comonomer incorporations, 8,9,[11][12][13][14][15][16][17][18] and (iii) syndiotactic ''living'' polypropylene with narrow molecular weight distribution or diblock copolymers of propylene and methyl methacrylate (MMA). 8 Indeed, such vanadiumbased catalyst systems are known to produce: (i) high molecular weight linear polyethylene (compared with Ti-based Ziegler catalysts) with narrow molecular weight distribution, 1,9,10 (ii) high molecular weight amorphous polymers applied to the synthesis of ethylene/propylene/diene copolymers used for the manufacture of synthetic rubber and elastomers (EPDM)) as well as ethylene/α-olefin and ethylene/cyclic olefin copolymers with high comonomer incorporations, 8,9,[11][12][13][14][15][16][17][18] and (iii) syndiotactic ''living'' polypropylene with narrow molecular weight distribution or diblock copolymers of propylene and methyl methacrylate (MMA).…”

Olefin Polymerization with Non-metallocene Catalysts (Early Transition Metals)

“…Only the configurationally stable 1,4-dithiabutanediyl-linked phenolates with bulky ortho-substituents appeared to be capable of stabilizing a C 2 -symmetric, helical ligand sphere at the titanium center and thereby provided an active site for the isospecific styrene polymerization [71]. [69][70][71] weight linear polyethylene with uniform molecular weight distribution [72][73][74], and (ii) high molecular weight amorphous polymers applied to syntheses of ethylene/propylene/diene copolymers (called EPDM, synthetic rubbers) [75][76][77], ethylene/cyclic olefin copolymers (COC). Moreover, (iii) the catalyst system [V(acac) 3 (acac = acetylacetonato)-Et 2 AlCl] polymerizes propylene to give not only a syndiotactic ''living'' polymer with narrow molecular weight distribution (M w /M n = 1.05-1.20) [78][79][80], but also diblock copolymers of propylene and methyl methacrylate (MMA) [78][79][80].…”

Facile, Efficient Copolymerization of Ethylene with Norbornene-Containing Dienes Promoted by Single Site Non-Metallocene Oxovanadium(V) Catalytic System

“…Among the classical Ziegler-Natta type catalysts, vanadium catalysts show outstanding catalytic properties for the manufacture of synthetic rubber and elastomers [23][24][25][26][27]. For example, Christman D.L.…”