Synthesis of a soluble vinyl‐type polynorbornene with a half‐titanocene/methylaluminoxane catalyst

Norbornene polymerization was performed with monocyclopentadienyltitanium tribenzyloxide activated with methylaluminoxane (MAO). The catalyst afforded a pure vinyl-type polymer at temperatures below 80 °C and at appropriate MAO concentrations. However, at higher temperatures or high MAO concentrations, a portion of the titanium species was pyrolyzed to form an alkylidene compound that catalyzed the ring-opening metathesis polymerization of norbornene. As a result, both vinyl-type and ring-opening polymers were produced under the reaction conditions.

[1]  Qing Wu,et al.  Atactic polymerization of propylene catalyzed by mono(η5-cyclopentadienyl) titanium tribenzyloxide combined with methylaluminoxane , 1998 .

[2]  B. Rieger,et al.  Polymerization of norbornene by palladium(II) complexes bearing ethylene-bridged bisindolinyl- or bis(1,2,3,4-tetrahydroquinolinyl) ligands , 1998 .

[3]  Walter Kaminsky,et al.  New polymers by metallocene catalysis , 1996 .

[4]  J. Wendorff,et al.  Polynorbornene: synthesis, properties and simulations , 1996 .

[5]  M. Bochmann.  Cationic Group 4 metallocene complexes and their role in polymerisation catalysis: the chemistry of well defined Ziegler catalysts , 1996 .

[6]  W. Kaminsky,et al.  Hydrooligomerization of cycloolefins -a view of the microstructure of polynorbornene , 1995 .

[7]  David Fischer,et al.  Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts , 1995 .

[8]  G. Rempel,et al.  Ziegler-Natta catalysts for olefin polymerization: Mechanistic insights from metallocene systems , 1995 .

[9]  I. S. Bhardwaj,et al.  Metallocene Complexes of Group 4 Elements in the Polymerization of Monoolefins , 1994 .

[10]  N. Petasis,et al.  Ring-opening metathesis polymerization of norbornene with titanium alkylidenes generated by thermolysis of dimethyltitanocene and related cyclopentadienyltitanium(IV) derivatives , 1993 .

[11]  N. Seehof,et al.  Pd2+ catalyzed addition polymerizations of norbornene and norbornene derivatives , 1992 .

[12]  W. Kaminsky,et al.  Stereospecific polymerization by metallocene/aluminoxane catalysts , 1992 .

[13]  R. Grubbs,et al.  Titanacyclobutanes derived from strained, cyclic olefins: the living polymerization of norbornene , 1986 .

[14]  A. Balaban,et al.  Olefin metathesis and ring-opening polymerization of cyclo-olefins , 1985 .

[15]  T. Saegusa,et al.  Polymerization of norbornene by modified Ziegler‐catalysts , 1965 .

[16]  I. Robinson,et al.  Polynorbornene by Coördination Polymerization1 , 1960 .