Vinyl addition polymerization of norbornene using cyclopentadienylzirconium trichloride activated by isobutyl‐modified methylaluminoxane

Abstract

Norbornene polymerization using the commercially available and inexpensive catalyst system, cyclopentadienylzirconium trichloride (CpZrCl3) and isobutyl‐modified methylaluminoxane (MMAO), were carried out over a wide range of polymerization temperatures and monomer concentrations. For the CpZrCl3 catalyst system activated by aluminoxane with a 40 mol % methyl group and a 60 mol % isobutyl group (MMAO40/60), the polymerization temperature and monomer concentration significantly affected the molecular weight (Mn) of the obtained polymer and the catalytic activity. With an increase in the polymerization temperature from 0 to 27 °C, the catalytic activity and Mn increased, but these values dramatically decreased with the increasing polymerization temperature from 27 to 70 °C, meaning that the most suitable temperature was 27 °C. The CpZrCl3/MMAO40/60 ([Al]/[Zr] = 1000) catalyst system with the [NB] of 2.76 mol L−1 at 27 °C showed the highest activity of 145 kg molZr−1 h−1 and molecular weight of 211,000 g mol−1. The polymerization using the CpZrCl3/MMAO40/60 catalyst system proceeds through the vinyl addition mechanism to produce atactic polynorbornene, which was soluble in chloroform, toluene, and 1,2‐dichlorobenzene, but insoluble in methanol. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1185–1191, 2008

Pd(II) complexes bearing di‐ and monochelate fluorinated β‐ketonaphthyliminato ligand and their catalytic properties towards vinyl‐addition polymerization and copolymerization of norbornene and ester‐functionalized norbornene derivative

“…Incorporation of functional groups into the polymer chains has proved to be an effective strategy for overcoming these drawbacks . A series of copolymers of norbornene (NB) with polar monomers, NB derivatives, have been studied. Among the family of cyclo‐olefin copolymers, some of the versatile and interesting ones are the copolymers of NB with functionalized NB derivatives.…”

“…Furthermore, the use of appropriately functionalized NB derivatives allows for post‐polymerization modification and further expands the range of properties of these copolymers, thus providing an entry into other kinds of polymeric materials . Catalysts containing the metals nickel, chromium, titanium, zirconium, cobalt and palladium have been variously reported for the vinyl polymerization of NB. Transition metal‐catalyzed addition polymerization of functional NBs, particularly those containing oxygen functionalities, has proved to be difficult due to catalyst inhibition by coordination of the functionality to the metal center.…”

Ni(II) and Pd(II) complexes bearing novel bis(β‐ketoamino) ligand and their catalytic activity toward copolymerization of norbornene and 5‐norbornene‐2‐yl acetate combined with B(C6F5)3

“…Norbornene (NB; bicycle[2.2.1]hept‐2‐ene) is polymerized by cationic or radical polymerization,1–3 ring‐opening metathesis polymerization,4–11 and vinyl‐type addition polymerization 12–21. The increasing interest in vinyl‐type polynorbornene (PNB) is due to its high glass transition temperature, high optical transparency, low dielectric constant, and low birefringence.…”

Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal‐catalyzed polymerizations

“…On the other hand, the addition polymerization of norbornene derivatives has attracted growing attention recently, because it gives the corresponding poly(norbornene)s without CC double bonds and thus highly durable even in the presence of oxygen. Various transition metal catalysts involving nickel,5 palladium,6 cobalt,7 iridium,8 titanium,9 and zirconium10 have been developed for the addition polymerization of norbornenes.…”