Pd-Catalyzed Addition Polymerization

The same norbornene-type monomers which may be polymerized via ROMP may be polymerized instead through the double bonds, retaining all the rings and eliminating the unsaturation (by converting the double bond to two single bonds that form the polymer backbone). The rigid nature of the polymer backbone in such addition polymers imbues them with very high glass transition temperatures (approximately 385°C for unsubstituted polynorbornene), and such polymers are employed as dielectrics in microelectronics applications. Monophosphine-ligated alkylpalladium or allylpalladium complexes are efficient initiators for such polymerizations (e.g., Lipian et al., Macromolecules, 35, 8969 (2002)). In collaboration with researchers at Promerus LLC, we are currently investigating the ability of such complexes to generate well-defined homopolymers, statistical copolymers, and block copolymers from a variety of norbornene-type monomers with a broad range of monomer functionality.

Pd-Catalyzed Addition Polymerization
Phenethylnorbornene (center) can be polymerized either by ROMP (right) or by Pd-catalyzed addition polymerization (left), to yield two distinct polymers, with very different repeat unit structures and physical properties (Bishop and Register, Macromol. Rapid Commun., 29, 713 (2008)).

Supported by Promerus LLC and the Princeton University Innovation Fund for Industrial Collaborations

Current/Recent Group Members Employing Pd-Catalyzed Addition Polymerization or Polymers Therefrom, and Their Project Titles:

Dong-Gyun Kim PDRA – “Novel Block Copolymers for Butanol Pervaporation Membranes”
John Bishop PhD *11 – “Structure-Property Relationships in Novel Polymers and Block Copolymers from Ring-Opening Metathesis Polymerization”

Selected Recent Publications:

J.M. Torres, C. Wang, E.B. Coughlin, J.P. Bishop, R.A. Register, R.A. Riggleman, C.M. Stafford, and B.D. Vogt, "Influence of Chain Stiffness on Thermal and Mechanical Properties of Polymer Thin Films", Macromolecules, 44, 9040-9045 (2011).

J.P. Bishop and R.A. Register, "Poly(phenylethylnorbornene)s and their Hydrogenated Derivatives", Macromol. Rapid Commun., 29, 713-718 (2008).