"Benzodithiophene homopolymers synthesized by Grignard metathesis (GRIM) and Stille coupling polymerizations." Journal of Materials Chemistry A 2(23): 8773-8781.
ABSTRACT: The Grignard metathesis (GRIM) polymerization of 3-alkylthiophenes proceeds by a quasi-“living ” chain growth mechanism, not by a step growth process. Kinetic studies of the Grignard metathesis polymerization of 2,5-dibromo-3-alkylthiophenes showed that the molecular weight of poly(3-alkylthiophenes) is a function of the molar ratio of the monomer to nickel initiator, and conducting polymers with predetermined molecular weights and relatively narrow molecular weight distributions (PDIs) 1.2-1.5) can be made. Sequential monomer addition resulted in new block copolymers containing different poly(3-alkylthiophene) segments.
Grignard Metathesis Polymerization and Properties of …
We describe a method for growing uniform, covalently attached polymer onto crystalline Si(111) surfaces. H-Terminated Si was first chlorinated, and the surface-bound chlorine was then replaced by a terminal olefin using a Grignard reaction. A ruthenium ring-opening metathesis polymerization catalyst was then crossed onto the terminal otefin, and the resulting surface was subsequently immersed into a solution of monomer to produce the desired surface-attached polymer. The method provides a direct linkage between the polymer and the Si without the presence of an electrically defective oxide layer. Growth of the polymeric layer could be controlled by varying the concentration of monomer in solution, and polynorbornene films between 0.9 and 5500 nm in thickness were produced through the use of 0.01-2.44 M solutions of norbornene.