Radical copolymerization of 2‐trifluoromethylacrylic monomers. I. Kinetics of their copolymerization with norbornenes and vinyl ethers as studied by in situ 1H NMR analysis

Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers and electron‐rich norbornene derivatives and vinyl ethers with azobisisobutyronitrile were investigated by analyzing the kinetics in situ with ¹H NMR. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. Terpolymerization involving these monomers was also investigated. The rates of copolymerization and kinetic chain lengths were determined in some cases on the basis of the in situ kinetics analysis. These radial copolymerizations of TFMA provide a basis for the preparation of chemical‐amplification resist polymers for emerging 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1468–1477, 2004