We demonstrate, in this article, the facile synthesis of a broad class of low-polydispersity ethylene–norbornene (E–NB) copolymers having various controllable comonomer composition distributions, including gradient, alternating, diblock, triblock, and block–gradient, through “living”/quasiliving E–NB copolymerization facilitated with a single Pd–diimine catalyst (1). This synthesis benefits from two remarkable features of catalyst 1, its high capability in NB incorporation and high versatility in rendering E–NB “living” copolymerization at various NB feed concentrations ([NB]0) while under an ethylene pressure of 1 atm and at 15 °C. At higher [NB]0 values between 0.42 and 0.64 M, E–NB copolymerization with 1 renders nearly perfect alternating copolymers. At lower [NB]0 values (0.11–0.22 M), gradient copolymers yield due to gradual reduction in NB concentration, with the starting chain end containing primarily alternating segments and the finishing end being hyperbranched polyethylene segments. Through two-stage or three-stage “living” copolymerization with sequential NB feeding, diblock or triblock copolymers containing gradient block(s) have been designed. This work thus greatly expands the family of E–NB copolymers. All the copolymers have controllable molecular weight and relatively low polydispersity (with polydispersity index below 1.20). Most notably, some of the gradient and block–gradient copolymers have been found to exhibit the characteristic broad glass transitions as a result of their possession of broad composition distribution. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013
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