Multicyclic Polymer Synthesis through Controlled/Living Cyclopolymerization of α,ω-Dinorbornenyl-Functionalized Macromonomers

A novel synthesis of multicyclic polymers that feature ultradense arrays of cyclic polymer units has been developed by exploiting the cyclopolymerization of α,ω-norbornenyl end-functionalized macromonomers mediated by the Grubbs third-generation catalyst (G3). Owing to the living polymerization nature, the number of cyclic repeating units in these multicyclic polymers was controlled to be between 1 and approximately 70 by varying the initial macromonomer-to-G3 ratio. The ring size was also tuned by choosing the molecular weight of the macromonomer; in this way we successfully prepared multicyclic polymers that possess cyclic repeating units composed of up to about 500 atoms, which by far exceeds those prepared to date by cyclopolymerization. Specifically, cyclopolymerizations of α,ω-norbornenyl end-functionalized poly­(l-lactide)­s (PLLAs) proceeded homogeneously under highly dilute conditions (∼0.1 mM in CH₂Cl₂) to give multicyclic polymers that feature cyclic PLLA repeating units on the polynorbornene backbone. The cyclic product architectures were confirmed not only by structural characterization based on NMR, MALDI-TOF MS, and SEC analyses but also by comparing their glass transition temperatures, viscosities, and hydrodynamic radii with their acyclic counterparts. The cyclopolymerization strategy was applicable to a variety of α,ω-norbornenyl end-functionalized macromonomers, such as poly­(ε-caprolactone), poly­(ethylene glycol) (PEG), poly­(tetrahydrofuran), and PLLA-<i>b</i>-PEG-<i>b</i>-PLLA. The successful statistical and block cyclocopolymerizations of the PLLA and PEG macromonomers gave amphiphilic multicyclic copolymers