Facile Preparation of Nanoparticles by Intramolecular Cross-Linking of Isocyanate Functionalized Copolymers.

graphical abstract
Beck, J.B.; Killops, K.L.; Kang, T.; Sivanandan, K.; Bayles, A.; Mackay, M.E.; Wooley, K.L.; Hawker, C.J.;
Macromolecules,
2009
42, 5629-5635.

A new synthetic approach to the preparation of intramolecularly collapsed nanoparticles under mild, room temperature conditions has been developed from commercially available vinyl monomers. Reaction of isocyanate functionalized linear copolymers with a diamine in dilute solution leads to the efficient formation of nanoparticles where the diameter of the nanoparticle can be varied by controlling both the molecular weight and mole percentage of isocyanate repeat units. Physical properties for the intramolecularly collapsed nanoparticles were fully consistent with a three-dimensional structure and analysis of the collapse reaction revealed that approximately 75% of the isocyanate groups along the backbone underwent cross-linking with 25% being available for further reaction with monofunctional amines. This stepwise consumption of the isocyanates allows the chemical and physical properties of the nanoparticles to be further tuned and significantly opens up the range of nanoparticles that can be prepared using this mild and highly efficient chemistry.