In this talk, I will introduce a newly developed strategy to effectively produce a myriad of 1D nanocrystals with unprecedented control over their dimensions, compositions, and architectures by capitalizing on a set of rationally designed bottlebrush-like block copolymers with well-defined molecular architecture and molecular weight (MW) as nanoreactors. These bottlebrush-like block copolymers (BBCPs) are unimolecular cylindrical polymer brushes possessing a cellulose backbone with densely grafted diblock or triblock copolymers as side chains (i.e., arms). Cellulose forms a rigid backbone because of intramolecular hydrogen bridges between the secondary hydroxyl groups at the C3 position of an anhydroglucose unit (AGU) and the oxygen of the pyrane ring in the adjacent AGU. As a result, the free rotation around the glycosidic bond is hindered. In addition, the three substitutable hydroxyl groups on each AGU offer easy access to graft dense polymer side chains from the cellulose backbone. Thus, we utilize these advantages peculiar to cellulose for the synthesis of straight cylindrical BBCPs carrying densely grafted functional block copolymer side chains. A family of BBCPs synthesized by either sequential atom transfer radical polymerization (ATRP) or ATRP(s) followed by a click reaction include cellulose-graft-[poly(acrylic acid)-block-polystyrene] (denoted cellulose-g-[PAA-b-PS]) and cellulose-graft-[poly(acrylic acid)-block-poly(ethylene glycol)] (cellulose-g-[PAA-b-PEG]) with linear amphiphlic PAA-b-PS and all hydrophilic PAA-b-PEG diblock copolymers as side chains, respectively, and cellulose-graft-[poly(4-vinylpyridine)-block-poly(tert-butyl acrylate)-block-polystyrene] (cellulose-g-[P4VP-b-PtBA-b-PS]), cellulose-graft-[poly(4-vinylpyridine)-block-poly(tert-butyl acrylate)-block-poly(ethylene glycol)] (cellulose-g-[P4VP-b-PtBA-b-PEG]), cellulose-graft-[polystyrene-block-poly(acrylic acid)-block-polystyrene] (cellulose-g-[PS-b-PAA-b-PS]) and cellulose-graft-[polystyrene-block-poly(acrylic acid)-block-poly(ethylene glycol)] (cellulose-g-[PS-b-PAA-b-PEG]) with linear amphiphlic P4VP-b-PtBA-b-PS, P4VP-b-PtBA-b-PEG, PS-b-PAA-b-PS and PS-b-PAA-b-PEG triblock copolymers as side chains, respectively. We then exploit these BBCPs as nanoreactors to produce an exciting variety of plain nanorods, core/shell nanorods, and nanotubes of varied diameters and chemical compositions .

Enticing and general strategy for 1D nanocrystals with unprecedented control over dimensions, compositions and architectures using bottlebrush-like block copolymers as nanoreactors

253rd National Meeting (2017)

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