that have been made in living polymerization methodologies during the last decade, especially those based on free-radical polymerizations, will open up the arena
to a much wider range of functional monomers than was ever possible during the
anionic polymerization era. In spite of the relatively poorer control over the molecular weight (and polydispersity), the simplicity of many of these controlled freeradical polymerizations and their unparalleled tolerance to functional groups, will
serve to propel these approaches to the fore, as the method of choice for generating
nanostructured polymeric materials. Conjugated polymers have seen a resurgence
of activity due to many new exciting properties, such as photoluminescence, electroluminescence, lasing etc. By virtue of being intrinsically rigid rod-like entities,
block copolymers based on conjugated polymers will continue to provide exciting
prospects for the development of nanostructured systems with novel and exciting
properties. Bicontinuous morphologies, using such conjugated rod–coil block copolymers, for instance, could serve as ideal systems for photovoltaic applications.
Polymerization of pre-organized entities, be it surfactant assemblies or block copolymer assemblies, is clearly an elegant way to construct permanent macromolecular objects, with wide-ranging sizes and shapes. Although impressive strides
have been taken in this approach, the basic building blocks, both block copolymers
and polymerizable surfactants, are still expensive and difficult to access. In this
context, the confinement of simple monomers, by selective partitioning within selected domains of surfactant assemblies and their subsequent polymerization, offers unique opportunities that could combine both the richness of structural variety and simplicity. Clearly greater understanding of the fundamental factors that
govern the selective partitioning of monomers and retention of morphology after
polymerization is needed before this approach becomes mature and of wider utility.
The richness and excitement of understanding and applying the fundamental
principles that govern organization from the atomic scale to the macroscopic one,
specifically in relation to polymeric systems, is what I hope this chapter will have
conveyed. It is evident that many milestones, such as the structural control of
polymer molecules using ‘‘living’’ polymerization methods, methodologies for
block copolymer preparation with precisely controllable block sizes, predictable
control of morphological features in block copolymer systems etc., have been
crossed. Armed with these successes, scientists are now free to explore and exploit
the structural and functional variety to create new polymeric systems with potentially exciting properties, both the expected and the as yet unseen.
Acknowledgements
The help of many of my students and coworkers, G. Padmanaban, Geeta Kheter
Paul and Arun Prasath, in retrieving references and figures is gratefully acknowledged.
15 Nanostructured Polymers
514
to a much wider range of functional monomers than was ever possible during the
anionic polymerization era. In spite of the relatively poorer control over the molecular weight (and polydispersity), the simplicity of many of these controlled freeradical polymerizations and their unparalleled tolerance to functional groups, will
serve to propel these approaches to the fore, as the method of choice for generating
nanostructured polymeric materials. Conjugated polymers have seen a resurgence
of activity due to many new exciting properties, such as photoluminescence, electroluminescence, lasing etc. By virtue of being intrinsically rigid rod-like entities,
block copolymers based on conjugated polymers will continue to provide exciting
prospects for the development of nanostructured systems with novel and exciting
properties. Bicontinuous morphologies, using such conjugated rod–coil block copolymers, for instance, could serve as ideal systems for photovoltaic applications.
Polymerization of pre-organized entities, be it surfactant assemblies or block copolymer assemblies, is clearly an elegant way to construct permanent macromolecular objects, with wide-ranging sizes and shapes. Although impressive strides
have been taken in this approach, the basic building blocks, both block copolymers
and polymerizable surfactants, are still expensive and difficult to access. In this
context, the confinement of simple monomers, by selective partitioning within selected domains of surfactant assemblies and their subsequent polymerization, offers unique opportunities that could combine both the richness of structural variety and simplicity. Clearly greater understanding of the fundamental factors that
govern the selective partitioning of monomers and retention of morphology after
polymerization is needed before this approach becomes mature and of wider utility.
The richness and excitement of understanding and applying the fundamental
principles that govern organization from the atomic scale to the macroscopic one,
specifically in relation to polymeric systems, is what I hope this chapter will have
conveyed. It is evident that many milestones, such as the structural control of
polymer molecules using ‘‘living’’ polymerization methods, methodologies for
block copolymer preparation with precisely controllable block sizes, predictable
control of morphological features in block copolymer systems etc., have been
crossed. Armed with these successes, scientists are now free to explore and exploit
the structural and functional variety to create new polymeric systems with potentially exciting properties, both the expected and the as yet unseen.
Acknowledgements
The help of many of my students and coworkers, G. Padmanaban, Geeta Kheter
Paul and Arun Prasath, in retrieving references and figures is gratefully acknowledged.
15 Nanostructured Polymers
514