Polymer Brushes by Anionic and Cationic Surface-Initiated Polymerization (SIP)

  • Rigoberto AdvinculaEmail author
Part of the Advances in Polymer Science book series (POLYMER, volume 197)


The formation of homopolymer and block copolymer brushes grafted from flat and nanoparticle surfaces via surface-initiated anionic and cationic polymerization methods is reviewed. Unique properties of these chain addition polymerization methods distinguish them from free-radical and living-radical methods, i.e., primarily the formation of charged reactive propagating centers. This involves the use of methods that preserve the reactivity of the charged species, where the monomer, solvent quality, and lack of terminating species allow for grafting to surfaces and for the formation of homopolymer and block copolymers. While these initiators are analogous to solution and bulk methods and adapted to surfaces, their mechanisms do not necessarily follow their counterparts. Several systems for surface-initiated polymerization (SIP) will be reviewed including early attempts at “grafting onto” and “grafting from” particles. For initiation, alkylsilane or alkylthiol anionic initiators are grafted onto planar and particle surfaces by self-assembled monolayer (SAM) techniques. For the cationic (carbocationic) polymerization methods, methods of tethering Lewis acids to surfaces have been reported. The grafted polymer chains can be investigated in situ using a number of surface-sensitive spectroscopic and microscopic techniques. They can also be analyzed ex situ when the polymer chains are removed from the substrate surface. Activation of the grafted initiator, control of polymerization conditions, and removal of excess activators are emphasized. Interesting differences in particle properties, morphology, thickness, grafting density, and polymerization conditions contrast anionic and cationic charged species from other SIP mechanisms. The problems and potential of these techniques will also be discussed. The formation of block copolymer sequences highlights a unique utility of living anionic and cationic polymerization techniques on surfaces.

Anionic Cationic Initiator Nanoparticles Surface initiated polymerization 



Surface-initiated polymerization


Self-assembled monolayers


Molecular weight


Radius of gyration


Living anionic surface-initiated polymerization


Atom-transfer radical polymerization


Ring-opening metathesis polymerization




Reversible addition fragmentation chain transfer


Nuclear magnetic resonance


Gel permeation chromatography


X-ray photoelectron spectroscopy


Atomic force microscopy


Transmission electron microscopy












Quartz crystal microbalance


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I would like to acknowledge my collaborators in this research area: QingYe Zhou, Mi-Kyoung Park, Shuangxi Wang, Jimmy Mays, George Sakellariou, Stergios Pispas, and Nikos Hadjichristidis. I would like to acknowledge the Advincula research group and especially Derek Patton for help in preparing updated references. I would also like to acknowledge technical support from Molecular Imaging (Agilent technologies), Optrel GmBH, and Maxtec Inc.


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Authors and Affiliations

  1. 1.Department of Chemistry and Department of Chemical EngineeringUniversity of HoustonHoustonUSA

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