Atom-transfer radical polymerization (ATRP) is one of the controlled/living radical polymerizations yielding well-defined (co)polymers, nanocomposites, molecular hybrids, and bioconjugates. ATRP, as in any radical process, has to be carried out in rigorously deoxygenated systems to prevent trapping of propagating radicals by oxygen. Herein, we report that ATRP can be performed in the presence of limited amount of air and with a very small (typically ppm) amount of copper catalyst together with an appropriate reducing agent. This technique has been successfully applied to the preparation of densely grafted polymer brushes, poly(n-butyl acrylate) homopolymer, and poly(n-butyl acrylate)-block-polystyrene copolymer from silicon wafers (0.4 chains/nm2). This simple new method of grafting well-defined polymers does not require any special equipment and can be carried out in vials or jars without deoxygenation. The grafting for "everyone" technique is especially useful for wafers and other large objects and may be also applied for molecular hybrids and bioconjugates.

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Surface-initiated atom transfer radical polymerization (SI-ATRP) has become an indispensable tool for engineering the structure and properties of polymer/inorganic and polymer/organic interfaces. This article describes the progress and challenges that are associated with the application of SI-ATRP to precisely control the molecular characteristics of polymer chains tethered to nanoparticle surfaces and explores the properties and potential applications of the resulting particle brush materials. Even for the conceptually most “simple” particle brush systemsthat is, spherical particles uniformly grafted with amorphous nonpolar polymersthe complex superposition of interactions as well as time- and length-scales related to particle core and tethered chains provides a rich and largely unexplored parameter space for the design of novel functional materials. The application of the particle brush approach to the development of materials for applications ranging from photonic inks and paints to advanced high “k” dielectrics for energy storage and advanced nanocomposite materials with improved optical, mechanical, or transport characteristics is discussed.

The effect of polymer-graft modification on the structure formation and mechanical characteristics of inorganic (silica) nanoparticle solids is evaluated as a function of the degree of polymerization of surface-grafted chains. A transition from 'hard-sphere-like' to 'polymer-like' mechanical characteristics of particle solids is observed for increasing degree of polymerization of grafted chains. The elastic modulus of particle solids increases by about 200% and levels off at intermediate molecular weights of surface-grafted chains, a trend that is rationalized as a consequence of the elastic modulus being determined by dispersion interactions between the polymeric grafts. A pronounced increase (of about one order of magnitude) of the fracture toughness of particle solids is observed as the degree of polymerization of grafted chains exceeds a threshold value that is similar for both polystyrene and poly(methyl methacrylate) grafts. The increased resistance to fracture is interpreted as a consequence of the existence of entanglements between surface-grafted chains that give rise to energy dissipation during fracture through microscopic plastic deformation and craze formation. Within the experimental uncertainty the transition to polymer-like deformation characteristics is captured by a mean field scaling model that interprets the structure of the polymer shell of polymer-grafted particles as effective 'two-phase' systems consisting of a stretched inner region and a relaxed outer region. The model is applied to predict the minimum degree of polymerization needed to induce polymer-like mechanical characteristics and thus to establish 'design criteria' for the synthesis of polymer-modified particles that are capable of forming mechanically robust and formable particle solid structures.

Dual responsive molecular brushes consisting of statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO 2 MA) and either methacrylic acid (MAA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) were synthesized by grafting from poly(2-(2-bromoisobutyroyloxy)ethyl methacrylate (PBIEM) macroinitiators using atom transfer radical polymerization (ATRP). Copolymer brushes with controlled composition and molecular weights ranging from M n ) 600 000 to 1 400 000 with polydispersity indexes (M w /M n ) between 1.18 and 1.45 were obtained. The lower critical solution temperature (LCST) of MEO 2 MA-stat-MAA decreased with the increasing molar fraction of MAA in the copolymer in deionized water but increased in buffer solution at pH 7. At pH 9, the hydrophilicity of polymer increased with ionization of carboxylic acid to further raise the LCST. On the other hand, the LCST of MEO 2 MA-stat-DMAEMA copolymers increased with increasing DMAEMA content at pH 4, 7, and 9. A bottle-brush terpolymer prepared from all three comonomers exhibited LCST at pH 4 and 7 but not at pH 9, which can be attributed to the stronger ionization of MAA. The responsive nature of the copolymer is enhanced by the densely graft structure of a brush copolymer.

Molecular brushes consisting of statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO 2 MA) and tri(ethylene glycol) methyl ether methacrylate (MEO 3 MA) were synthesized by grafting from poly(2-(2-bromoisobutyryloxy)ethyl methacrylate (PBIEM) macroinitiators using atom transfer radical polymerization (ATRP) providing copolymers with controlled composition and molecular weights ranging from M n ) 601 500 to 2 731 000 with polydispersity indexes (M w /M n ) between 1.06 and 1.20. The lower critical solution temperature (LCST) of the brushes increased with the mole fraction of MEO 3 MA in the side chain, and the hysteresis between the heating and cooling cycles decreased with the length of the side chain. Brush copolymers with different graft density were also prepared, and the average hydrodynamic diameter, measured by dynamic light scattering (DLS), varied with temperature above the LCST, and the maximum diameter of the aggregates increased according to the graft density of side chain along the brush backbone. These two monomers were also incorporated into side chain block copolymer brushes by ATRP. The cloud point of the block brushes solution displayed two stages of aggregation during heating, exhibiting the results of both intermolecular and intramolecular aggregation. This behavior was strongly dependent on the sequence of the side chain segments. As the temperature increased, particles consisting of collapsed PMEO 2 MA and PMEO 3 MA segments aggregated upon further heating to precipitate as larger particles.

Statistical copolymers of di(ethylene glycol) methyl ether methacrylate (MEO2MA) and tri(ethylene glycol) methyl ether methacrylate (MEO3MA) were synthesized by atom transfer radical polymerization (ATRP) providing copolymers with controlled composition and molecular weights ranging from Mn = 8,300–56,500 with polydispersity indexes (Mw/Mn) between 1.19 and 1.28. The lower critical solution temperature (LCST) of the copolymers increased with the mole fraction of MEO3MA in the copolymer over the range from 26 to 52 °C. The average hydrodynamic diameter, measured by dynamic light scattering, varied with temperature above the LCST. These two monomers were also block copolymerized by ATRP to form polymers with molecular weight of Mn = 30,000 and Mw/Mn from 1.12 to 1.21. The LCST of the block copolymers shifted toward the LCST of the major segment, as compared to the value measured for the statistical copolymers at the same composition. As temperature increased, micelles, consisting of aggregated PMEO2MA cores and PMEO3MA shell, were formed. The micelles aggregated upon further heating to precipitate as larger particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 194–202, 2008

The propensity of particle brush materials to form long-ranged ordered assembly structures is shown to sensitively depend on the brush architecture (i.e., the particle radius as well as molecular weight and grafting density of surface-bound chains). In the limit of stretched chain conformations of surface-grafted chains the formation of regular particle array structures is observed and interpreted as a consequence of hard-sphere-type interactions between polymer-grafted particles. As the degree of polymerization of surface-grafted chains increases beyond a threshold value, a reduction of the structural regularity is observed that is rationalized with the increased volume occupied by relaxed polymer segments. The capacity of polymer grafts to increase or decrease order in particle brush assembly structures is interpreted on the basis of a mean-field scaling model, and "design criteria" are developed to help guide the future synthesis of colloidal systems that are capable of forming mechanically robust yet ordered assembly structures.