The atom transfer radical polymerization (ATRP) of styrene and acrylates from silicon wafers modified with an initiator layer composed of 2-bromoisobutyrate fragments is described. In the presence of the proper ratio of activating and deactivating transition-metal species, controlled radical polymerizations of styrene were observed such that the thickness of the layer consisting of chains grown from the surface increased linearly with the molecular weight of chains polymerized in solution in identical, yet separate, experiments. The layer thickness increased linearly with reaction time for ATRP of styrene and methyl acrylate due to both the extremely low initiator concentration relative to monomer and the low monomer conversion. Further evidence for control was observed by the polymerization of blocks of either methyl or tert-butyl acrylate from the polystyrene layer. Modification of the hydrophilicity of the surface layer was achieved by hydrolysis of the poly(styrene-b-tert-butyl acrylate) to poly(styrene-b-acrylic acid) and confirmed by decrease in water contact angle from 86° to 18°. The mechanistic aspects of ATRP in the polymerization process were confirmed by the growth of very thick polystyrene films in the presence of a pure copper(I) complex. Since no deactivator was present, the metal complex served only to facilitate initiation by a redox process. Attempts to extend chain with methyl acrylate under controlled conditions were unsuccessful in those films. The simulation of polymerization of surface layers suggests broader molecular weight and chain end distributions, confirming XPS results on the progressive decrease of Br absorption intensity.

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Multifunctional initiators, derived from cyclotriphosphazenes, cyclosiloxanes, and organic polyols, were used in the synthesis of styrenic and (meth)acrylic star polymers by atom transfer radical polymerization (ATRP). Conditions were identified in each system which provided linear first-order kinetics for polymers with narrow, monomodal molecular weight distributions. Molecular weight measurements relative to linear polystyrene standards showed that the star polymers had lower molecular weights than theoretically predicted. Triple detection SEC measured on poly(n-butyl acrylate) samples demonstrated that the absolute molecular weight matched the theoretical valuethe smaller relative chain length was due to lower hydrodynamic volumes of the star-branched polymers relative to linear analogues. Kinetic arguments were used to demonstrate that each alkyl halide moiety bound to the initiators was participating in ATRP. Well-defined poly(methyl acrylate) stars of molecular weights M n > 500 000 and low polydispersity (M w/M n < 1.2) have been prepared. Star−block copolymers with a soft poly(methyl acrylate) core and a hard poly(isobornyl acrylate) shell were also synthesized.

Immobilization of the catalyst system for atom transfer radical polymerization (ATRP) on various silica and cross-linked polystyrene supports was studied. The catalyst system comprises a copper halide, complexed by various amines. The effect of size of support particles, the amount of immobilized catalyst, and the addition of Cu(II) species as deactivator in the polymerization were investigated. In all cases, polymerization occurred, but generally the reactions were not as well controlled in terms of molecular weight and polydispersities as homogeneous systems. The molecular weights did not match the predicted values, and polydispersities were high (1.5 < M w/M n < 10). However, control was improved by either an increase in catalyst concentration or the addition of deactivator still bound to support to the system. Potential reasons for the reduced control could be the low mobility of the supported catalyst and/or the steric hindrance and incompatibilities between the immobilized catalyst and the polymer chain, thus resulting in a less efficient halogen transfer process compared with homogeneous ATRP.