Synthesis of Well-Defined Block Copolymers Tethered to Polysilsesquioxane Nanoparticles and Their Nanoscale Morphology on Surfaces

Pyun, Jeffrey; Matyjaszewski, Krzysztof; Kowalewski, Tomasz; Savin, Daniel A.; Patterson, G. D.; Kickelbick, Guido; Huesing, Nicola

doi:10.1021/ja010241m

Cited by 177 publications

(166 citation statements)

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“…[8,9,18,103] Brushes were grown by surface-initiated ATRP, from organic latex colloids emulsions, [43][44][45]47,[104][105][106] shells of shell-crosslinked micelles [107,108] and from functionalized inorganic particles, such as silica, [8,9,18,[33][34][35][37][38][39]42,76,81,99,100,103,[109][110][111][112] gold, [41,113] alumina, [114] polysilsesquioxane, [36] titanium oxide clusters, [40,115] iron oxides [116] and germanium. [117] Herein we focus on the ATRP synthesis of spherical brushes from functionalized nanoparticles serving as colloidal initiators.…”

Section: Polymer Brushes From Particlesmentioning

confidence: 99%

“…Polysilsesquioxane-graft-(polystyrene-block-poly(benzyl acrylate)) (SiO 1.5 -g-(pS-b-pBzA)) hybrid nanoparticles with approximately 1 000 grafted chains were prepared by ATRP. [36] Spherical block copolymer brushes were also prepared from 2-bromoisobutyrate functional silica colloids (D eff ¼ 20 nm) using various combinations of Sty, MMA and BA. [118] For block copolymer brushes from SiO 1.5 or SiO 2 cores, destruction of the interior and recovery of cleaved [37] copolymers enabled evaluation of molar mass and polydispersity using SEC.…”

Section: Multilayered Core-shell Colloidsmentioning

confidence: 99%

“…The variation of polymer-brush composition and degree of polymerization (DP) using ATRP has been extensively investigated to modify surface properties, [10,18,19] nanopattern [20,21] and design stimuli-responsive materials. [22][23][24][25] ATRP of various monomers from preformed polymeric, [26][27][28][29][30][31][32] or colloidal initiators [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] has been achieved yielding nano-objects of precise dimension and functionality. The characterization of nanoscale features in these materials was performed by various techniques.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Polymer Brushes Using Atom Transfer Radical Polymerization

Pyun

Kowalewski

Matyjaszewski

2003

Macromol. Rapid Commun.

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684

591

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Atom transfer radical polymerization (ATRP) is a robust method for the preparation of well‐defined (co)polymers. This process has also enabled the preparation of a wide range of polymer brushes where (co)polymers are covalently attached to either curved or flat surfaces. In this review, the general methodology for the synthesis of polymer brushes from flat surfaces, polymers and colloids is summarized focusing on reports using ATRP. Additionally, the morphology of ultrathin films from polymer brushes is discussed using atomic force microscopy (AFM) and other techniques to confirm the formation of nanoscale structure and organization.Formation of polymer brushes by ATRP.magnified imageFormation of polymer brushes by ATRP.

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Section: Polymer Brushes From Particlesmentioning

confidence: 99%

Section: Multilayered Core-shell Colloidsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Polymer Brushes Using Atom Transfer Radical Polymerization

Pyun

Kowalewski

Matyjaszewski

2003

Macromol. Rapid Commun.

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684

591

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“…There have been several attempts to remove and recycle the catalyst efficiently by extraction, precipitation, immobilization, or by using biphasic systems. [24][25][26][27][28][29][30] However, there is always some loss of polymerization control in biphasic systems or added cost associated with catalyst preparation.…”

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confidence: 99%

Activators Regenerated by Electron Transfer for Atom‐Transfer Radical Polymerization of (Meth)acrylates and Related Block Copolymers

2006

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Atom-transfer radical polymerization (ATRP) is a controlled or living radical polymerization (CRP) technique [1,2] that enables the preparation of new nanostructured materials that are not accessible by conventional free-radical polymerization (FRP). Reported herein is the ATRP of polar monomers such as (meth)acrylates and related block copolymers by means of a new initiating/catalytic method based on activators regenerated by electron transfer (ARGET) with ppm (10 À4 mol % vs. monomer) amounts of Cu catalyst. [3] ATRP [4][5][6][7] provides a simple route to many well-defined (co)polymers with precisely controlled functionalities, topologies, and compositions. [8][9][10] It has been very successfully applied to the preparation of many nanocomposites, hybrids, and bioconjugates. [11][12][13][14][15][16][17][18][19][20][21][22][23] The advantages of ATRP, in comparison with other CRP processes, include the large range of available monomers and (macro)initiators, the simplicity of reaction setup, and the ability to conduct the process over a large range of temperatures, solvents, and dispersed media. [6,7,24] ATRP (Scheme 1) is a repetitive atom-transfer process between a macromolecular alkyl halide P n ÀX and a redoxactive transition-metal complex Cu I ÀX/ligand in which P n C radicals propagate (rate constant of propagation k p ) and are reversibly formed (rate constants k a and k da ). The growing radicals also terminate by coupling or disproportionation (rate constant k t ).An inherent feature, but also a limitation of ATRP, is the presence of a catalyst (a transition-metal complex with Scheme 1. Mechanism for ATRP.

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“…27 It also has been proved to be an excellent tool to introduce organic (co) polymers with precise molar mass, composition, and functionality onto nanoparticles. 28,29 Recently, organic polymer chains graed from particles by using SI-ATRP have been used as carbon precursors to prepare mesocarbon materials.…”

mentioning

confidence: 99%