Poly atom transfer radical

ORl OX w di-Miutyl peroxyoxalalc deactivation by reversible chain transfer and bioinolecular aclivaiion 456 atom transfer radical polymerization 7, 250, 456,457, 458,461.486-98 deactivation by reversible coupling and untmolecular activation 455-6, 457-86 carbon-centered radical-mediated poly nierizaiion 467-70 initiators, inferlers and iriiters 457-8 metal complex-mediated radical polymerization 484... 

Polystyrene-Woc -polysulfone-/ /oc -polystyrene and poly(butyl acrylate)-Woc -polysulfone-/ /oc -poly(butyl acrylate) triblock copolymers were prepared using a macroinitiator.214 The hydroxyl-terminated polysulfone was allowed to react with 2-bromopropionyl bromide, an atomic transfer radical polymerization (ATRP) initiator, in the presence of pyridine. The modified macroinitiator could initiate die styrene polymerization under controlled conditions. 

Block copolymers were synthesized by a combination of fipase-catalyzed polymerization and atom transfer radical polymerization (ATRE). " " At first, the polymerization of 10-hydroxydecanoic acid was carried out by using lipase CA as catalyst. The terminal hydroxy group was modified by the reaction with a-bromopropionyl bromide, followed by ATRP of styrene using CuCE2,2 -bipyridine as catalyst system to give the polyester-polystyrene block copolymer. Trichloromethyl-terminated poly(e-CL), which was synthesized by lipase CA-catalyzed polymerization with 2,2,2-trichloroethanol initiator, was used as initiator for ATRP of styrene. 

Recently, Kong et al. [159] functionalized MWNT with polyacrylic acid (PAA) and poly(sodium 4-styrenesulfonate) (PSS) by surface-initiating ATRP (atom transfer radical polymerization) following the Schemes 1 and 2 ... 

Matyjaszewski et al. [281-285] succeeded in the synthesis of poly(St) with a narrow molecular weight distribution, comparable to the living anionic polymerization, in the atom transfer radical polymerization (ATRP) using Cu complex and alkyl halides (Eq. 74) ... 

Matyjaszewski, K. Miller, P. J. Kickelbick, G. Nakagawa, Y. Diamanti, S. Pacis, C. Organic-Inorganic Hybrid Polymers from Atom Transfer Radical Polymerization and Poly(dimethylsiloxane). In Silicones and Silicone-Modified Materials Clarson, S. J., Fitzgerald, J. J., Owen, M. J., Smith, S. D., Eds. ACS Symposium Series 729 American Chemical Society Washington, DC, 2000 pp 270-283. 

In this review, synthesis of block copolymer brushes will be Hmited to the grafting-from method. Hussemann and coworkers [35] were one of the first groups to report copolymer brushes. They prepared the brushes on siUcate substrates using surface-initiated TEMPO-mediated radical polymerization. However, the copolymer brushes were not diblock copolymer brushes in a strict definition. The first block was PS, while the second block was a 1 1 random copolymer of styrene/MMA. Another early report was that of Maty-jaszewski and coworkers [36] who reported the synthesis of poly(styrene-h-ferf-butyl acrylate) brushes by atom transfer radical polymerization (ATRP). 

Ruthenium(II)-NHC systems ean be used for atom transfer radical polymerization (ATRP). Generally, similar results as for the analogous phosphine complexes are obtained. For the ATRP of styrene and methyl methacrylate (MMA) [(NHC)2peBr2] was found to rival copper(I)-based systems and to yield poly (MMA) with low polydispersities. Polymerizations based on olefin metathesis that are catalyzed by ruthenium-NHC complexes are discussed separately vide supra). 

Becer CR, Paulus RM, Hoppener S et al. (2008) Synthesis of poly(2-ethyl-2-oxazoline)-h-poly(styrene) copolymers via a dual initiator route combining cationic ring opening polymerization and atom transfer radical polymerization. Macromolecules 41 5210-5215... 

Lenoir S, Riva R, Lou X, Detrembleur C, Jerome R, Lecomte P (2004) Ring-opening polymerization of a-chloro- -caprolactone and chemical modification of poly(a-chloro- -caprolactone) by atom transfer radical processes. Macromolecules 37 4055 061... 

In a recent report, new nanocomposites of Au NPs and poly(4-vinylpyridine) were obtained through surface-initiated atom-transfer radical polymerization (SI-ATRP). The citrate-stabilized gold nanoparticles were first modified by the disulfide initiator [BrC(CH3)2COO(CH2)iiS]2 for ATRP initiation, and the subsequent polymerization of 4-vinylpyridine occurred on the surface of the gold particles. The assembled Au PVP nanocomposites are pH-responsive because of the pyridyl groups, which are facially protonated and positively charged. The micrographs show Au N Ps of around 15 nm size [92] (Scheme 3.14). 

The Cu(II)/Cu(I) redox system added as bromide has recently been used to prepare well-defined polymers (controlled molecular weight, reduced poly-dispersity, terminal functionalities). One of the most successful methods to make well-defined polymers is atom transfer radical polymerisation (ATRP)18 ... 

Recently, living radical polymerizations have been well developed, and various methods such as (1) iniferter mediated radical polymerization [31], (2) transition metal-mediated radical polymerization or atom transfer radical polymerization (ATRP) [32-34] (3) nitroxide-mediated free-radical poly-... 

Thermally responsive polymers, such as poly( V-isopropyl acrylamide) (NI-PAm), have also been studied extensively for applications related to those previously discussed [112], De las Heras et al. described the synthesis and patterning of NIPAm brushes on SAMs and their subsequent performance during temperature-dependent adhesion assays of BSA and Streptococcus mutans (Fig. 7). The authors employed p.CP to pattern features of hydrophobic hexadecanethiol and backfilled the surface with an initiator-functionalized alkanethiol. Polymer brushes were grown via surface-initiated atom transfer radical polymerization (ATRP). FITC-BSA was then... 

Furthermore, Fu et al.140 developed a transport system that responds to thermal stimuli. This system is based on chains of poly-iV-isopropylacrylamide (a known thermosensitive polymer), which exists in a collapsed, hydrophobic state when exposed to heat, but in an expanded, hydrophilic state in the cold. In this way, samples of mesoporous, spherical silica particles (particle diameter 10 p,m) that were lined and coated with the thermosensitive polymer by atom transfer radical polymerization... 

In this paper, we first present a model study on blending a a,co-3,5-dinitrobenzoate PDMS and free 9H-carbazole-9-ethanol, in order to check whether the recently proposed 1 1 stoechiometry between carbazole and dinitrobenzoate molecules indeed applies (Scheme 1). [26] Then, we describe the preparation of triblock copolymers, poly[2-(N-carbazolyl)ethyl methacrylate]-fc-PDMS-fc-poly[2-(N-carbazolyl)ethyl methacrylate] (P(CzEMA)-fe-PDMS-fc-P(CzEMA)), using Atom Transfer Radical Polymerization (ATRP), and their blending with the acceptor-functionalized PDMS. In both studies, the physical association and thermal reversibility of these were followed by different techniques, including UV-Vis spectroscopy, DSC or Rheology. 

AFM=atomic force microscopy ATRP=atom transfer radical polymerisation PEO=poly(ethylene oxide)... 

Nakagawa [5] prepared poly(styrene-b-isobutylene) through atom transfer radical polymerization that had good weatherability properties. 

This catalytic sequence is known as Kharasch addition or atom transfer radical addition (ATRA) [4]. Various polyhalogenated compounds such as CCI4 and CCI3CO2R are used as the organic halides, and transition metal salts or complexes are used as the catalyst [3]. Intramolecular version of the Kharasch addition reaction (atom transfer radical cyclization, ATRC) has opened novel synthetic protocols to the synthesis of carbocyde or heterocyles catalyzed by transition metals [5-7], and this has become a very important field in free radical cydization in organic synthesis. Transition metal-catalyzed Kharasch reactions sometimes afford telomers or poly-... 

There are only a few cases in which polyelectrolyte stars have been prepared by the arm-first strategy. Qiao et al. prepared pH responsive poly(acrylic acid) stars by the MI method using atom transfer radical polymerization (ATRP), which was used to form layer-by-layer (LBL) polyelectrolyte multilayers with linear cationic polyelectrolytes [54], Matyjaszewski et al. obtained cationic poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) stars and anionic PAA stars also using the MI method, which formed all-star LBL layers [55], Ishizu et al. obtained... 

Controlled/ Living radical polymerization (CRP) of vinyl acetate (VAc) via nitroxide-mediated polymerization (NMP), organocobalt-mediated polymerization, iodine degenerative transfer polymerization (DT), reversible radical addition-fragmentation chain transfer polymerization (RAFT), and atom transfer radical polymerization (ATRP) is summarized and compared with the ATRP of VAc catalyzed by copper halide/2,2 6 ,2 -terpyridine. The new copper catalyst provides the first example of ATRP of VAc with clear mechanism and the facile synthesis of poly(vinyl acetate) and its block copolymers. 

VAc has been successfully polymerized via controlled/ living radical polymerization techniques including nitroxide-mediated polymerization, organometallic-mediated polymerization, iodine-degenerative transfer polymerization, reversible radical addition-fragmentation chain transfer polymerization, and atom transfer radical polymerization. These methods can be used to prepare well-defined various polymer architectures based on PVAc and poly(vinyl alcohol). The copper halide/t is an active ATRP catalyst for VAc, providing a facile synthesis of PVAc and its block copolymers. Further developments of this catalyst will be the improvements of catalytic efficiency and polymerization control. 

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