Atom transfer radical polymerization methacrylate

In 2003, the van Hest group produced elastin-based side-chain polymers [123]. This research was motivated by the demonstration of the occurrence of an inverse temperature transition in a single repeat of VPGVG [124]. A methacrylate-functionalized VPGVG was synthesized and used as a monomer to perform atom transfer radical polymerization (ATRP) to produce homopolymers (Fig. 16b) or... 

Ejaz, M., Yamamoto, S., Ohno, K., Tsujii, Y. and Fukuda, T. (1998) Controlled graft polymerization of methyl methacrylate on silicon substrate by the combined use of the Langmuir-Blodgett and atom transfer radical polymerization techniques. Macromolecules, 31, 5934-5936. 

Qin, S., et al., Polymer brushes on single-walled carbon nanotubes by atom transfer radical polymerization ofn-butyl methacrylate. Journal of the American Chemical Society, 2003. 126(1) p. 170-176. 

The last decades have witnessed the emergence of new living Vcontrolled polymerizations based on radical chemistry [81, 82]. Two main approaches have been investigated the first involves mediation of the free radical process by stable nitroxyl radicals, such as TEMPO while the second relies upon a Kharash-type reaction mediated by metal complexes such as copper(I) bromide ligated with 2,2 -bipyridine. In the latter case, the polymerization is initiated by alkyl halides or arenesulfonyl halides. Nitroxide-based initiators are efficient for styrene and styrene derivatives, while the metal-mediated polymerization system, the so called ATRP (Atom Transfer Radical Polymerization) seems the most robust since it can be successfully applied to the living Vcontrolled polymerization of styrenes, acrylates, methacrylates, acrylonitrile, and isobutene. Significantly, both TEMPO and metal-mediated polymerization systems allow molec-... 

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). 

Zhang H, Fijten MWM, Hoogenboom R, Schubert US (2003) Atom-transfer radical polymerization of methyl methacrylate utilizing an automated synthesizer. ACS Symp Ser 854 193-205... 

Fig. 2 Effects of metal salts, ligands, and initiators on Cmma (s)> / (b), PDls (c) of the polymers in the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p-xylene at 90°C. [MMA]o [initiator]o [metal salt]o [ligand]o = 150 1 1 2, MMA/p —xylene = l 2v/v. EBIB, MBP, BEB, and TsCl were used as initiator from right to left in each ligand column, respectively (Reprinted with permission from [34]. Copyright (2004) John Wiley Sons, Inc.)...

The ruthenium indenylidene Schiff base complexes XXVIIIa and XXVIIId, synthesized by Verpoort, were evaluated in atom-transfer radical polymerization of methyl methacrylate. The polymerization was initiated by ethyl 2-bromo-2-methyl-... 

Indenylidene compounds VIII, K, XXI, XXIII, XXVIIIa and XXVIIIb act as atom transfer radical polymerization catalysts for the polymerization of methyl methacrylate and styrene in high yields and with good control (Table 8.7). The catalytic activity can be dramatically improved by transforming the complexes into cationic species by treatment with AgBp4 [61]. 

Controlled free-radical polymerization methods, like atom-transfer radical polymerization (ATRP), can yield polymer chains that have a very narrow molecular-weight distribution and allow the synthesis of block copolymers. In a collaboration between Matyjaszewski and DeSimone (Xia et al., 1999), ATRP was performed in C02 for the first time. PFOMA-/)-PMMA, PFOMA-fr-PDMAEMA [DMAEMA = 2-(dimethylamino)ethyl methacrylate], and PMMA-/)-PFOA-/)-PM M A copolymers were synthesized in C02 using Cu(0), CuCl, a functionalized bipyridine ligand, and an alkyl halide initiator. The ATRP method was also conducted as a dispersion polymerization of MMA in C02 with PFOA as the stabilizer, generating a kine-... 

Louie and Grubbs prepared an iron-based catalyst for atom transfer radical polymerization (ATRP) [49]. By heating a solution of Iz Prim and FeX2 (X = Br, Cl), crystals of Fe(Iz Prim)2X2 were obtained. These complexes mediated the homogeneous ATRP of styrene and methyl methacrylate with... 

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. 

Zeng F, Shen Y, Zhu S, Pelton R. (2000) Synthesis and Characterization of Comb-Branched Polyelectrolytes. 1. Preparation of Cationic Macromonomer of 2-(Dimethylamino)ethyl Methacrylate by Atom Transfer Radical Polymerization. Macromolecules 33 1628-1635. 

Pansier [2] used the bromomethyl analogue, (II), of the Step 2 product in the atom transfer radical polymerization of methyl methacrylate. Lewandowski [3] prepared the tribromomethyl analogue, (111), by reacting with trimethylolpro-pane and then used this reagent to prepare methyl methacrylate star polymers. A reaction profile is provided in Table 3. 

Figure 33 Surface initiated block copolymerization of styrene and methyl methacrylate through atom transfer radical polymerization ...

Three key conditions must be met to design a uniformly reactive, recoverable, and recyclable polymerization catalyst (1) the synthetic protocol used to make the immobilized catalyst must lead to only one type of active site on the surface, (2) the support material must be able to allow sufficient transport of reactants to and polymer from the active site, and (3) at the end of the reaction, the active site must not be irreversibly changed or decomposed [23]. Research in our lab has thus far sought to investigate these points using the atom transfer radical polymerization (ATRP) of methyl methacrylate as a model reaction. 

Nguyen JV, Jones CW (2004) Effect of the synthetic method and support porosity on the structure and performance of sihca-supported CuBr/pyridyhnethanimine atom transfer radical polymerization catalysts. 11. Polymerization of methyl methacrylate. J Polym Sci. Part A 42 1384... 

Recently diblock copolymers of PEG and ionic segments were prepared by atom-transfer radical polymerization of methacrylic aminoester using a monofunctionalized PEG macroinitiator and then subsequent quaternization. Like others [60] these polymers form so called polyion complex micelles by electrostatic interaction with oppositely charged molecules (e.g. drugs, oligonucleotides), where the PEG block acts as a steric stabilizer [67]. 

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