Atom transfer radical polymerization precursors

Ma, Q., and Wooley, K. L. (2000). The preparation of t-butyl acrylate, methyl acrylate, and styrene block copolymers by atom transfer radical polymerization precursors to amphiphilic and hydrophilic block copolymers and conversion to complex nanostructured materials. /. Polym. Sci., Part A Polym. Chem., 3 (Suppl.) 4805-4820. 

Other catalytic reactions involving a transition-metal allenylidene complex, as catalyst precursor or intermediate, include (1) the dehydrogenative dimerization of tributyltin hydride [116], (2) the controlled atom-transfer radical polymerization of vinyl monomers [144], (3) the selective transetherification of linear and cyclic vinyl ethers under non acidic conditions [353], (4) the cycloisomerization of (V2V-dia-llyltosylamide into 3-methyl-4-methylene-(V-tosylpyrrolidine [354, 355], and (5) the reduction of protons from HBF4 into dihydrogen [238]. 

Figure 1 Atom transfer radical polymerization (ATRP) of tert-butyl acrylate for preparation of model radical precursors.

In this review, the term macromer is used to describe oligomer or polymer precursors that undergo reversible association to form supramolecular polymers or networks. Macromer synthesis, although a crucial aspect of supramolecular science, is also out of the scope of this review. Several comprehensive reviews of the synthesis of H-bonding polymers are available [10, 11,42] and primarily describe the application of controlled radical polymerization techniques, including atom-transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and nitroxide-mediated polymerization (NMP). For synthesis of telechelic polymers, avoiding monofunctional impurities that can act as chain stoppers is crucially important [43],... 

Singha et al. reported DA cross-linked products [158] using furan-modified polymethacrylate (PFMA) as the polymeric precursor, which was prepared through atom transfer radical polymerization (ATRP) and free-radical polymerization (FRP). Furthermore, the self-healing behavior of a triblock copolymer (PFMA-co-MMA) prepared by ATRP was demonstrated by means of scanning electron microscopy (SEM). With the modification, an almost fully recovered surface from knife-cut samples has been observed [159]. Chen et al. also reported the DA polymer product of PFMA-BM possessing thermal reversibility, whereas the homopolymer was prepared from anionic polymerization [160]. 

Haas, M., Solari, E., Nguyen, Q.T., Gautier, S., Seopelliti, R., Severin, K, A bimetallic ruthenium complex as a catalyst precursor for the atom transfer radical polymerization of methacrylates at ambient temperature, Adv. Synth. Catal. 2006, 348 439-442. 

L. Z. Qiu, W. Chen, and B. J. Qu, Exfoliation of layered double hydroxide in polystyrene by in-situ atom transfer radical polymerization using initiator-modified precursor. Colloid and Polymer Science, 283 (2005), 1241-5. 

Krzysztof Matyjaszewsld, Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, ESR Study of Radicals in Conventional Radical Polymerization Using Radical Precursors Prepared by Atom Transfer Radical Polymerization (Chapters). 

ESR STUDY OF RADICALS IN CONVENTIONAL RADICAL POLYMERIZATION USING RADICAL PRECURSORS PREPARED BY ATOM TRANSFER RADICAL POLYMERIZATION... 

Kavitha, A.A. and Singha, N.K. (2009) Tailor-made poly(methyl acrylate) bearing amantadine functionality (amino adamanty 1) via atom transfer radical polymerization (ATRP). A precursor of a supramolecular cross-linked polymer. Macromolecules, 42,5499-5508. 

Whenever vinyl monomers are electropolymerized, two situations must be distinguished depending on whether the vinyl monomer is the precursor of the initiating species or not. Either the polymerization is directly initiated by the activated monomer or the initiation is indirect whenever the active species (radical, anion, or cation) is generated by a compound other than the monomer (conducting salt, solvent, or properly selected additives). Besides these electroinitiated polymerization processes, a very recent report also demonstrated that electrochemistry is a valuable tool to mediate atom transfer radical polymerization (ATRP). Indeed, an externally applied electrochemical potential can activate the copper catalyst by a one-electron reduction of an irutially added air-stable cupric species (Cu /ligand) allowing... 

In addition, Cai et al. have proposed a reverse atom transfer radical polymerization (RATRP) approach to prepare end-functionalized PMMA with > and C70 [88]. The Cl-terminated PMMA-Cl as reaction precursor was synthesized through RATRP in the presence of an AlBN/FeCl3/PPh3 initiating system in solution and in bulk, respectively. The polymer was then functionalized with C > or C70 by ATRA using Cu/CuBr/bipy or EeCh/bipy as catalyst to form well-defined PMMA-Cgo. 

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