Controlled/living radical polymerization: Features, developments, and perspectives

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Living Radical Polymerization by the RAFT Process - A Second Update

Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States

Design and Preparation of Porous Polymers

The use of light to mediate controlled radical polymerization has emerged as a powerful strategy for rational polymer synthesis and advanced materials fabrication. This review provides a comprehensive survey of photocontrolled, living radical polymerizations (photo-CRPs). From the perspective of mechanism, all known photo-CRPs are divided into either (1) intramolecular photochemical processes or (2) photoredox processes. Within these mechanistic regimes, a large number of methods are summarized and further classified into subcategories based on the specific reagents, catalysts, etc., involved. To provide a clear understanding of each subcategory, reaction mechanisms are discussed. In addition, applications of photo-CRP reported so far, which include surface fabrication, particle preparation, photoresponsive gel design, and continuous flow technology, are summarized. We hope this review will not only provide informative knowledge to researchers in this field but also stimulate new ideas and applications to further advance photocontrolled reactions.

http://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.5b00671

Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications

Synthesis and optical properties of ZnS:Cu(II) nanoparticles

Metal-free aerobic oxidative coupling of amines to imines

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

Degenerative Transfer and Reversible Termination Mechanisms for Living Radical Polymerizations Mediated by Cobalt Porphyrins

Visible light induced living radical polymerization of a wide scope of acrylates mediated by organocobalt porphyrins was developed. The photocleavage of the Co–C bond of organocobalt porphyrin produced carbon centered radicals, which initiated polymerization, and porphyrin cobalt(II), a persistent metal-centered radical. The organocobalt porphyrins were highly sensitive to external visible light irradiation so that photostimulus was used to control the initiation steps and regulate chain growth by reversibly activating the Co–C bond. Polymerization occurred spontaneously under irradiation and stopped promptly once shutting down light source. The scope of monomers was successfully extended from acrylamides to various hydrophobic and hydrophilic acrylates via the control of the light intensity. The structure of polyacrylate obtained was confirmed by 2D NMR, 13C NMR, GPC, and MALDI-TOF-MS. One of the unique features of this neat visible light induced polymerization process is that organocobalt porphyrins pla...

Xuefeng Fu

Papers

Synthesis and optical properties of ZnS:Cu(II) nanoparticles

Metal-free aerobic oxidative coupling of amines to imines

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

Degenerative Transfer and Reversible Termination Mechanisms for Living Radical Polymerizations Mediated by Cobalt Porphyrins

Visible Light Induced Living/Controlled Radical Polymerization of Acrylates Catalyzed by Cobalt Porphyrins