Radical addition-fragmentation chemistry in polymer synthesis
TL;DR: In this paper, a review of the development of addition-fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas is presented, including dithioesters, trithiocarbonates, dithioco-baramates and xanthates.
About: This article is published in Polymer.The article was published on 2008-03-03 and is currently open access. It has received 1309 citations till now. The article focuses on the topics: Reversible addition−fragmentation chain-transfer polymerization & Degenerative chain transfer.
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TL;DR: The current status and future perspectives in atom transfer radical polymerization (ATRP) are presented in this paper, with a special emphasis on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP.
Abstract: Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.
2,188 citations
TL;DR: A comprehensive overview of recent progress on the production and modification of polyvinylidene fluoride (PVDF) membranes for liquid-liquid or liquid-solid separation can be found in this article.
1,776 citations
TL;DR: The authors 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.
Abstract: 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.
1,612 citations
TL;DR: This review covers the principles, advantages, and drawbacks of passive and active targeting based on various polymer and magnetic iron oxide nanoparticle carriers with drug attached by both covalent and noncovalent pathways.
Abstract: Targeted delivery combined with controlled drug release has a pivotal role in the future of personalized medicine. This review covers the principles, advantages, and drawbacks of passive and active targeting based on various polymer and magnetic iron oxide nanoparticle carriers with drug attached by both covalent and noncovalent pathways. Attention is devoted to the tailored conjugation of targeting ligands (e.g., enzymes, antibodies, peptides) to drug carrier systems. Similarly, the approaches toward controlled drug release are discussed. Various polymer–drug conjugates based, for example, on polyethylene glycol (PEG), N-(2-hydroxypropyl)methacrylamide (HPMA), polymeric micelles, and nanoparticle carriers are explored with respect to absorption, distribution, metabolism, and excretion (ADME scheme) of administrated drug. Design and structure of superparamagnetic iron oxide nanoparticles (SPION) and condensed magnetic clusters are classified according to the mechanism of noncovalent drug loading involving...
1,241 citations
TL;DR: Catalytic Solvents: Catalyst Disproportionation 4981 2.2.1.
Abstract: 2.1.6. Tacticity and Sequence: Advanced Control 4967 2.2. Transition Metal Catalysts 4967 2.2.1. Overviews of Catalysts 4967 2.2.2. Ruthenium 4967 2.2.3. Copper 4971 2.2.4. Iron 4971 2.2.5. Nickel 4975 2.2.6. Molybdenum 4975 2.2.7. Manganese 4976 2.2.8. Osmium 4976 2.2.9. Cobalt 4976 2.2.10. Other Metals 4976 2.3. Cocatalysts (Additives) 4977 2.3.1. Overview of Cocatalysts 4977 2.3.2. Reducing Agents 4977 2.3.3. Free Radical Initiators 4977 2.3.4. Metal Alkoxides 4977 2.3.5. Amines 4978 2.3.6. Halogen Source 4978 2.4. Initiators 4978 2.4.1. Overview of Initiators: Scope and Design 4978 2.4.2. Alkyl Halides 4978 2.4.3. Arenesulfonyl Halides 4979 2.4.4. N-Chloro Compounds 4979 2.4.5. Halogen-Free Initiators 4979 2.5. Solvents 4980 2.5.1. Overview of Solvents 4980 2.5.2. Catalyst Solubility and Coordination of Solvent 4981 2.5.3. Environmentally Friendly Solvents 4981 2.5.4. Water 4981 2.5.5. Catalytic Solvents: Catalyst Disproportionation 4981
1,131 citations
References
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TL;DR: The authors proposed a reversible additive-fragmentation chain transfer (RAFT) method for living free-radical polymerization, which can be used with a wide range of monomers and reaction conditions and in each case it provides controlled molecular weight polymers with very narrow polydispersities.
Abstract: mechanism involves Reversible Addition-Fragmentation chain Transfer, and we have designated the process the RAFT polymerization. What distinguishes RAFT polymerization from all other methods of controlled/living free-radical polymerization is that it can be used with a wide range of monomers and reaction conditions and in each case it provides controlled molecular weight polymers with very narrow polydispersities (usually <1.2; sometimes <1.1). Living polymerization processes offer many benefits. These include the ability to control molecular weight and polydispersity and to prepare block copolymers and other polymers of complex architecturesmaterials which are not readily synthesized using other methodologies. Therefore, one can understand the current drive to develop a truly effective process which would combine the virtues of living polymerization with versatility and convenience of free-radical polymerization.2-4 However, existing processes described under the banner “living free-radical polymerization” suffer from a number of disadvantages. In particular, they may be applicable to only a limited range of monomers, require reagents that are expensive or difficult to remove, require special polymerization conditions (e.g. high reaction temperatures), and/or show sensitivity to acid or protic monomers. These factors have provided the impetus to search for new and better methods. There are three principal mechanisms that have been put forward to achieve living free-radical polymerization.2,5 The first is polymerization with reversible termination by coupling. Currently, the best example in this class is alkoxyamine-initiated or nitroxidemediated polymerization as first described by Rizzardo et al.6,7 and recently exploited by a number of groups in syntheses of narrow polydispersity polystyrene and related materials.4,8 The second mechanism is radical polymerization with reversible termination by ligand transfer to a metal complex (usually abbreviated as ATRP).9,10 This method has been successfully applied to the polymerization of various acrylic and styrenic monomers. The third mechanism for achieving living character is free-radical polymerization with reversible chain transfer (also termed degenerative chain transfer2). A simplified mechanism for this process is shown in
4,561 citations
TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.
2,869 citations
TL;DR: A review of living radical polymerization achieved with thiocarbonylthio compounds by a mechanism of reversible addition-fragmentation chain transfer (RAFT) is presented in this article.
Abstract: This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.
2,127 citations
26 Jul 2002
TL;DR: Krzysztof Matyjaszewski and Thomas P. Davis as discussed by the authors discussed the fundamental concepts and history of living radical polymers and their application in industrial applications and processes.
Abstract: Introduction (Krzysztof Matyjaszewski and Thomas P. Davis). Contributors. 1. Theory of Radical Reactions (Johan P. A. Heuts). 2. Small Radical Chemistry (Martin Newcomb). 3. General Chemistry of Radical Polymerization (Bunichiro Yamada and Per B. Zetterlund). 4. The Kinetics of Free Radical Polymerization (Christopher Barner-Kowollik, Philipp Vana, and Thomas P. Davis). 5. Copolymerization Kinetics (Michelle L. Coote and Thomas P. Davis). 6. Heterogeneous Systems (Alex M. van Herk and Michael Monteiro). 7. Industrial Applications and Processes (Michael Cunningham and Robin Hutchinson). 8. General Concepts and History of Living Radical Polymerization (Krzysztof Matyjaszewski). 9. Kinetics of Living Radical Polymerization (Takeshi Fukuda, Atsushi Goto, and Yoshinobu Tsujii). 10. Nitroxide Mediated Living Radical Polymerization (Craig J. Hawker). 11. Fundamentals of Atom Transfer Radical Polymerization (Krzysztof Matyjaszewski and Jianhui Xia). 12. Control of Free Radical Polymerization by Chain Transfer Methods (John Chiefari and Ezio Rizzardo). 13. Control of Stereochemistry of Polymers in Radical Polymerization (Akikazu Matsumoto). 14. Macromolecular Engineering by Controlled Radical Polymerization (Yves Gnanou and Daniel Taton). 15. Experimental Procedures and Techniques for Radical Polymerization (Stefan A. F. Bon and David M. Haddleton). 16. Future Outlook and Perspectives (Krzysztof Matyjaszewski and Thomas P. Davis). Index.
1,407 citations
1,364 citations