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.

/pdf/living-radical-polymerization-by-the-raft-process-qf42rfce4m.pdf

Living radical polymerization by the RAFT process

Molecular imprinting technology (MIT) concerns formation of selective sites in a polymer matrix with the memory of a template. Recently, molecularly imprinted polymers (MIPs) have aroused extensive attention and been widely applied in many fields, such as solid-phase extraction, chemical sensors and artificial antibodies owing to their desired selectivity, physical robustness, thermal stability, as well as low cost and easy preparation. With the rapid development of MIT as a research hotspot, it faces a number of challenges, involving biological macromolecule imprinting, heterogeneous binding sites, template leakage, incompatibility with aqueous media, low binding capacity and slow mass transfer, which restricts its applications in various aspects. This critical review briefly reviews the current status of MIT, particular emphasis on significant progresses of novel imprinting methods, some challenges and effective strategies for MIT, and highlighted applications of MIPs. Finally, some significant attempts in further developing MIT are also proposed (236 references).

http://ir.yic.ac.cn/bitstream/133337/4853/1/Recent%20advances%20in%20molecular%20imprinting%20technology%20current%20status%2c%20challenges%20and%20highlighted%20applications.pdf

Recent advances in molecular imprinting technology: current status, challenges and highlighted applications

Radical addition-fragmentation chemistry in polymer synthesis

Molecular imprinting science and technology: a survey of the literature for the years up to and including 2003

This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.

50th Anniversary Perspective: RAFT Polymerization—A User Guide

HP‐RAFT: A Free‐Radical Polymerization Technique for Obtaining Living Polymers of Ultrahigh Molecular Weights

Telechelic high molecular weight polystyrene (PS-A) and poly(methyl methacrylate) (PMMA-A) containing anthracene end groups undergo end-coupling reaction in THF solution to form [4 + 4] anthracene ...

Synthesis and Thin Film Characterization of Poly(styrene-block-methyl methacrylate) Containing an Anthracene Dimer Photocleavable Junction Point

A model system for the characterization of molecular recognition events in molecularly imprinted polymers (MIPs) is presented. The use of a biologically inspired, three-point hydrogen-bonding motif and a thin film polymeric matrix allows for pre- and post-polymerization binding properties to be characterized by infrared spectroscopy. A method to determine binding constants was developed and utilized before and after cross-linking. These values showed a 10-fold decrease in binding after polymerization, which was attributed to an increase in molecular confinement after polymerization and a change in the local structural environment of the binding cavity. Transport of the guest molecule was shown to be reversible.

Binding efficiency and transport properties of molecularly imprinted polymer thin films

Polystyrene-block-poly(methyl methacrylate) copolymers containing [4π + 4π] anthracene photodimer at the junction point between the blocks (PS-AA-PMMA) can be cleaved to the parent homopolymer blocks upon heating above 130 °C or by UV irradiation at 280 nm. PS-AA-PMMA was characterized and then used in thin films to create micro- to macroscale poly(methyl methacrylate) (PMMA) domains in a polystyrene (PS) matrix. Microphase-separated morphologies in thin films were initially achieved by annealing spin-coated films in supercritical carbon dioxide at 80 °C. Subsequent heating and/or UV irradiation was used to cleave the copolymer junction point, affecting an in situ conversion of the diblock copolymer to its parent homopolymers. The evolution of phase separation, from microdomains of PMMA in a matrix of PS to macrophase-separated structures, was investigated by SFM. Subsequent washing with selective solvents removed homopolymer, producing raised nanostructures or nanoporous templates.

Nano- to Macro-Sized Heterogeneities Using Cleavable Diblock Copolymers

Carbonaceous templates with nanopores <10 nm in diameter have been produced using low molecular weight diblock copolymers of poly(styrene-b-acrylonitrile). PS-b-PAN was synthesized using sequential living and controlled polymerization approaches, where the first block was anionically synthesized while the second block was added using atom transfer radical polymerization (ATRP). Polystyrene with a hydroxy end group was synthesized anionically and then reacted with 2-bromoisobutyryl bromide to create the ATRP macroinitiator. Acrylonitrile was polymerized using ATRP procedures. Polymer microphase separation, stabilization, and subsequent pyrolysis were characterized by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM).

Synthesis and Microphase Separation of Poly(styrene-b-acrylonitrile) Prepared by Sequential Anionic and ATRP Techniques

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