ORCID Profile
0000-0002-4375-5580
Current Organisation
Commonwealth Scientific and Industrial Research Organisation
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Research Topics
In Research Link Australia (RLA), "Research Topics" refer to ANZSRC FOR and SEO codes. These topics are either sourced from ANZSRC FOR and SEO codes listed in researchers' related grants or generated by a large language model (LLM) based on their publications.
Top 5 Research Topics
ANZSRC Field of Research (FoR)
Synthesis of Materials | Macromolecular and Materials Chemistry | Chemical Engineering Design | Chemical Engineering | Materials engineering | Polymerisation mechanisms | Synthesis Of Macromolecules | Functional Materials | Chemical Engineering not elsewhere classified | Separation Science | Polymerisation Mechanisms | Polymerisation Mechanisms | Physical Chemistry Of Macromolecules | Polymers and plastics
ANZSRC Socio-Economic Objective (SEO)
Polymeric Materials (e.g. Paints) | Expanding Knowledge in the Chemical Sciences | Expanding Knowledge in Engineering | Paints | Plastics in primary forms | Plastics in Primary Forms |
Related Links
Publications
Multiblock Copolymer Synthesis via Reversible Addition–Fragmentation Chain Transfer Emulsion Polymerization: Effects of Chain Mobility within Particles on Control over Molecular Weight Distribution
Publisher: American Chemical Society (ACS)
Date: 05-04-2021
The scope for synthesis of macro-RAFT agents by sequential insertion of single monomer units
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2PY00529H
Macro-RAFT synthesis by single unit monomer insertion (SUMI) into dithiobenzoate RAFT agents – Towards biological precision
Publisher: MDPI
Date: 26-05-2014
DOI: 10.3390/ECM-1-D004
Emerging Polymer Technologies
Publisher: Walter de Gruyter GmbH
Date: 04-2019
DOI: 10.1515/CI-2019-0217
Morphology-property relationships in ABS/PET blends .1. Compositional effects
Publisher: Wiley
Date: 05-12-1996
DOI: 10.1002/(SICI)1097-4628(19961205)62:10<1699::AID-APP21>3.0.CO;2-W
Advances in switchable RAFT polymerization
Publisher: Wiley
Date: 04-2015
Definitions and notations relating to tactic polymers (IUPAC Recommendations 2020)
Publisher: Walter de Gruyter GmbH
Date: 02-10-2020
Abstract: This document summarizes and extends definitions and notations for the description of tactic polymers and the diad structures of which they are composed. It formally recognizes and resolves apparent inconsistencies between terminology used in the polymer field to describe tactic polymers and terminology in more common use in organic chemistry. Specifically, the terms m and r diads are recommended to replace the terms meso and racemo diads. The definitions are also updated from those in the existing Stereochemistry Document to use the term ‘stereogenic centre’, rather than ‘chiral or prochiral atoms’. Further, the terms relating to tacticity have been defined for the constituent macromolecules, rather than for the polymers composed of those macromolecules. Therefore, this document also forms an addendum and corrigendum to the 1981 document, ‘Stereochemical definitions and notations relating to polymers’.
RAFT-mediated, visible light-initiated single unit monomer insertion and its application in the synthesis of sequence-defined polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY00713B
Abstract: In this communication, we report a catalyst-free methodology for single unit monomer insertion (SUMI) into reversible addition–fragmentation chain transfer (RAFT) agents initiated by low intensity visible light.
Effect of ethyl aluminium sesquichloride on the relative reactivities of styrene and methyl methacrylate towards the 1-cyano-1-methylethyl and the 1-methyl-1-(methoxycarbonyl)ethyl radicals
Publisher: Elsevier BV
Date: 02-1993
Thiocarbonylthio end group removal from RAFT‐synthesized polymers by a radical‐induced process
Publisher: Wiley
Date: 27-10-2009
DOI: 10.1002/POLA.23711
Abstract: The removal of thiocarbonylthio end groups by radical‐addition‐fragmentation‐ coupling from polymers synthesized by RAFT polymerization has been studied. We found that a method, which involves heating the polymer with a large excess (20 molar equivalents) of azobis(isobutyronitrile) (AIBN), while successful with methacrylic polymers, is less effective with styrenic or acrylic polymers and provides only partial end group removal. This is attributed to the propagating radicals generated from the latter polymers being poor radical leaving groups relative to the cyanoisopropyl radical. Similar use of lauroyl peroxide (LPO) completely removes the thiocarbonylthio groups from styrenic or acrylic polymers but, even with LPO in large excess, produces a polymer with a bimodal molecular weight distribution. The formation of a peak of double molecular weight is indicative of the occurrence of self‐termination and ineffective radical trapping. We now report that by use of a combination of LPO (2 molar equivalents) and AIBN (20 molar equivalents) we are able to completely remove thiocarbonylthio end groups of styrenic or acrylic polymers and minimize the occurrence of self termination. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6704–6714, 2009
Ring-opening of some radicals containing the cyclopropylmethyl system
Publisher: Royal Society of Chemistry (RSC)
Date: 1980
DOI: 10.1039/P29800001473
A 20th anniversary perspective on the life of RAFT (RAFT coming of age)
Publisher: Wiley
Date: 18-12-2020
DOI: 10.1002/PI.5944
Characterization of poly(ethylene terephthalate) and poly(ethylene terephthalate) blends
Publisher: Elsevier BV
Date: 06-1997
Effect of ethyl aluminium sesquichloride on the specificity of the reactions of 1-methyl-1-methoxycarbonylethyl radical
Publisher: Springer Science and Business Media LLC
Date: 1992
DOI: 10.1007/BF00309700
Synthesis of Defined Polymers by Reversible Addition—Fragmentation Chain Transfer: The RAFT Process
Publisher: American Chemical Society
Date: 15-08-2000
Preparation of Macromonomers via Chain Transfer with and without Added Chain Transfer Agent
Publisher: American Chemical Society
Date: 15-08-2000
Reversible Addition Fragmentation Chain Transfer Polymerization of Methyl Methacrylate in the Presence of Lewis Acids: An Approach to Stereocontrolled Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 28-11-2007
DOI: 10.1021/MA071100T
Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT Process
Publisher: American Chemical Society (ACS)
Date: 22-07-1998
DOI: 10.1021/MA9804951
Radical Addition-Fragmentation Chemistry and RAFT Polymerization
Publisher: Elsevier
Date: 2012
Multiblock copolymer synthesis via RAFT emulsion polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2CS00115B
Abstract: Emulsion polymerization mediated by RAFT confers a plenty of advantages for the synthesis of multiblock copolymers, including but not limited to control over particle morphology, molecular weight, livingness, composition, and time.
Synthesis of novel architectures by radical polymerization with reversible addition fragmentation chain transfer (RAFT polymerization)
Publisher: Wiley
Date: 03-2003
A brief guide to polymerization terminology (IUPAC Technical Report)
Publisher: Walter de Gruyter GmbH
Date: 15-08-2022
Abstract: The use of self-consistent terminology to describe polymerizations is important for litigation, patents, research and education. Imprecision in these areas can be both costly and confusing. To address this situation the International Union of Pure and Applied Chemistry (IUPAC) has made recommendations, which are summarized below. In the version shown as the supplementary material, references and hyperlinks lead to source documents screen tips contain definitions published in IUPAC recommendations. More details can also be found in the IUPAC Purple Book. This guide is one of a series on terminology and nomenclature. Refer to the supplementary material for the complete and interactive version of this brief guide.
Effect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent
Publisher: American Chemical Society (ACS)
Date: 05-01-2018
Effects of solvent on model copolymerization reactions. A 13C-NMR study
Publisher: Elsevier BV
Date: 03-1992
Ab initio RAFT emulsion polymerization mediated by small cationic RAFT agents to form polymers with low molar mass dispersity
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY00893D
Abstract: We report on low molar mass cationic RAFT agents that provide predictable molar mass and low molar mass dispersities ( Đ m ) in ab initio emulsion polymerization.
The EORTC module for quality of life in patients with thyroid cancer: phase III
Publisher: Bioscientifica
Date: 04-2017
DOI: 10.1530/ERC-16-0530
Abstract: The purpose of the study was to pilot-test a questionnaire measuring health-related quality of life (QoL) in thyroid cancer patients to be used with the European Organisation for Research and Treatment of Cancer (EORTC) core questionnaire EORTC QLQ-C30. A provisional questionnaire with 47 items was administered to patients treated for thyroid cancer within the last 2 years. Patients were interviewed about time and help needed to complete the questionnaire, and whether they found the items understandable, confusing or annoying. Items were kept in the questionnaire if they fulfilled pre-defined criteria: relevant to the patients, easy to understand, not confusing, few missing values, neither floor nor ceiling effects, and high variance. A total of 182 thyroid cancer patients in 15 countries participated ( n = 115 with papillary, n = 31 with follicular, n = 22 with medullary, n = 6 with anaplastic, and n = 8 with other types of thyroid cancer). Sixty-six percent of the patients needed 15 min or less to complete the questionnaire. Of the 47 items, 31 fulfilled the predefined criteria and were kept unchanged, 14 were removed, and 2 were changed. Shoulder dysfunction was mentioned by 5 patients as missing and an item covering this issue was added. To conclude, the EORTC quality of life module for thyroid cancer (EORTC QLQ-THY34) is ready for the final validation phase IV.
Terminology and the naming of conjugates based on polymers or other substrates (IUPAC Recommendations 2021)
Publisher: Walter de Gruyter GmbH
Date: 17-03-2022
Abstract: A number of human activities require that certain complex molecules, referred to as active species (drugs, dyes, peptides, proteins, genes, radioactive labels, etc.), be combined with substrates, often a macromolecule, to form temporary or permanent conjugates. The existing IUPAC organic, polymer, and inorganic nomenclature principles can be applied to name such conjugates but it is not always appropriate. These nomenclatures have two major shortcomings: (1) the resulting names are often excessively long and (2) identification of the components (substrate, active species, and link) can be difficult. The new IUPAC naming system elaborates rules for unambiguous and facile naming of any conjugate. This naming system is not intended to replace the existing nomenclature but to provide a suitable alternative when dictated by necessity. Although the rules are intended to be primarily applicable to the naming of polymer conjugates, they are also applicable to naming conjugates with other substrates, which include micelles, particles, minerals, surfaces, pores, etc. The naming system should be used when recognition of the substrate and active substance is essential and will also be useful when constraints of name length make the otherwise preferred IUPAC nomenclatures untenable. The proposed rules for the new naming system are complemented by a glossary of relevant terms.
Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion
Publisher: American Chemical Society (ACS)
Date: 19-09-2018
DOI: 10.1021/JACS.8B08386
Abstract: Natural biopolymers, such as DNA and proteins, have uniform microstructures with defined molecular weight, precise monomer sequence, and stereoregularity along the polymer main chain that affords them unique biological functions. To reproduce such structurally perfect polymers and understand the mechanism of specific functions through chemical approaches, researchers have proposed using synthetic polymers as an alternative due to their broad chemical ersity and relatively simple manipulation. Herein, we report a new methodology to prepare sequence-controlled and stereospecific oligomers using alternating radical chain growth and sequential photoinduced RAFT single unit monomer insertion (photo-RAFT SUMI). Two families of cyclic monomers, the indenes and the N-substituted maleimides, can be alternatively inserted into RAFT agents, one unit at a time, allowing the monomer sequence to be controlled through sequential and alternating monomer addition. Importantly, the stereochemistry of cyclic monomer insertion into the RAFT agents is found to be trans-selective along the main chains due to steric hindrance from the repeating monomer units. All investigated cyclic monomers provide such trans-selectivity, but analogous acyclic monomers give a mixed cis- and trans-insertion.
Advances in RAFT polymerization: the synthesis of polymers with defined end-groups
Publisher: Elsevier BV
Date: 09-2005
RAFT agent design and synthesis
Publisher: American Chemical Society (ACS)
Date: 21-05-2012
DOI: 10.1021/MA300410V
A small-angle X-ray scattering study of the effect of chain architecture on the shear-induced crystallization of branched and linear poly(ethylene terephthalate)
Publisher: International Union of Crystallography (IUCr)
Date: 17-02-2007
Functional polymers for optoelectronic applications by RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C0PY00179A
RAFT Polymerization: Adding to the Picture
Publisher: Wiley
Date: 13-04-2007
Chain Transfer to Polymer: A Convenient Route to Macromonomers
Publisher: American Chemical Society (ACS)
Date: 06-10-1999
DOI: 10.1021/MA990488S
The synthesis of polyolefin graft copolymers by reactive extrusion
Publisher: Elsevier BV
Date: 04-1999
Consistent values of rate parameters in free radical polymerization systems. II. Outstanding dilemmas and recommendations
Publisher: Wiley
Date: 04-1992
Azo and Peroxy Initiators
Publisher: Elsevier
Date: 1989
End groups of poly(methyl methacrylate-co-styrene) prepared with tert-butoxy, methyl, and/or phenyl radical initiation: effects of solvent, monomer composition, and conversion
Publisher: American Chemical Society (ACS)
Date: 05-1988
DOI: 10.1021/MA00183A050
ChemInform Abstract: Toward Living Radical Polymerization
Publisher: Wiley
Date: 20-11-2008
Kinetics of the coupling reactions of the nitroxyl radical 1,1,3,3-tetramethylisoindoline-2-oxyl with carbon-centered radicals
Publisher: American Chemical Society (ACS)
Date: 04-1988
DOI: 10.1021/JO00243A008
Evaluation of the kinetic parameters for styrene polymerization and their chain length dependence by kinetic simulation and pulsed laser photolysis
Publisher: Wiley
Date: 06-1993
Fate of the initiator in the azobisisobutyronitrile-initiated polymerization of styrene
Publisher: American Chemical Society (ACS)
Date: 05-1984
DOI: 10.1021/MA00135A021
Rapid and systematic access to quasi-diblock copolymer libraries covering a comprehensive composition range by sequential RAFT polymerization in an automated synthesizer
Publisher: Wiley
Date: 29-08-2014
Abstract: A versatile, cost-effective approach to the rapid, fully unattended preparation of systematic quasi-diblock copolymer libraries via sequential RAFT polymerization in an automated synthesizer is reported. The procedure is demonstrated with the synthesis of a 23 member library of low dispersity poly(butyl methacrylate)-quasiblock-poly(methyl methacrylate) covering a wide (fivefold) range of molar mass for the second block in a one-pot, sequential, RAFT polymerization.
Compatibilisation of polystyrene-polyolefin blends
Publisher: Springer Science and Business Media LLC
Date: 04-1994
DOI: 10.1007/BF00587891
Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT Polymerization) Using Dithiocarbamates as Chain Transfer Agents
Publisher: American Chemical Society (ACS)
Date: 24-09-1999
DOI: 10.1021/MA9906837
RAFT polymerization with phthalimidomethyl trithiocarbonates or xanthates. On the origin of bimodal molecular weight distributions in living radical polymerization
Publisher: American Chemical Society (ACS)
Date: 11-07-2006
DOI: 10.1021/MA0604338
High-throughput concurrent synthesis of core-crosslinked star-polydimethylsiloxane using an arm-first approach
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3PY00331K
Abstract: In this work we use RAFT crosslinking polymerisation coupled with a Chemspeed robotic synthesis platform to optimise conditions to produce PDMS-arm star polymers by an arm-first strategy.
New Free-Radical Ring-Opening Acrylate Monomers
Publisher: American Chemical Society (ACS)
Date: 12-1994
DOI: 10.1021/MA00104A062
Porous, functional, poly(styrene-co-divinylbenzene) monoliths by RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C3PY01015E
A brief guide to polymer nomenclature
Publisher: Elsevier BV
Date: 2013
RAFT Polymerization: Methods, Synthesis and Applications
Publisher: Wiley
Date: 29-10-2021
Substituent effects on RAFT polymerization with benzyl aryl trithiocarbonates
Publisher: Wiley
Date: 26-02-2010
Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/MA960852C
A brief guide to polymer nomenclature
Publisher: Elsevier BV
Date: 2013
A novel method for determination of polyester end-groups by NMR spectroscopy
Publisher: Elsevier BV
Date: 06-2005
Terminology for aggregation and self-assembly in polymer science (IUPAC Recommendations 2013)
Publisher: Walter de Gruyter GmbH
Date: 16-12-2012
Abstract: In the past, aggregation and self-assembly have been associated principally with micellar and colloidal systems of molecules however, with the advent of supramolecular chemistry, molecular self-assembly has been opened to a much wider understanding that has facilitated access to a variety of different shapes and sizes, along with the construction of new and fascinating molecular topologies. This document aims at defining more than 150 terms related to aggregation and self-assembly in the particular case of macromolecules. The list is restricted to the most commonly encountered terms.
Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06229
Abstract: Thermolysis provides a simple and efficient way of eliminating thiocarbonylthio groups from RAFT-synthesized polymers. The course of thermolysis of poly(methyl methacrylate) (PMMA) prepared with dithiobenzoate and trithiocarbonate RAFT agents was followed by thermogravimetric analysis (TGA), 1H NMR spectroscopy, and gel permeation chromatography (GPC). The weight loss profile observed depends strongly on the RAFT agent used during polymer synthesis. PMMA with a methyl trithiocarbonate end group undergoes loss of that end group at ~180°C, at least in part, by a mechanism believed to involve homolysis of the C–CS2SCH3 bond and subsequent depropagation. In contrast, PMMA with a dithiobenzoate end appears more stable. Only the end group is lost at ~180°C and the dominant mechanism is proposed to be a concerted elimination process analogous to that involved in the Chugaev reaction.
TACTICITY OF POLY(METHYL METHACRYLATE) - EVIDENCE FOR A PENPENULTIMATE GROUP EFFECT IN FREE-RADICAL POLYMERIZATION
Publisher: CSIRO Publishing
Date: 1986
DOI: 10.1071/CH9860043
Abstract: The tacticity of poly(methyl methacrylate ) prepared by free-radical polymerization has been determined by analysing the carbonyl region of the 13C n.m.r . spectrum. This analysis demonstrates that the addition of poly(methyl methacrylyl ) radical to methyl methacrylate in benzene at 60°C is subject to a significant penpenultimate unit effect. The probability of forming a meso dyad is some 20% less if the preceding dyad in the chain is also meso . The polymerization (60°C, benzene) is described by the following parameters P(m) = 0.202, P(m|m) = 0.159, P(r | m) = 0.212.
Aqueous hydrogen peroxide-induced degradation of polyolefins: A greener process for controlled-rheology polypropylene
Publisher: Elsevier BV
Date: 07-2015
Definitions of terms relating to the structure and processing of sols, gels, networks, and inorganic-organic hybrid materials (IUPAC Recommendations 2007)
Publisher: Walter de Gruyter GmbH
Date: 2007
Abstract: This document defines terms related to the structure and processing of inorganic, polymeric, and inorganic-organic hybrid materials from precursors, through gels to solid products. It is ided into four sections - precursors, gels, solids, and processes - and the terms have been restricted to those most commonly encountered. For the sake of completeness and where they are already satisfactorily defined for the scope of this document, terms from other IUPAC publications have been used. Otherwise, the terms and their definitions have been assembled in consultation with experts in the relevant fields. The definitions are intended to assist the reader who is unfamiliar with sol-gel processing, ceramization, and related technologies and materials, and to serve as a guide to the use of standard terminology by those researching in these areas.
Kinetics and mechanism for thermal and photochemical decomposition of 4,4’-azobis(4-cyanopentanoic acid) in aqueous media
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY00507B
Abstract: The two diastereoisomers of 4,4′-azobis(4-cyanopentanoic acid) decompose at different rates in aqueous media. The major products ( %) are amides produced by trapping the ketenimines formed by C–N coupling.
Electrochemically-Initiated RAFT Synthesis of Low Dispersity Multiblock Copolymers by Seeded Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 20-02-2023
Exploitation of the nanoreactor concept for efficient synthesis of multiblock copolymers via macroraft-mediated emulsion polymerization
Publisher: American Chemical Society (ACS)
Date: 23-07-2019
DOI: 10.1021/ACSMACROLETT.9B00534
Abstract: Multiblock copolymers are a class of polymeric materials with a range of potential applications. We report here a strategy for the synthesis of multiblock copolymers based on methacrylates. Reversible addition-fragmentation chain transfer (RAFT) polymerization is implemented as an emulsion polymerization to generate seed particles as nanoreactors, which can subsequently be employed in sequential RAFT emulsion polymerizations. The segregation effect allowed the synthesis of a high molar mass (>100,000 g·mol
RAFT polymerization and some of its applications
Publisher: Wiley
Date: 18-04-2013
Abstract: Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents.
Thiocarbonylthio End Group Removal from RAFT-Synthesized Polymers by Radical-Induced Reduction
Publisher: American Chemical Society (ACS)
Date: 22-05-2007
DOI: 10.1021/MA062919U
Chain Transfer Kinetics of Acid/Base Switchable N-Aryl-N-Pyridyl Dithiocarbamate RAFT Agents in Methyl Acrylate, N-Vinylcarbazole and Vinyl Acetate Polymerization
Publisher: American Chemical Society (ACS)
Date: 14-05-2012
DOI: 10.1021/MA300616G
Polymerization-induced self-assembly: Via RAFT in emulsion: Effect of Z-group on the nucleation step
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0PY01311K
Abstract: It is demonstrated that the nature of the Z-group of trithiocarbonate RAFT agents can have a major effect on the nucleation step of aqueous RAFT PISA performed as emulsion polymerization.
Toward Living Radical Polymerization
Publisher: American Chemical Society (ACS)
Date: 14-08-2008
DOI: 10.1021/AR800075N
Abstract: Radical polymerization is one of the most widely used processes for the commercial production of high-molecular-weight polymers. The main factors responsible for the preeminent position of radical polymerization are the ability to polymerize a wide array of monomers, tolerance of unprotected functionality in monomer and solvent, and compatibility with a variety of reaction conditions. Radical polymerization is simple to implement and inexpensive in relation to competitive technologies. However, conventional radical polymerization severely limits the degree of control that researchers can assert over molecular-weight distribution, copolymer composition, and macromolecular architecture. This Account focuses on nitroxide-mediated polymerization (NMP) and polymerization with reversible addition-fragmentation chain transfer (RAFT), two of the more successful approaches for controlling radical polymerization. These processes illustrate two distinct mechanisms for conferring living characteristics on radical polymerization: reversible deactivation (in NMP) and reversible or degenerate chain transfer (in RAFT). We devised NMP in the early 1980s and have exploited this method extensively for the synthesis of styrenic and acrylic polymers. The technique has undergone significant evolution since that time. New nitroxides have led to faster polymerization rates at lower temperatures. However, NMP is only applicable to a restricted range of monomers. RAFT was also developed at CSIRO and has proven both more robust and more versatile. It is applicable to the majority of monomers subject to radical polymerization, but the success of the polymerization depends upon the selection of the RAFT agent for the monomers and reaction conditions. We and other groups have proposed guidelines for selection, and the polymerization of most monomers can be well-controlled to provide minimal retardation and a high fraction of living chains by using one of just two RAFT agents. For ex le, a tertiary cyanoalkyl trithiocarbonate is suited to (meth)acrylate, (meth)acrylamide, and styrenic monomers, while a cyanomethyl xanthate or dithiocarbamate works with vinyl monomers, such as vinyl acetate or N-vinylpyrrolidone. With the appropriate choice of reagents and polymerization conditions, these reactions possess most of the attributes of living polymerization. We have used these methods in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, including microgels and polymer brushes. Applications of these polymers include novel surfactants, dispersants, coatings and adhesives, biomaterials, membranes, drug-delivery media, electroactive materials, and other nanomaterials.
Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media
Publisher: American Chemical Society (ACS)
Date: 03-09-2020
Selective and Rapid Light-Induced RAFT Single Unit Monomer Insertion in Aqueous Solution
Publisher: Wiley
Date: 10-11-2020
Abstract: The photocatalyst Zn(II) meso-tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) is found to substantially accelerate visible-light-initiated (red, yellow, green light) single unit monomer insertion (SUMI) of N,N-dimethylacrylamide into the reversible addition-fragmentation chain transfer (RAFT) agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (RAFT
Glossary of terms relating to thermal and thermomechanical properties of polymers (IUPAC recommendations 2013),Glosar naziva vezanih uz toplinska i termomehanička svojstva polimera (IUPAC-ove preporuke 2013.)
Publisher: Croatian Society of Chemical Engineers/HDKI
Date: 12-05-2015
Fungal Planet description sheets: 868–950
Publisher: Naturalis Biodiversity Center
Date: 19-07-2019
DOI: 10.3767/PERSOONIA.2019.42.11
Abstract: Novel species of fungi described in this study include those from various countries as follows: Australia , Chaetomella pseudocircinoseta and Coniella pseudodiospyri on Eucalyptus microcorys leaves, Cladophialophora eucalypti , Teratosphaeria dunnii and Vermiculariopsiella dunnii on Eucalyptus dunnii leaves, Cylindrium grande and Hypsotheca eucalyptorum on Eucalyptus grandis leaves, Elsinoe salignae on Eucalyptus saligna leaves, Marasmius lebeliae on litter of regenerating subtropical rainforest, Phialoseptomonium eucalypti (incl. Phialoseptomonium gen. nov.) on Eucalyptus grandis × camaldulensis leaves, Phlogicylindrium pawpawense on Eucalyptus tereticornis leaves, Phyllosticta longicauda as an endophyte from healthy Eustrephus latifolius leaves, Pseudosydowia eucalyptorum on Eucalyptus sp. leaves, Saitozyma wallum on Banksia aemula leaves, Teratosphaeria henryi on Corymbia henryi leaves. Brazil , Aspergillus bezerrae , Backusella azygospora , Mariannaea terricola and Talaromyces pernambucoensis from soil, Calonectria matogrossensis on Eucalyptus urophylla leaves, Calvatia brasiliensis on soil, Carcinomyces nordestinensis on Bromelia antiacantha leaves, Dendryphiella stromaticola on small branches of an unidentified plant, Nigrospora brasiliensis on Nopalea cochenillifera leaves, Penicillium alagoense as a leaf endophyte on a Miconia sp., Podosordaria nigrobrunnea on dung, Spegazzinia bromeliacearum as a leaf endophyte on Tilandsia catimbauensis , Xylobolus brasiliensis on decaying wood. Bulgaria , Kazachstania molopis from the gut of the beetle Molops piceus . Croatia , Mollisia endocrystallina from a fallen decorticated Picea abies tree trunk. Ecuador , Hygrocybe rodomaculata on soil. Hungary , Alfoldia vorosii (incl. Alfoldia gen. nov.) from Juniperus communis roots, Kiskunsagia ubrizsyi (incl. Kiskunsagia gen. nov.) from Fumana procumbens roots. India , Aureobasidium tremulum as laboratory contaminant, Leucosporidium himalayensis and Naganishia indica from windblown dust on glaciers. Italy , Neodevriesia cycadicola on Cycas sp. leaves, Pseudocercospora pseudomyrticola on Myrtus communis leaves, Ramularia pistaciae on Pistacia lentiscus leaves, Neognomoniopsis quercina (incl. Neognomoniopsis gen. nov.) on Quercus ilex leaves. Japan , Diaporthe fructicola on Passiflora edulis × P . edulis f. flavicarpa fruit, Entoloma nipponicum on leaf litter in a mixed Cryptomeria japonica and Acer spp. forest. Macedonia , Astraeus macedonicus on soil. Malaysia , Fusicladium eucalyptigenum on Eucalyptus sp. twigs, Neoacrodontiella eucalypti (incl. Neoacrodontiella gen. nov.) on Eucalyptus urophylla leaves. Mozambique , Meliola gorongosensis on dead Philenoptera violacea leaflets. Nepal , Coniochaeta dendrobiicola from Dendriobium lognicornu roots. New Zealand , Neodevriesia sexualis and Thozetella neonivea on Archontophoenix cunninghamiana leaves. Norway , Calophoma sandfjordenica from a piece of board on a rocky shoreline, Clavaria parvispora on soil, Didymella finnmarkica from a piece of Pinus sylvestris driftwood. Poland , Sugiyamaella trypani from soil. Portugal , Colletotrichum feijoicola from Acca sellowiana. Russia , Crepidotus tobolensis on Populus tremula debris, Entoloma ekaterinae , Entoloma erhardii and Suillus gastroflavus on soil, Nakazawaea ambrosiae from the galleries of Ips typographus under the bark of Picea abies. Slovenia , Pluteus ludwigii on twigs of broadleaved trees. South Africa , Anungitiomyces stellenboschiensis (incl. Anungitiomyces gen. nov.) and Niesslia stellenboschiana on Eucalyptus sp. leaves, Beltraniella pseudoportoricensis on Podocarpus falcatus leaf litter, Corynespora encephalarti on Encephalartos sp. leaves, Cytospora pavettae on Pavetta revoluta leaves, Helminthosporium erythrinicola on Erythrina humeana leaves, Helminthosporium syzygii on a Syzygium sp. barkcanker, Libertasomyces aloeticus on Aloe sp. leaves, Penicillium lunae from Musa sp. fruit, Phyllosticta lauridiae on Lauridia tetragona leaves, Pseudotruncatella bolusanthi (incl. Pseudotruncatellaceae fam. nov.) and Dactylella bolusanthi on Bolusanthus speciosus leaves. Spain , Apenidiella foetida on submerged plant debris, Inocybe grammatoides on Quercus ilex subsp. ilex forest humus, Ossicaulis salomii on soil, Phialemonium guarroi from soil. Thailand , Pantospora chromolaenae on Chromolaena odorata leaves. Ukraine , Cadophora helianthi from Helianthus annuus stems. USA , Boletus pseudopinophilus on soil under slash pine, Botryotrichum foricae , Penicillium americanum and Penicillium minnesotense from air. Vietnam , Lycoperdon vietnamense on soil. Morphological and culture characteristics are supported by DNA barcodes.
RAFT Copolymerization and Its Application to the Synthesis of Novel Dispersants—Intercalants—Exfoliants for Polymer—Clay Nanocomposites
Publisher: American Chemical Society
Date: 07-09-2006
Fundamentals of reversible addition-fragmentation chain transfer (RAFT)
Publisher: Walter de Gruyter GmbH
Date: 30-12-2021
Abstract: Radical polymerization is transformed into what is known as reversible addition–fragmentation chain transfer (RAFT) polymerization by the addition of a RAFT agent. RAFT polymerization enables the preparation of polymers with predictable molar mass, narrow chain length distribution, high end-group integrity and provides the ability to construct macromolecules with the intricate architectures and composition demanded by modern applications in medicine, electronics and nanotechnology. This paper provides a background to understanding the mechanism of RAFT polymerization and how this technique has evolved.
Morphology-property relationships in ABS/PET blends. II. Influence of processing conditions on structure and properties
Publisher: Wiley
Date: 05-12-1996
DOI: 10.1002/(SICI)1097-4628(19961205)62:10<1709::AID-APP22>3.0.CO;2-V
KINETIC SIMULATION OF POLYMERIZATION INVOLVING TERMINATION BY REVERSIBLE CHAIN TRANSFER
Publisher: CSIRO Publishing
Date: 1986
DOI: 10.1071/CH9861943
Abstract: Numerical integration has been used as a means of simulating the title polymerization so that the variation of molecular weight and molecular weight distribution with reaction time (conversion) can be evaluated. The time/conversion dependence of the polydispersity (R) has been evaluated as a function of the relative magnitude of the rate constants associated with the initiation/termination equilibria . It is shown that the short term behaviour of R and the rate of approach to the value (R = 4/3) predicted by the steady state treatment have a marked dependence on the choice of rate constants.
Absolute rate constants for radical-monomer reactions
Publisher: Springer Science and Business Media LLC
Date: 12-1992
DOI: 10.1007/BF01041150
Direct Measurement of Primary Radical Concentrations in Pulsed Laser Photolysis
Publisher: American Chemical Society (ACS)
Date: 12-1997
DOI: 10.1021/MA9708095
Taxonomy based on science is necessary for global conservation
Publisher: Public Library of Science (PLoS)
Date: 14-03-2018
Living and controlled reversible-activation polymerization (RAP) on the way to reversible-deactivation radical polymerization (RDRP)
Publisher: Wiley
Date: 20-06-2022
DOI: 10.1002/PI.6424
Abstract: In 2010, an IUPAC task group comprising Aubrey Jenkins, Dick Jones and Graeme Moad coined ‘reversible‐deactivation radical polymerization (RDRP)’ as a new term to describe what up to that time had been known variously as living or controlled radical polymerization. This paper describes the steps and missteps in the terminological development of RDRP. The paper that introduced the term is currently one of the more highly cited IUPAC terminology papers. © 2022 Commonwealth of Australia. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.
In Focus Emerging Polymer Technologies Summit (EPTS'16)
Publisher: Wiley
Date: 04-10-2017
DOI: 10.1002/PI.5456
Use of Chain Length Distributions in Determining Chain Transfer Constants and Termination Mechanisms
Publisher: American Chemical Society (ACS)
Date: 1996
DOI: 10.1021/MA960851K
Synthesis of Multicompositional Onion‐like Nanoparticles via RAFT Emulsion Polymerization
Publisher: Wiley
Date: 15-09-2021
Abstract: Synthesis of multicompositional polymeric nanoparticles of diameters 100–150 nm comprising well‐defined multiblock copolymers reaching from the particle surface to the particle core was conducted using surfactant‐free aqueous macroRAFT emulsion polymerization. The imposed constraints on chain mobility as well as chemical incompatibility between the blocks result in microphase separation, leading to formation of an onion‐like multilayered particle morphology with in idual layer thicknesses of approximately 20 nm. The approach provides considerable versatility in particle morphology design as the composition of in idual layers as well as the number of layers can be tailored as desired, offering more complex particle design compared to approaches relying on self‐assembly of preformed diblock copolymers within particles. Microphase separation can occur in these systems under conditions where the corresponding bulk system would not theoretically result in microphase separation.
End-functional polymers, thiocarbonylthio group removal/transformation and reversible addition-fragmentation-chain transfer (RAFT) polymerization
Publisher: Wiley
Date: 23-12-2011
DOI: 10.1002/PI.2988
Block copolymers containing organic semiconductor segments by RAFT polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1OB05276D
Abstract: Approaches to the synthesis of block copolymers containing organic semiconductor segments (polythiophene, perylene diimide) by RAFT polymerization have been explored. A method involving transformation of a vinyl derivative to a macro-RAFT agent provides for the synthesis of block copolymers which are joined by a short non-hydrolysable linkage.
A brief guide to polymer nomenclature
Publisher: Elsevier BV
Date: 02-2013
Tailored polymer architectures by reversible addition-frasmentation chain transfer
Publisher: Wiley
Date: 09-2001
DOI: 10.1002/1521-3900(200109)174:1<209::AID-MASY209>3.0.CO;2-O
Is α-tocopherol a reservoir for α-tocopheryl hydroquinone?
Publisher: Elsevier BV
Date: 08-1995
DOI: 10.1016/0891-5849(95)00010-U
Abstract: The products of oxidation of the alpha-tocopherol model compound, 2,2,5,7,8-pentamethyl-6-chromanol (PH) by t-butyl hydroperoxide in chloroform varied with the amount of water present. In the presence of a trace of water, the main products were the spirodimer (PSD) and spirotrimer (PST). As the content of water increased, the main product became 2-(3-hydroxy-3-methylbutyl)-3,5,6-trimethyl-1,4-benzoquinone (PQ). Oxidation of PH in aqueous liposome suspension also produced PQ as the major product. These results suggested that, in aqueous solutions, the major oxidation product of PH would be PQ and of alpha-tocopherol (TH) would be alpha-tocopheryl quinone (TQ). The ease of reduction of PQ and TQ was studied in chemical and biological systems. PQ, TQ, and ubiquinone-10 (UQ) were rapidly reduced to their respective hydroquinones (PQH2, TQH2, and UQH2) at pH 7.3 by NADH plus FAD. Whole blood reduced PQ rapidly at 37 degrees C to PQH2 but did not reduce TQ to TQH2. Human peripheral blood mononuclear cells took up TQ from a bovine serum albumin complex and reduced it to TQH2. Ingestion of TQ (350 mg) by one of us (PSK) resulted in the formation of TQH2 during a 5 h period. These results demonstrate that several biological systems are able to reduce TQ to TQH2 and that it is a reaction that may occur normally in vivo.
Thermolysis of RAFT-synthesized polymers. A convenient method for trithiocarbonate group elimination
Publisher: American Chemical Society (ACS)
Date: 28-05-2005
DOI: 10.1021/MA050402X
Frontispiece: Synthesis of Discrete Oligomers by Sequential PET‐RAFT Single‐Unit Monomer Insertion
Publisher: Wiley
Date: 05-07-2217
Fundamentals of RAFT polymerization
Publisher: The Royal Society of Chemistry
Date: 04-04-2013
DOI: 10.1039/9781849737425-00205
Abstract: This chapter sets out to describe the fundamental aspects of radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). Following a description of the mechanism we describe aspects of the kinetics of RAFT polymerization, how to select a RAFT agent to achieve optimal control over polymer molecular weight, composition and architecture, and how to avoid side reactions which might lead to retardation or inhibition.
Living Radical Polymerization
Publisher: Elsevier
Date: 2005
Living Radical Polymerization by the RAFT Process—A First Update
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06250
Abstract: This paper provides a first update to the review of living radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of Reversible Addition–Fragmentation chain Transfer (RAFT) published in June 2005. The time since that publication has witnessed an increased rate of publication on the topic with the appearance of well over 200 papers covering various aspects of RAFT polymerization ranging over reagent synthesis and properties, kinetics, and mechanism of polymerization, novel polymer syntheses, and erse applications.
Definitions of terms relating to reactions of polymers and to functional polymeric materials (IUPAC Recommendations 2003)
Publisher: Walter de Gruyter GmbH
Date: 2004
Abstract: The document defines the terms most commonly encountered in the field of polymer reactions and functional polymers. The scope has been limited to terms that are specific to polymer systems. The document is organized into three sections. The first defines the terms relating to reactions of polymers. Names of in idual chemical reactions are omitted from the document, even in cases where the reactions are important in the field of polymer reactions. The second section defines the terms relating to polymer reactants and reactive polymeric materials. The third section defines the terms describing functional polymeric materials.
Combination Anti-HIV therapy via tandem release of prodrugs from macromolecular carriers
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6PY01882C
Abstract: Reversible addition-fragmentation chain transfer (RAFT) polymerisation has been used to create a library of copolymers outfitted with a combination of self-immolative reverse transcriptase inhibitor prodrug pendents comprising zidovudine (AZT) and lamivudine (3TC).
Crystallisation kinetics of novel branched poly(ethylene terephthalate): a small-angle X-ray scattering study
Publisher: Wiley
Date: 31-07-2006
DOI: 10.1002/PI.2097
A Brief Guide to Polymer Nomenclature
Publisher: Elsevier BV
Date: 2013
Further studies on the thermal decomposition of AIBN—implications concerning the mechanism of termination in methacrylonitrile polymerization
Publisher: Elsevier BV
Date: 02-1993
Enhancement of MHC-I Antigen Presentation via Architectural Control of pH-Responsive, Endosomolytic Polymer Nanoparticles
Publisher: Springer Science and Business Media LLC
Date: 12-12-2014
The reactivity of N-vinylcarbazole in RAFT polymerization: Trithiocarbonates deliver optimal control for the synthesis of homopolymers and block copolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C3PY00487B
RAFT Emulsion Polymerization for (Multi)block Copolymer Synthesis: Overcoming the Constraints of Monomer Order
Publisher: American Chemical Society (ACS)
Date: 05-01-2021
Nonmigratory Poly(vinyl chloride)-block-polycaprolactone Plasticizers and Compatibilizers Prepared by Sequential RAFT and Ring-Opening Polymerization (RAFT-T̵-ROP)
Publisher: American Chemical Society (ACS)
Date: 11-02-2019
A More Versatile Route to Block Copolymers and Other Polymers of Complex Architecture by Living Radical Polymerization: The RAFT Process
Publisher: American Chemical Society (ACS)
Date: 24-02-1999
DOI: 10.1021/MA981472P
Slow nitrogen inversion–N–O rotation in 2-alkoxy-1,1,3,3-tetramethylisoindolines
Publisher: Royal Society of Chemistry (RSC)
Date: 1985
DOI: 10.1039/C39850001249
Kinetics and Mechanism of RAFT Polymerization
Publisher: American Chemical Society
Date: 26-06-2003
RAFT Polymerization in Bulk Monomer or in (Organic) Solution
Publisher: Wiley
Date: 23-01-2008
Approaches to phthalimido and amino end-functional polystyrene by atom transfer radical polymerisation (ATRP)
Publisher: Elsevier BV
Date: 2006
Characterization of polyolefin melts using the polymer reference interaction site model integral equation theory with a single-site united atom model
Publisher: Wiley
Date: 2001
DOI: 10.1002/POLB.1155
Polymerization-Induced Phase Segregation and Self-Assembly of Siloxane Additives to Provide Thermoset Coatings with a Defined Surface Topology and Biocidal and Self-Cleaning Properties
Publisher: MDPI AG
Date: 13-11-2019
DOI: 10.3390/NANO9111610
Abstract: In this work, we report on the incorporation of a siloxane copolymer additive, poly((2-phenylethyl) methylsiloxane)-co(1-phenylethyl) methylsiloxane)-co-dimethylsiloxane), which is fully soluble at room temperature, in a rapid-cure thermoset polyester coating formulation. The additive undergoes polymerization-induced phase segregation (PIPS) to self-assemble on the coating surface as discrete discoid nanofeatures during the resin cure process. Moreover, the copolymer facilitates surface co-segregation of titanium dioxide pigment microparticulate present in the coating. Depending on the composition, the coatings can display persistent superhydrophobicity and self-cleaning properties and, surprisingly, the titanium dioxide pigmented coatings that include the siloxane copolymer additive display high levels of antibacterial performance against Gram-positive (Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa) bacteria. This antibacterial performance is believed to be associated with the unique surface topology of these coatings, which comprise stimuli-responsive discoid nanofeatures. This paper provides details of the surface morphology of the coatings and how these relates to the antimicrobial properties of the coating.
The Critical Importance of Adopting Whole-of-Life Strategies for Polymers and Plastics
Publisher: MDPI AG
Date: 23-07-2021
DOI: 10.3390/SU13158218
Abstract: Plastics have been revolutionary in numerous sectors, and many of the positive attributes of modern life can be attributed to their use. However, plastics are often treated only as disposable commodities, which has led to the ever-increasing accumulation of plastic and plastic by-products in the environment as waste, and an unacceptable growth of microplastic and nanoplastic pollution. The catchphrase “plastics are everywhere”, perhaps once seen as extolling the virtues of plastics, is now seen by most as a potential or actual threat. Scientists are confronting this environmental crisis, both by developing recycling methods to deal with the legacy of plastic waste, and by highlighting the need to develop and implement effective whole-of-life strategies in the future use of plastic materials. The importance and topicality of this subject are evidenced by the dramatic increase in the use of terms such as “whole of life”, “life-cycle assessment”, “circular economy” and “sustainable polymers” in the scientific and broader literature. Effective solutions, however, are still to be forthcoming. In this review, we assess the potential for implementing whole-of-life strategies for plastics to achieve our vision of a circular economy. In this context, we consider the ways in which given plastics might be recycled into the same plastic for potential use in the same application, with minimal material loss, the lowest energy cost, and the least potential for polluting the environment.
Radical Polymerization
Publisher: Elsevier
Date: 2012
The Mechanism and Kinetics of the RAFT Process: Overview, Rates, Stabilities, Side Reactions, Product Spectrum and Outstanding Challenges
Publisher: Wiley
Date: 23-01-2008
The philicity of tert-butoxy radicals. What factors are important in determining the rate and regiospecificity of tert-butoxy radical addition to olefins?
Publisher: American Chemical Society (ACS)
Date: 03-1989
DOI: 10.1021/JO00268A022
Control of polymer structure by chain transfer processes
Publisher: Wiley
Date: 12-1996
Glossary of terms relating to thermal and thermo mechanical properties of polymers (IUPAC recommendations 2013)
Publisher: Walter de Gruyter GmbH
Date: 27-03-2013
Abstract: The document gives definitions of terms met in the conventional thermal and thermomechanical characterisation of polymeric materials.
The Emergence of RAFT Polymerization
Publisher: CSIRO Publishing
Date: 2006
DOI: 10.1071/CH06376
A new form of controlled growth free radical polymerization
Publisher: Wiley
Date: 12-1996
Elements of RAFT Navigation
Publisher: American Chemical Society
Date: 2018
Versatile Approach for Preparing PVC-Based Mikto-Arm Star Additives Based on RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 19-05-2020
Switchable reversible addition-fragmentation chain transfer (raft) polymerization in aqueous solution, n, n -dimethylacrylamide
Publisher: American Chemical Society (ACS)
Date: 15-08-2011
DOI: 10.1021/MA200760Q
Initiating free radical polymerization
Publisher: Wiley
Date: 06-2002
DOI: 10.1002/1521-3900(200206)182:1<65::AID-MASY65>3.0.CO;2-E
Some recent developments in RAFT polymerization
Publisher: American Chemical Society
Date: 2012
Terminology for chain polymerization (IUPAC Recommendations 2021)
Publisher: Walter de Gruyter GmbH
Date: 09-2022
Abstract: Chain polymerizations are defined as chain reactions where the propagation steps occur by reaction between monomer(s) and active site(s) on the polymer chains with regeneration of the active site(s) at each step. Many forms of chain polymerization can be distinguished according to the mechanism of the propagation step (e.g., cyclopolymerization – when rings are formed, condensative chain polymerization – when propagation is a condensation reaction, group-transfer polymerization, polyinsertion, ring-opening polymerization – when rings are opened), whether they involve a termination step or not (e.g., living polymerization – when termination is absent, reversible-deactivation polymerization), whether a transfer step is involved (e.g., degenerative-transfer polymerization), and the type of chain carrier or active site (e.g., radical, ion, electrophile, nucleophile, coordination complex). The objective of this document is to provide a language for describing chain polymerizations that is both readily understandable and self-consistent, and which covers recent developments in this rapidly evolving field.
Controlled RAFT polymerization in a continuous flow microreactor
Publisher: American Chemical Society (ACS)
Date: 10-03-2011
DOI: 10.1021/OP1003314
Measurements of Primary Radical Concentrations Generated by Pulsed Laser Photolysis Using Fluorescence Detection
Publisher: American Chemical Society (ACS)
Date: 08-1999
DOI: 10.1021/JP990892T
Universal (Switchable) RAFT Agents
Publisher: American Chemical Society (ACS)
Date: 29-04-2009
DOI: 10.1021/JA901955N
Abstract: The polymerization of most monomers that are polymerizable by radical polymerization can be controlled by the reversible addition-fragmentation chain transfer (RAFT) process. However, it is usually required that the RAFT agent be selected according to the types of monomer being polymerized. Thus, RAFT agents (dithioesters, trithiocarbonates) suitable for controlling polymerization of "more activated" monomers (MAMs e.g., styrene, acrylates, methacrylates, etc.) tend to inhibit polymerization of "less activated" monomers (LAMs e.g., vinyl acetate, N-vinylpyrrolidone, etc.). Similarly RAFT agents suitable for polymerizations of LAMs (xanthates, certain dithiocarbamates) tend to give little or poor control over polymerizations of MAMs. We now report a new class of "switchable" RAFT agents, N-(4-pyridinyl)-N-methyldithiocarbamates, that provide excellent control over polymerization of LAMs and, after addition of 1 equiv of a protic or Lewis acid, become effective in controlling polymerization of MAMs, allowing the synthesis of poly(MAM)-block-poly(LAM) with narrow molecular weight distributions.
RAFT polymerization to form stimuli-responsive polymers
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6PY01849A
Abstract: Stimuli-responsive polymers respond to a variety of external stimuli, which include optical, electrical, thermal, mechanical, redox, pH, chemical, environmental and biological signals. This paper is concerned with the process of forming such polymers by RAFT polymerization.
Controlling Polymerization
Publisher: Elsevier
Date: 2005
Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible Addition–Fragmentation Chain Transfer Polymerization
Publisher: American Chemical Society (ACS)
Date: 25-11-2020
One pot synthesis of higher order quasi-block copolymer libraries via sequential RAFT polymerization in an automated synthesizer
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4PY00496E
Abstract: The utility of automated high-throughput methods for the one pot synthesis of functional polymers of increased complexity is reported.
Intramolecular addition in hex-5-enyl, hept-6-enyl, and oct-7-enyl radicals
Publisher: Royal Society of Chemistry (RSC)
Date: 1974
DOI: 10.1039/C39740000472
Cyclization of 3-allylhex-5-enyl radical: mechanism, and implications concerning the structures of cyclopolymers
Publisher: Royal Society of Chemistry (RSC)
Date: 1975
DOI: 10.1039/P29750001726
Glossary of terms related to kinetics, thermodynamics, and mechanisms of polymerization (IUPAC Recommendations 2008)
Publisher: Walter de Gruyter GmbH
Date: 2008
Abstract: This document presents recommended definitions of basic terms related to polymerization processes. Recent developments relating to the kinetics, thermodynamics, and mechanisms of polymerization have necessitated the introduction of new terms and some revision or augmentation of terms previously defined in the Compendium of Chemical Terminology (the "Gold Book") or the IUPAC "Glossary of Basic Terms in Polymer Science".
4-Halogeno-3,5-dimethyl-1H-pyrazole-1-carbodithioates: versatile reversible addition fragmentation chain transfer agents with broad applicability
Publisher: Wiley
Date: 02-08-2017
DOI: 10.1002/PI.5423
Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors
Publisher: American Chemical Society (ACS)
Date: 17-03-2021
Viscoelastic properties of vis-breaking polypropylenes
Publisher: AIP Publishing LLC
Date: 2015
DOI: 10.1063/1.4937335
Synthesis of the radical scavenger 1,1,3,3-Tetramethylisoindolin-2-yloxyl
Publisher: CSIRO Publishing
Date: 1983
DOI: 10.1071/CH9830397
Abstract: A versatile free-radical trapping agent, 1,1,3,3-tetramethylisoindolin-2-yloxyl, has been prepared from N-benzylphthalimide by reaction with 'methylmagnesium iodide' in refluxing toluene followed by hydrogenolysis and oxidation. The Grignard reaction gives 2-benzyl-1,1,3,3-tetramethylisoindoline along with a small proportion of an unexpected by-product, 2-benzyl-1-ethyl-1,3,3-trimethyliso-indoline.
Selectivity of the reaction of free radicals with styrene
Publisher: American Chemical Society (ACS)
Date: 05-1982
DOI: 10.1021/MA00231A042
Thermal stability of poly(methyl methacrylate)
Publisher: Springer Science and Business Media LLC
Date: 11-1988
DOI: 10.1007/BF01153444
Dithiocarbamates in RAFT Polymerization
Publisher: Wiley
Date: 29-10-2021
“Weak links” in polystyrene—thermal degradation of polymers prepared with AIBN or benzoyl peroxide as initiator
Publisher: Elsevier BV
Date: 1989
Aluminium-chloride-promoted reactions of ethyl acrylate with olefins
Publisher: CSIRO Publishing
Date: 1977
DOI: 10.1071/CH9772733
Abstract: Contrary to an earlier report,1 the aluminium-chloride-promoted reaction of ethyl acrylate with olefins does not afford cyclobutane derivatives. In benzene, ethyl acrylate reacts with isobutylene or 2,3-dimethylbut- 2-ene to afford the terminally unsaturated products (5) and (9) respectively. In 1,2-dichloroethane-nitromethane the initial products undergo isomerization or rearrangement. Un-ambiguous routes to 2,2- dimethylcyclobutanecarboxylic acid (19) and (2,2,3,3- tetramethylcyclobutyl)- methanol (26) are described.
Initiation. The reactions of primary radicals
Publisher: Wiley
Date: 10-1987
Living Radical Polymerization by the RAFT Process - A Second Update
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09311
Abstract: This paper provides a second update to the review of reversible deactivation radical polymerization 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, 379–410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669–692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a erse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.
“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization
Publisher: American Chemical Society (ACS)
Date: 21-05-2021
Mechanism and Kinetics of Dithiobenzoate‐Mediated RAFT Polymerization – Status of the Dilemma
Publisher: Wiley
Date: 14-08-2017
Frontispiz: Synthesis of Discrete Oligomers by Sequential PET‐RAFT Single‐Unit Monomer Insertion
Publisher: Wiley
Date: 05-07-2017
Understanding Key Factors Influencing Consumers’ Willingness to Try, Buy, and Pay a Price Premium for Mycoproteins
Publisher: MDPI AG
Date: 11-08-2022
DOI: 10.3390/NU14163292
Abstract: Mycoprotein is a fungal-based meat alternative sold in food retail in various countries around the world. The present study builds on a multi-national s le and uses partial least square structural equation modeling. The proposed conceptual model identified key factors that are driving and inhibiting consumer willingness to try, buy, and pay a price premium for mycoprotein. The results relate to the overall s le of 4088 respondents and to two subs le comparisons based on gender and meat consumption behavior. The results show that the biggest drivers of willingness to consume mycoprotein were healthiness, followed by nutritional benefits, safe to eat, and sustainability. Affordability and taste had mixed results. Willingness to consume mycoprotein was inhibited if nutritional importance was placed on meat and, to a lesser extent, if the taste, texture, and smell of meat were deemed important. Best practice recommendations address issues facing marketing managers in the food industry.
Living Radical Polymerization by the RAFT Process
Publisher: CSIRO Publishing
Date: 2005
DOI: 10.1071/CH05072
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.
Enhanced properties of well-defined polymer networks prepared by a sequential thiol-Michael - radical thiol-ene (STMRT) strategy
Publisher: Elsevier BV
Date: 05-2021
Invited Review. Understanding and Controlling Radical Polymerization
Publisher: CSIRO Publishing
Date: 1990
DOI: 10.1071/CH9900215
Abstract: The present state of our understanding of the mechanism of radical polymerization is summarized. The scope for control over the polymerization process so as to obtain predictable microstructure and reaction kinetics as well as optimal polymer properties is discussed and, where possible, illustrated by ex les from current research.
RAFT Polymerization: Materials of The Future, Science of Today: Radical Polymerization - The Next Stage
Publisher: CSIRO Publishing
Date: 2009
DOI: 10.1071/CH09549
A Brief Guide to Polymer Nomenclature
Publisher: Wiley
Date: 18-12-2012
DOI: 10.1002/PI.4442
Evaluation of propagation rate constants for the free radical polymerization of methacrylonitrile by pulsed laser photolysis
Publisher: Wiley
Date: 11-1995
An Industrial History of RAFT Polymerization
Publisher: Wiley
Date: 29-10-2021
An arm-first approach to cleavable mikto-arm star polymers by RAFT polymerization
Publisher: Wiley
Date: 06-02-2014
Abstract: Redox-cleavable mikto-arm star polymers are prepared by an "arm-first" approach involving copolymerization of a dimethacrylate mediated by a mixture of macroRAFT agents. Thus, RAFT copolymerization of the monomers BMA, DMAEMA, and OEGMA, with the disulfide dimethacrylate cross-linker (DSDMA), bis(2-methacryloyl)oxyethyl disulfide, mediated by a 1:1:1 mixture of three macroRAFT agents with markedly different properties [hydrophilic, poly[oligo(ethylene glycol) methacrylate]-P(OEGMA)8-9 cationizable, poly[2-(dimethylamino)ethyl methacrylate]-P(DMAEMA) hydrophobic, poly(n-butyl methacrylate)-P(BMA)] provides low dispersity mikto-arm star polymers. Good control (Đ < 1.3) is observed for the target P(DMAEMA)/P(OEGMA)/P(BMA) (3:3:1) mikto-arm star, a double hydrophilic P(DMAEMA)/P(OEGMA) (3:3) mikto-arm star and a hydrophobic P(BMA) homo-arm star. However, Đ for the target mikto-arm stars increases with an increase in either the ratio [DSDMA]:[total macroRAFT] or the fraction of hydrophobic P(BMA) macroRAFT agent. The quaternized mikto-arm star in dilute aqueous solution shows a monomodal particle size distribution and an average size of ≈145 nm.
Living Polymers by the Use of Trithiocarbonates as Reversible Addition−Fragmentation Chain Transfer (RAFT) Agents: ABA Triblock Copolymers by Radical Polymerization in Two Steps
Publisher: American Chemical Society (ACS)
Date: 2000
DOI: 10.1021/MA991451A
The effect of Z-group modification on the RAFT polymerization of N-vinylpyrrolidone mediated by switchable N-pyridyl-functional dithiocarbamates
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5PY01021G
Abstract: The polymerization of N -vinylpyrrolidone was examined with a series of cyanomethyl N -aryl- N -pyridyldithiocarbamates varying in the substituent at the 4-position on the phenyl ring.
Solvent effects on the reaction of t-butoxy radicals with methyl methacrylate
Publisher: CSIRO Publishing
Date: 1983
DOI: 10.1071/CH9832447
Abstract: Examination of the title reaction in a range of solvents shows that the ratio of hydrogen abstraction to t-butoxy radical addition increases with increasing solvent polarity. In several cases there is a competition between solvent and methyl methacrylate for reaction with t-butoxy radicals. The implications of these findings for polymer structure are discussed.
Mechanism and Kinetics of Dithiobenzoate‐Mediated RAFT Polymerization – Status of the Dilemma
Publisher: Wiley
Date: 09-12-2013
High‐Throughput/High‐Output Experimentation in
RAFT
Polymer Synthesis
Publisher: Wiley
Date: 29-10-2021
Binary copolymerization with catalytic chain transfer. A method for synthesizing macromonomers based on monosubstituted monomers
Publisher: American Chemical Society (ACS)
Date: 04-10-2005
DOI: 10.1021/MA0501949
Chemical modification of starch by reactive extrusion
Publisher: Elsevier BV
Date: 02-2011
Living radical polymerization by the RAFT process a third update
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH12295
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 erse 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.
Structural defects in polymers - their identification and significance
Publisher: Walter de Gruyter GmbH
Date: 1985
Mechanism and Kinetics of RAFT-Based Living Radical Polymerizations of Styrene and Methyl Methacrylate
Publisher: American Chemical Society (ACS)
Date: 2001
DOI: 10.1021/MA0009451
HOW POWERFUL ARE COMPOSITION DATA IN DISCRIMINATING BETWEEN THE TERMINAL AND PENULTIMATE MODELS FOR BINARY COPOLYMERIZATION
Publisher: American Chemical Society (ACS)
Date: 03-1989
DOI: 10.1021/MA00193A025
Polystyrene-block-poly(vinyl acetate) through the Use of a Switchable RAFT Agent
Publisher: American Chemical Society (ACS)
Date: 16-11-2009
DOI: 10.1021/MA9021086
Light‐Induced RAFT Single Unit Monomer Insertion in Aqueous Solution—Toward Sequence‐Controlled Polymers
Publisher: Wiley
Date: 13-06-2018
Abstract: First report on the sequential, visible light-initiated, single unit monomer insertion (SUMI) of N,N-dimethylacrylamide (DMAm) into the reversible addition fragmentation chain transfer (RAFT) agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (CTA
Developments in the synthesis of maleated polyolefins by reactive extrusion
Publisher: Wiley
Date: 03-1998
13C-1H heteronuclear chemical shift correlation spectroscopy applied to poly(methyl [carbonyl-13C]methacrylate): an unambiguous method for assigning resonances to configurational sequences
Publisher: American Chemical Society (ACS)
Date: 10-1986
DOI: 10.1021/MA00164A006
Reversible Addition–Fragmentation Chain Transfer Polymerization
Publisher: Wiley
Date: 2009
DOI: 10.1002/0471440264.PST564
Abstract: This article reviews the mechanistic and practical aspects of free radical polymerization with reversible addition–fragmentation chain transfer—the reversible addition–fragmentation chain transfer (RAFT) process. RAFT is conducted by the addition of a thiocarbonylthio compound (ZC(S)SR) to a conventional radical polymerization. Suitable RAFT agents include dithioesters, trithiocarbonates, dithiocarbamates, and xanthates. These thiocarbonylthio compounds confer living characteristics to the radical polymerization by a mechanism of reversible addition–fragmentation chain transfer and provide exceptional control over molecular weight, molecular weight distribution, composition, and architecture of the resulting polymers. The process can be applied to most monomers polymerizable by radical polymerization and offers a convenient route to well‐defined homo‐, gradient, diblock, triblock, and star polymers as well as more complex architectures including microgels and polymer brushes.
The Application of Supercomputers in Modeling Chemical Reaction Kinetics: Kinetic Simulation of 'Quasi-Living' Radical Polymerization
Publisher: CSIRO Publishing
Date: 1990
DOI: 10.1071/CH9901215
Abstract: A computer program has been written which employs an implicit Euler method to solve directly the complete set of coupled differential equations which result from an analysis of polymerization kinetics. The program was written to make full use of the speed and power of modern supercomputers, and is suited to the solution of very large stiff systems of differential equations. The benefit of treating each propagation step as a discrete reaction is that information on the evolution of the molecular weight distribution is obtained directly without the need to make perhaps unjustified assumptions such as the steady-state approximation. For illustrative purposes, the method has been applied in the kinetic simulation of 'quasi-living' radical polymerization to assess the effect of experimental variables on the molecular weight, molecular weight distribution, and rate of polymerization. The calculations show that 'quasi-living' radical polymerization can produce polymers with polydispersities approaching those obtained with anionic 'living' polymerizations. Some necessary conditions for the formation of polymers with narrow molecular weight distribution are defined.
Triphenylphosphine-grafted, RAFT-synthesised, porous monoliths as catalysts for Michael addition in flow synthesis
Publisher: Elsevier BV
Date: 11-2015
Living Free Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT Polymerization): Approaches to Star Polymers
Publisher: American Chemical Society (ACS)
Date: 14-02-2003
DOI: 10.1021/MA021219W
Electrochemical behavior of thiocarbonylthio chain transfer agents for RAFT polymerization
Publisher: American Chemical Society (ACS)
Date: 24-09-2019
Kinetic modelling of the reversible addition–fragmentation chain transfer polymerisation of N-isopropylacrylamide
Publisher: Elsevier BV
Date: 11-2019
Radical addition–fragmentation chemistry in polymer synthesis
Publisher: Elsevier BV
Date: 03-2008
Reconsidering terms for mechanisms of polymer growth: the “step-growth” and “chain-growth” dilemma
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00086E
Abstract: Terms used for mechanisms of polymer growth are varied and problematic we detail here our concerns with the terms “step-growth” and “chain-growth.” Ultimately, we seek terms that are simple, accurate, and attractive to the polymer community.
Radical-promoted single-unit monomer insertion (SUMI) [aka. reversible-deactivation radical addition (RDRA)]
Publisher: Elsevier BV
Date: 03-2023
COMPUTER-SIMULATION OF THE CHEMICAL-PROPERTIES OF COPOLYMERS
Publisher: Wiley
Date: 10-1991
Exploiting NIR Light-Mediated Surface-Initiated PhotoRAFT Polymerization for Orthogonal Control Polymer Brushes and Facile Postmodification of Complex Architecture through Opaque Barriers
Publisher: American Chemical Society (ACS)
Date: 22-09-2023
Alkoxyamine-Initiated Living Radical Polymerization: Factors Affecting Alkoxyamine Homolysis Rates
Publisher: American Chemical Society (ACS)
Date: 12-1995
DOI: 10.1021/MA00130A003
Thiocarbonylthio Compounds [SC(Ph)S−R] in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Role of the Free-Radical Leaving Group (R)
Publisher: American Chemical Society (ACS)
Date: 15-03-2003
DOI: 10.1021/MA020882H
Living Radical Polymerization with Reversible Addition−Fragmentation Chain Transfer (RAFT): Direct ESR Observation of Intermediate Radicals
Publisher: American Chemical Society (ACS)
Date: 22-07-1999
DOI: 10.1021/MA990316V
Thiocarbonylthio Compounds (SC(Z)S−R) in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Effect of the Activating Group Z
Publisher: American Chemical Society (ACS)
Date: 15-03-2003
DOI: 10.1021/MA020883+
Exploitation of Compartmentalization in RAFT Miniemulsion Polymerization to Increase the Degree of Livingness
Publisher: Wiley
Date: 05-02-2019
DOI: 10.1002/POLA.29329
Controlled growth free radical polymerization of methacrylate esters-reversible chain transfer vs. reversible termination
Publisher: American Chemical Society
Date: 08-01-1998
Head additon of radicals to methyl methacrylate
Publisher: Springer Science and Business Media LLC
Date: 1982
DOI: 10.1007/BF00255168
The kinetics and mechanism of ring opening of radicals containing the cyclobutylcarbinyl system
Publisher: Royal Society of Chemistry (RSC)
Date: 1980
DOI: 10.1039/P29800001083
The Reaction of Benzoyloxy Radicals with Styrene—Implications Concerning the Structure of Polystyrene
Publisher: Informa UK Limited
Date: 1982
A novel synthesis of functional dithioesters, dithiocarbamates, xanthates and trithiocarbonates
Publisher: Elsevier BV
Date: 03-1999
Imidazolidinone Nitroxide-Mediated Polymerization
Publisher: American Chemical Society (ACS)
Date: 10-1999
DOI: 10.1021/MA9904868
Block copolymer synthesis through the use of switchable RAFT agents
Publisher: American Chemical Society
Date: 2011
Selektive Bindungsspaltung in RAFT Agenzien durch niederenergetische Elektronenanlagerung
Publisher: Wiley
Date: 20-07-2021
Abstract: Radikalische Polymerisation mit reversibler Additions‐Fragmentierungs‐Kettenübertragung (RAFT Polymerisation) wird erfolgreich eingesetzt, um Polymere mit wohldefinierter Architektur zu erzeugen. Für die RAFT‐Polymerisation wird eine Quelle von Radikalen benötigt. Jüngste Arbeiten haben gezeigt, dass diese, für minimale Nebenreaktionen und hohe räumlich‐zeitliche Kontrolle, direkt aus dem RAFT‐Agens oder makroRAFT‐Agens (meist Carbonothiosulfanylverbindungen) thermisch, photochemisch oder durch elektrochemische Reduktion gebildet werden sollten. In dieser Arbeit untersuchten wir die niederenergetische Elektronenanlagerung an ein gängiges RAFT‐Agens (Cyanomethylbenzodithioat), und zum Vergleich eine einfache Carbonothioylsulfanylverbindung (Dimethyltrithiocarbonat, DMTTC), in der Gasphase mittels Massenspektrometrie sowie quantenchemischen Berechnungen. Wir beobachteten für beide Verbindungen, dass die spezifische Spaltung der C‐S‐Bindung bei niederenergetischer Elektronenanlagerung, bei Elektronenenergien nahe 0 eV erfolgt. Dies gilt auch im Falle einer schlechten homolytischen Abgangsgruppe ( . CH 3 in DMTTC). Alle anderen Dissoziationsreaktionen, die bei höheren Elektronenenergien auftreten, sind deutlich seltener. Die vorliegenden Ergebnisse zeigen eine hohe Kontrolle der durch Elektronenanlagerung induzierten chemischen Reaktionen.
15N CP/MAS solid-state NMR spectroscopy of a 15N-enriched hindered amine light stabilizer photolyzed in acrylic/melamine and acrylic/urethane coatings
Publisher: Elsevier BV
Date: 2000
Chemistry of Bimolecular Termination
Publisher: Elsevier
Date: 1989
Living polymerization: Rationale for uniform terminology
Publisher: Wiley
Date: 15-05-2000
DOI: 10.1002/(SICI)1099-0518(20000515)38:10<1706::AID-POLA20>3.0.CO;2-5
Tailored polymers by free radical processes
Publisher: Wiley
Date: 08-1999
Controlled synthesis of multifunctional polymers by RAFT for personal care applications
Publisher: American Chemical Society
Date: 2013
Consistent values of rate parameters in free radical polymerization systems
Publisher: Wiley
Date: 07-1988
Chapter 1: The history of nitroxidemediated polymerization
Publisher: Royal Society of Chemistry
Date: 2016
Structure of benzoyl peroxide initiated polystyrene: determination of the initiator-derived functionality by carbon-13 NMR
Publisher: American Chemical Society (ACS)
Date: 07-1982
DOI: 10.1021/MA00232A045
The mechanism of oxidation of 6-methyl-5-carba-5-deazatetrahydropterin. Evidence for the involvement cf a 4a-adduct in the oxidation of tetrahydropterins.
Publisher: Elsevier BV
Date: 1978
Controlled synthesis of block polyesters by reactive extrusion
Publisher: Wiley
Date: 10-2003
Synthesis of Discrete Oligomers by Sequential PET‐RAFT Single‐Unit Monomer Insertion
Publisher: Wiley
Date: 07-12-2016
Abstract: Uniform synthetic polymers with precisely defined molar mass and monomer sequence (primary structure) have many potential high-value applications. However, a robust and versatile synthetic strategy for these materials remains one of the great challenges in polymer synthesis. Herein we describe proof-of-principle experiments for a modular strategy to produce discrete oligomers by a visible-light-mediated radical chain process. We utilize the high selectivity provided by photo-induced electron/energy transfer (PET) activation to develop efficient single unit monomer insertion (SUMI) into reversible addition-fragmentation chain-transfer (RAFT) agents. A variety of discrete oligomers (single unit species, dimers, and, for the first time, trimers) have been synthesized by sequential SUMI in very high yield under mild reaction conditions. The trimers were used as building blocks for the construction of uniform hexamers and graft copolymers with precisely defined branches.
High-Throughput Process for the Discovery of Antimicrobial Polymers and Their Upscaled Production via Flow Polymerization
Publisher: American Chemical Society (ACS)
Date: 16-01-2020
Reversible addition–fragmentation chain transfer (co)polymerization of conjugated diene monomers: butadiene, isoprene and chloroprene
Publisher: Wiley
Date: 30-06-2017
DOI: 10.1002/PI.5173
On the mechanism of decomposition of geminal diamines
Publisher: American Chemical Society (ACS)
Date: 08-1978
DOI: 10.1021/JA00485A038
Effect of the Z‐ and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base “Switchable” Dithiocarbamate RAFT Agents
Publisher: Wiley
Date: 11-05-2018
Abstract: Thermolysis is examined as a method for complete desulfurization of reversible addition-fragmentation chain transfer (RAFT)-synthesized polymers prepared with acid/base "switchable" N-methyl-N-pyridyldithiocarbamates [RS
RAFT (Reversible addition-fragmentation chain transfer) crosslinking (co)polymerization of multi-olefinic monomers to form polymer networks
Publisher: Wiley
Date: 11-06-2015
DOI: 10.1002/PI.4767
Mechanism and kinetics of dithiobenzoate‐mediated RAFT polymerization. I. The current situation
Publisher: Wiley
Date: 11-09-2006
DOI: 10.1002/POLA.21589
Fungal Planet description sheets: 716–784
Publisher: Naturalis Biodiversity Center
Date: 30-06-2018
A Brief Guide to Polymer Nomenclature
Publisher: Elsevier BV
Date: 2013
A simple method for determining protic end-groups of synthetic polymers by H-1 NMR spectroscopy
Publisher: Elsevier BV
Date: 03-2006
Multiarm organic compounds for use as reversible chain-transfer agents in living radical polymerizations
Publisher: Elsevier BV
Date: 09-2002
A Comprehensive Platform for the Design and Synthesis of Polymer Molecular Weight Distributions
Publisher: American Chemical Society (ACS)
Date: 08-10-2020
A potential new RAFTClick reaction or a cautionary note on the use of diazomethane to methylate RAFT-synthesized polymers
Publisher: CSIRO Publishing
Date: 2011
DOI: 10.1071/CH10471
Abstract: It has been found that diazomethane undergoes a facile 1,3‐dipolar cycloaddition with both dithiobenzoate RAFT agents and the dithiobenzoate end‐groups of polymers formed by RAFT polymerization. Thus, 2‐cyanoprop‐2‐yl dithiobenzoate on treatment with diazomethane at room temperature provided a mixture of stereoisomeric 1,3‐dithiolanes in near quantitative ( %) yield. A low‐molecular‐weight RAFT‐synthesized poly(methyl methacrylate) with dithiobenzoate end‐groups underwent similar reaction as indicated by immediate decolourization and a quantitative doubling of molecular weight. Higher‐molecular‐weight poly(methyl methacrylate)s were also rapidly decolourized by diazomethane and provided a product with a bimodal molecular weight distribution. Under similar conditions, the trithiocarbonate group does not react with diazomethane.
Thermal stability of benzoyl peroxide-initiated polystyrene
Publisher: American Chemical Society (ACS)
Date: 03-1988
DOI: 10.1021/MA00181A051
The reaction of acyl peroxides with 2,2,6,6-tetramethylpiperidinyl-1-oxy
Publisher: Elsevier BV
Date: 1981
A Critical Survey of Dithiocarbamate Reversible Addition‐Fragmentation Chain Transfer (RAFT) Agents in Radical Polymerization
Publisher: Wiley
Date: 14-09-2019
DOI: 10.1002/POLA.29199
Abstract: This article provides a critical review of the properties, synthesis, and applications of dithiocarbamates Z′Z″NC(=S)SR as mediators in reversible addition‐fragmentation chain transfer (RAFT) polymerization. These are among the most versatile RAFT agents. Through choice of substituents on nitrogen (Z′, Z″), the polymerization of most monomer types can be controlled to provide living characteristics (i.e., low dispersities, high end‐group fidelity, and access to complex architectures). These include the more activated monomers (MAMs e.g., styrenes and acrylates) and the less activated monomers (LAMs e.g., vinyl esters and vinylamides). Dithiocarbamates with balanced activity (e.g., 1 H ‐pyrazole‐1‐carbodithioates) or switchable RAFT agents [e.g., a N ‐methyl‐ N ‐(4‐pyridinyl)dithiocarbamate] allow control MAMs and LAMs with a single RAFT agent and provide a pathway to low‐dispersity poly(MAM)‐ block ‐poly(LAM). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57 , 216–227
Triple Activity of Lamivudine Releasing Sulfonated Polymers against HIV-1
Publisher: American Chemical Society (ACS)
Date: 15-06-2016
DOI: 10.1021/ACS.MOLPHARMACEUT.6B00156
Abstract: In this article a library of polymeric therapeutic agents against the human immunodeficiency virus (HIV) is presented. The library of statistical copolymers of varied molar mass was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The synthesized polymers comprise pendent hydroxyl and sulfonated side chains as well as the reverse transcriptase prodrug lamivudine (3TC) attached via a disulfide self-immolative linker. The glutathione mediated release of 3TC is demonstrated as well as the antiviral efficacy against HIV entry and polymerase activity. Although a high degree of polymer sulfonation is required for effective HIV entry inhibition, polymers with approximately ∼50% sulfonated monomer demonstrated potent kinase independent reverse transcriptase inhibition. In addition, the sulfonated polymers demonstrate activity against DNA-DNA polymerase, which suggests that these polymers may exhibit activity against a broad spectrum of viruses. In summary, the polymers described provide a triple-active arsenal against HIV with extracellular activity via entry inhibition and intracellular activity by kinase-dependent lamivudine-based and kinase-independent sulfonated polymer based inhibition. Since these sulfonated copolymers are easily formulated into gels, we envision them to be particularly suited for topical application to prevent the mucosal transmission of viruses, particularly HIV.
A brief guide to polymer nomenclature (IUPAC Technical Report)
Publisher: Wiley
Date: 25-12-2012
DOI: 10.1002/PAT.3099
CRITICAL-POINTS (AZEOTROPIC COMPOSITIONS) IN MULTICOMPONENT COPOLYMERIZATION
Publisher: CSIRO Publishing
Date: 1986
DOI: 10.1071/CH9861877
Abstract: The necessary and sufficient conditions for the existence of critical points ( azeotropic compositions) in multicomponent copolymerization are defined, and the preferred method for calculating critical points for a given set of reactivity ratios is provided. This method offers considerable advantages in both simplicity and computation speed over methods already in the literature. A computer program for performing the calculation on systems with up to 10 components is briefly described. Approximate probabilities for the existence of critical points in ternary and quaternary systems have been evaluated as a function of whether binary critical points exist for pairs of the monomers involved. These data show that, contrary to the widely held view, in systems of three or more components all rij 1 or all rij 1is neither a necessary nor a sufficient condition for the existence of a critical point. Those systems which always and those systems which never give rise to critical points are indicated.
INFLUENCES OF THE INITIATION AND TERMINATION REACTIONS ON THE MOLECULAR-WEIGHT DISTRIBUTION AND COMPOSITIONAL HETEROGENEITY OF FUNCTIONAL COPOLYMERS - AN APPLICATION OF MONTE-CARLO SIMULATION
Publisher: American Chemical Society (ACS)
Date: 03-1987
DOI: 10.1021/MA00169A035
Studies on 6-methyl-5-deazatetrahydropterin and its 4a adducts
Publisher: American Chemical Society (ACS)
Date: 09-1979
DOI: 10.1021/JA00514A033
Narrow Polydispersity Block Copolymers by Free-Radical Polymerization in the Presence of Macromonomers
Publisher: American Chemical Society (ACS)
Date: 07-1995
DOI: 10.1021/MA00119A034
RAFT for the control of monomer sequence distribution - Single unit monomer insertion (SUMI) into dithiobenzoate RAFT agents
Publisher: American Chemical Society
Date: 2014
Kinetic data for coupling of primary alkyl radicals with a stable nitroxide
Publisher: Royal Society of Chemistry (RSC)
Date: 1986
DOI: 10.1039/C39860001003
Living free radical polymerization with reversible addition - fragmentation chain transfer (the life of RAFT)
Publisher: Wiley
Date: 2000
DOI: 10.1002/1097-0126(200009)49:9<993::AID-PI506>3.0.CO;2-6
Nano-Engineered Multiblock Copolymer Nanoparticles via Reversible Addition-Fragmentation Chain Transfer Emulsion Polymerization
Publisher: American Chemical Society (ACS)
Date: 03-04-2019
Chain Length Dependence of Radical−Radical Termination in Free Radical Polymerization: A Pulsed Laser Photolysis Investigation
Publisher: American Chemical Society (ACS)
Date: 22-02-2003
DOI: 10.1021/MA0209951
A brief guide to polymer nomenclature from IUPAC
Publisher: Springer Science and Business Media LLC
Date: 20-01-2013
Synthesis of well-defined polystyrene with primary amine end groups through the use of phthalimido-functional RAFT agents
Publisher: American Chemical Society (ACS)
Date: 08-07-2006
DOI: 10.1021/MA060245H
Non‐Ionic, Poly(ethylene oxide)‐Based Surfactants as Intercalants/Dispersants/Exfoliants for Poly(propylene)‐Clay Nanocomposites
Publisher: Wiley
Date: 22-12-2005
13C=O NMR Signal Assignments for Poly(n-butyl methacrylate-co-methyl methacrylate). Application of 13C-1H Correlation Spectroscopy and 13C Labelling
Publisher: Springer Science and Business Media LLC
Date: 11-1991
Terminology for reversible-deactivation radical polymerization previously called controlled radical or living radical polymerization (IUPAC recommendations 2010)
Publisher: Walter de Gruyter GmbH
Date: 18-11-2010
Abstract: This document defines terms related to modern methods of radical polymerization, in which certain additives react reversibly with the radicals, thus enabling the reactions to take on much of the character of living polymerizations, even though some termination inevitably takes place. In recent technical literature, these reactions have often been loosely referred to as, inter alia, "controlled", "controlled/living", or "living" polymerizations. The use of these terms is discouraged. The use of "controlled" is permitted as long as the type of control is defined at its first occurrence, but the full name that is recommended for these polymerizations is "reversible-deactivation radical polymerization".
Corrigendum to “The synthesis of polyolefin graft copolymers by reactive extrusion” [Progress in Polymer Science 1999;24:81–142]
Publisher: Elsevier BV
Date: 12-1999
Synthesis of cleavable multi-functional mikto-arm star polymer by RAFT polymerization: Example of an anti-cancer drug 7-ethyl-10-hydroxycamptothecin (SN-38) as functional moiety
Publisher: Springer Science and Business Media LLC
Date: 05-06-2014
Other Initiating Systems
Publisher: Elsevier
Date: 1989
Dithiocarbamate RAFT agents with broad applicability-the 3,5-dimethyl-1H-pyrazole-1-carbodithioates
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C5PY01382H
Abstract: The RAFT agents offer Đ 1.1 for MAMs, methyl acrylate (MA), N , N -dimethylacrylamide (DMA) and styrene, and Đ 1.3 for LAMs, vinyl acetate (VAc) versatility and end-group fidelity was proved with synthesis both polyDMA- block -polyMA and polyDMA- block -polyVAc.
Critical Points in Binary Copolymerization and the Penultimate Group Effect
Publisher: CSIRO Publishing
Date: 1985
DOI: 10.1071/CH9851287
Abstract: In order to examine the influence that a penultimate group effect can have on the number and magnitude of critical points ( azeotropic compositions) in binary copolymerization an expression for the critical point(s) has been derived. Analysis of this relationship shows that in a situation where one critical point would have been expected on the basis of terminal-model kinetics (no penultimate group effect) a modest penultimate group effect can mean that zero, one or three critical points may exist, or, in systems where no critical points would have been predicted, two critical points may exist.
Trithiocarbonates in RAFT Polymerization
Publisher: Wiley
Date: 29-10-2021
Rheological properties of high melt strength poly(ethylene terephthalate) formed by reactive extrusion
Publisher: Wiley
Date: 27-03-2006
DOI: 10.1002/APP.23166
Dithioesters in RAFT Polymerization
Publisher: Wiley
Date: 29-10-2021
Chapter 5: RAFT Polymerization: Mechanistic Considerations
Publisher: Wiley
Date: 29-10-2021
Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers
Publisher: CSIRO Publishing
Date: 2021
DOI: 10.1071/CH20260
Abstract: We report on two important advances in radical polymerization with reversible addition–fragmentation chain transfer (RAFT polymerization). (1) Electrochemically initiated emulsion RAFT (eRAFT) polymerization provides rapid polymerization of styrene at ambient temperature. The electrolytes and mediators required for eRAFT are located in the aqueous continuous phase separate from the low-molar-mass-dispersity macroRAFT agent mediator and product in the dispersed phase. Use of a poly(N,N-dimethylacrylamide)-block-poly(butyl acrylate) hiphilic macroRAFT agent composition means that no added surfactant is required for colloidal stability. (2) Direct photoinitiated (visible light) RAFT polymerization provides an effective route to high-purity, low-molar-mass-dispersity, side chain liquid-crystalline polymers (specifically, poly(4-biphenyl acrylate)) at high monomer conversion. Photoinitiation gives a product free from low-molar-mass initiator-derived by-products and with minimal termination. The process is compared with thermal dialkyldiazene initiation in various solvents. Numerical simulation was found to be an important tool in discriminating between the processes and in selecting optimal polymerization conditions.
Chapter 2: Terminology in reversible deactivation radical polymerization (RDRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization
Publisher: Wiley
Date: 29-10-2021
Expanding the Scope of RAFT Multiblock Copolymer Synthesis Using the Nanoreactor Concept: The Critical Importance of Initiator Hydrophobicity
Publisher: American Chemical Society (ACS)
Date: 03-03-2022
Evolution of Molar Mass Distributions Using a Method of Partial Moments: Initiation of RAFT Polymerization
Publisher: MDPI AG
Date: 18-11-2022
Abstract: We describe a method of partial moments devised for accurate simulation of the time/conversion evolution of polymer composition and molar mass. Expressions were derived that enable rigorous evaluation of the complete molar mass and composition distribution for shorter chain lengths (e.g., degree of polymerization, Xn = N 200 units) while longer chains (Xn ≥ 200 units) are not neglected, rather they are explicitly considered in terms of partial moments of the molar mass distribution, μxN(P)=∑n=N+1∞nx[Pn] (where P is a polymeric species and n is its’ chain length). The methodology provides the exact molar mass distribution for chains Xn N, allows accurate calculation of the overall molar mass averages, the molar mass dispersity and standard deviations of the distributions, provides closure to what would otherwise be an infinite series of differential equations, and reduces the stiffness of the system. The method also allows for the inclusion of the chain length dependence of the rate coefficients associated with the various reaction steps (in particular, termination and propagation) and the various side reactions that may complicate initiation or initialization. The method is particularly suited for the detailed analysis of the low molar mass portion of molar mass distributions of polymers formed by radical polymerization with reversible addition-fragmentation chain transfer (RAFT) and is relevant to designing the RAFT-synthesis of sequence-defined polymers. In this paper, we successfully apply the method to compare the behavior of thermally initiated (with an added dialkyldiazene initiator) and photo-initiated (with a RAFT agent as a direct photo-iniferter) RAFT-single-unit monomer insertion (RAFT-SUMI) and oligomerization of N,N-dimethylacrylamide (DMAm).
Synthesis of Discrete Oligomers by Sequential PET‐RAFT Single‐Unit Monomer Insertion
Publisher: Wiley
Date: 07-12-2016
Selective Bond Cleavage in RAFT Agents Promoted by Low‐Energy Electron Attachment
Publisher: Wiley
Date: 20-07-2021
Abstract: Radical polymerization with reversible addition‐fragmentation chain transfer (RAFT polymerization) has been successfully applied to generate polymers of well‐defined architecture. For RAFT polymerization a source of radicals is required. Recent work has demonstrated that for minimal side‐reactions and high spatio‐temporal control these should be formed directly from the RAFT agent or macroRAFT agent (usually carbonothiosulfanyl compounds) thermally, photochemically or by electrochemical reduction. In this work, we investigated low‐energy electron attachment to a common RAFT agent (cyanomethyl benzodithioate), and, for comparison, a simple carbonothioylsulfanyl compound (dimethyl trithiocarbonate, DMTTC) in the gas phase by means of mass spectrometry as well as quantum chemical calculations. We observe for both compounds that specific cleavage of the C−S bond is induced upon low‐energy electron attachment at electron energies close to zero eV. This applies even in the case of a poor homolytic leaving group ( . CH 3 in DMTTC). All other dissociation reactions found at higher electron energies are much less abundant. The present results show a high control of the chemical reactions induced by electron attachment.
A Critical Assessment of the Kinetics and Mechanism of Initiation of Radical Polymerization with Commercially Available Dialkyldiazene Initiators.
Publisher: Elsevier BV
Date: 2019
Correction: Polymerization-Induced Self-Assembly via RAFT in Emulsion: Effect of Z-Group on the Nucleation Step
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY90021H
Abstract: Correction for ‘Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step’ by Thiago R. Guimarães et al. , Polym. Chem. , 2021, 12 , 122–133, DOI: 10.1039/D0PY01311K.
On the regioselectivity of free radical processes ; reactions of benzoyloxy, phenyl and t-butoxy radicals with some α,β-unsaturated esters
Publisher: CSIRO Publishing
Date: 1983
DOI: 10.1071/CH9831573
Abstract: The reactions of three electrophilic radicals, benzoyloxy, phenyl, and t-butoxy, have been examined with a series of α, β unsaturated esters methyl acrylate, methyl methacrylate, and methyl crotonate. For the three monomers the ratio of hydrogen abstraction to double bond addition was found to increase and the ratio of head against tail addition to decrease in the series: benzoyloxy phenyl t-butoxy. Relative rates for these reactions have been determined and the factors influencing the mode of reaction are discussed.
Preparation of 1 : 1 alternating, nucleobase-containing copolymers for use in sequence-controlled polymerization
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4PY01247J
Abstract: Despite recent advances in template polymerization, control of repeat unit sequence requires further development. We describe herein the synthesis of StyThy- alt -MAh sequence-regulated copolymers.
Chain Transfer Activity of ω-Unsaturated Methacrylic Oligomers in Polymerizations of Methacrylic Monomers
Publisher: American Chemical Society (ACS)
Date: 18-05-2004
DOI: 10.1021/MA049813O
New Features of the Mechanism of RAFT Polymerization
Publisher: American Chemical Society
Date: 13-08-2009
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Commonwealth Scientific And Industrial Research Organisation
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