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Prof. Graeme Moad
CSIRO Manufacturing

Basic Info


Research Keywords & Expertise

0 Polymer Chemistry
0 Polymer Synthesis
0 Polymer Design
0 Radical Polymerization
0 Polymerization Mechanisms

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Radical Polymerization
Polymer Chemistry
Polymer Synthesis
Polymerization Mechanisms

Honors and Awards

Citation Laureate 2014

Clarivate Analytics


Clunies Ross Award 2014

Better ways of making plastics

Australian Academy of Techology & Engineering


David Craig Medal 2020

outstanding achievement in the field of Chemistry

Australian Academy of Science




Career Timeline

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Short Biography

Graeme Moad obtained his BSc (Hons, First Class, 1974) and PhD (1978) from the University of Adelaide in organic free radical chemistry. Between 1977 and 1979, he undertook post-doctoral research at Pennsylvania State University with Prof Steven J. Benkovic in the field of biological organic chemistry. He joined CSIRO in 1979 where he is currently a CSIRO fellow. Dr Moad is (co)author of over 200 publications, co-inventor on 38 patent families and co-author of the book “The Chemistry of Radical Polymerization” (3rd edition in preparation). His research interests lie in the fields of polymerization mechanisms, and polymer design and synthesis. In recognition of his work Dr Moad was awarded a CSIRO medal in 2003, the RACI’s Battaerd-Jordan Polymer Medal in 2012, a Clunies Ross Award and a Thomson-Reuters' Citation Laureate in 2014, a Warwick University IAS Fellowship, a CSIRO Newton-Turner award and Thomson-Reuters' Highly Cited List in 2015 and the Australian Academy of Science's David Craig Medal for outstanding achievement in the field of Chemistry in 2020. Dr Moad is currently also an adjunct professor at Monash University, and an honorary professor at the Beijing University of Chemical Technology. He is an Associate Member of the IUPAC Polymer Division and the Division representative on the International Committee for Terminology, Nomenclature and Standards (ICTNS). He is a Fellow of the Royal Australian Chemical Institute and the Australian Academy of Science.

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Review
Published: 23 July 2021 in Sustainability
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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.

ACS Style

Graeme Moad; David Solomon. The Critical Importance of Adopting Whole-of-Life Strategies for Polymers and Plastics. Sustainability 2021, 13, 8218 .

AMA Style

Graeme Moad, David Solomon. The Critical Importance of Adopting Whole-of-Life Strategies for Polymers and Plastics. Sustainability. 2021; 13 (15):8218.

Chicago/Turabian Style

Graeme Moad; David Solomon. 2021. "The Critical Importance of Adopting Whole-of-Life Strategies for Polymers and Plastics." Sustainability 13, no. 15: 8218.

Communication
Published: 02 July 2021 in Angewandte Chemie
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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 and 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.

ACS Style

Farhad Izadi; Eugene Arthur‐Baidoo; Lisa T. Strover; Li‐Juan Yu; Michelle L. Coote; Graeme Moad; Stephan Denifl. Selektive Bindungsspaltung in RAFT Agenzien durch niederenergetische Elektronenanlagerung. Angewandte Chemie 2021, 133, 19276 -19281.

AMA Style

Farhad Izadi, Eugene Arthur‐Baidoo, Lisa T. Strover, Li‐Juan Yu, Michelle L. Coote, Graeme Moad, Stephan Denifl. Selektive Bindungsspaltung in RAFT Agenzien durch niederenergetische Elektronenanlagerung. Angewandte Chemie. 2021; 133 (35):19276-19281.

Chicago/Turabian Style

Farhad Izadi; Eugene Arthur‐Baidoo; Lisa T. Strover; Li‐Juan Yu; Michelle L. Coote; Graeme Moad; Stephan Denifl. 2021. "Selektive Bindungsspaltung in RAFT Agenzien durch niederenergetische Elektronenanlagerung." Angewandte Chemie 133, no. 35: 19276-19281.

Communication
Published: 02 July 2021 in Angewandte Chemie International Edition
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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 and 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.

ACS Style

Farhad Izadi; Eugene Arthur‐Baidoo; Lisa T. Strover; Li‐Juan Yu; Michelle L. Coote; Graeme Moad; Stephan Denifl. Selective Bond Cleavage in RAFT Agents Promoted by Low‐Energy Electron Attachment. Angewandte Chemie International Edition 2021, 60, 19128 -19132.

AMA Style

Farhad Izadi, Eugene Arthur‐Baidoo, Lisa T. Strover, Li‐Juan Yu, Michelle L. Coote, Graeme Moad, Stephan Denifl. Selective Bond Cleavage in RAFT Agents Promoted by Low‐Energy Electron Attachment. Angewandte Chemie International Edition. 2021; 60 (35):19128-19132.

Chicago/Turabian Style

Farhad Izadi; Eugene Arthur‐Baidoo; Lisa T. Strover; Li‐Juan Yu; Michelle L. Coote; Graeme Moad; Stephan Denifl. 2021. "Selective Bond Cleavage in RAFT Agents Promoted by Low‐Energy Electron Attachment." Angewandte Chemie International Edition 60, no. 35: 19128-19132.

Research article
Published: 21 May 2021 in Macromolecules
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Xanthate-mediated RAFT polymerization has been used to prepare 3-star and 4-star-poly(vinyl chloride) (star-PVC) with a number average molar mass (Mn) in the range of 1 to 7 kg mol–1. The Tg of star-PVC reduces with molar mass and with the number of arms. The star-PVC have substantially lower glass-transition temperatures (Tg) than that of linear PVC of similar Mn, with the Tg of low-molar mass 4-star-PVC being −7.4 °C. The star-PVC are effective in lowering the Tg of blends with commercial PVC when added at 10–30 wt % PVC. When added even at 10 wt %, they are effective in improving the ductility of PVC with an elongation at break (EB) of ∼350% (4-star-PVC) and ∼300% (3-star-PVC) relative to commercial PVC, which is substantially higher than that for PVC conventionally plasticized with 30 wt % dioctyl phthalate under similar conditions (EB ∼160%). Importantly, the star-PVC, despite their low molar mass, do not migrate from the PVC blends when tested under standard conditions. The performance of the star-PVC as non-migratory plasticizers for PVC demonstrates the potential for an “all-PVC” flexible PVC.

ACS Style

Zhonghe Sun; Xing Mi; Yanan Yu; Wencheng Shi; Anchao Feng; Graeme Moad; San H. Thang. “All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization. Macromolecules 2021, 54, 5022 -5032.

AMA Style

Zhonghe Sun, Xing Mi, Yanan Yu, Wencheng Shi, Anchao Feng, Graeme Moad, San H. Thang. “All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization. Macromolecules. 2021; 54 (11):5022-5032.

Chicago/Turabian Style

Zhonghe Sun; Xing Mi; Yanan Yu; Wencheng Shi; Anchao Feng; Graeme Moad; San H. Thang. 2021. "“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization." Macromolecules 54, no. 11: 5022-5032.

Research article
Published: 05 April 2021 in Macromolecules
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Synthesis of multiblock copolymers using seeded reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization has been explored with a view to elucidate how certain experimental conditions influence the control over molecular weight distribution (MWD). Two separate parameters have been explored in detail: (i) the ratio of monomer concentration to the RAFT end group concentration within particles and (ii) the glass transition temperature (Tg) of the particles. The parameters (i) and (ii) are interrelated as an increase in the ratio [monomer]:[RAFT] leads to a lower Tg because of the increased plasticization of the polymer particle by the monomer. Three different monomers were employed, each giving a polymer of different Tg values: n-butyl methacrylate (Tg = 20 °C), iso-butyl methacrylate (Tg = 57 °C), and tert-butyl methacrylate (Tg = 118 °C). The results show that the level of control over the MWDs via the RAFT mechanism is markedly reduced under conditions where Tg of the polymer particles is high. This is attributed to the high Tg value, leading to low radical penetration rates (low diffusion rates) of radicals generated via initiation in the aqueous phase, preventing propagating radicals from reaching the core region of the particles before bimolecular termination occurs. In the present system, the RAFT end groups are predominantly (but not at all exclusively) located in the core region of the particles.

ACS Style

Glenn K. K. Clothier; Thiago R. Guimarães; Graeme Moad; Per B. Zetterlund. Multiblock Copolymer Synthesis via Reversible Addition–Fragmentation Chain Transfer Emulsion Polymerization: Effects of Chain Mobility within Particles on Control over Molecular Weight Distribution. Macromolecules 2021, 54, 3647 -3658.

AMA Style

Glenn K. K. Clothier, Thiago R. Guimarães, Graeme Moad, Per B. Zetterlund. Multiblock Copolymer Synthesis via Reversible Addition–Fragmentation Chain Transfer Emulsion Polymerization: Effects of Chain Mobility within Particles on Control over Molecular Weight Distribution. Macromolecules. 2021; 54 (8):3647-3658.

Chicago/Turabian Style

Glenn K. K. Clothier; Thiago R. Guimarães; Graeme Moad; Per B. Zetterlund. 2021. "Multiblock Copolymer Synthesis via Reversible Addition–Fragmentation Chain Transfer Emulsion Polymerization: Effects of Chain Mobility within Particles on Control over Molecular Weight Distribution." Macromolecules 54, no. 8: 3647-3658.

Research article
Published: 17 March 2021 in Macromolecules
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In this work, we demonstrate the controlled synthesis of graft and branched copolymers using one-pot (batch) or one-pass (flow) processes without intermediate purification. The formation of poly(methacrylate) copolymers with pendent reversible addition–fragmentation chain transfer (RAFT) agent functionalities was performed using a selective photoactivation approach in the first step, specifically via green light-mediated direct photoRAFT polymerization. A nonselective photoinduced chain extension using red light-triggered photoinduced energy/electron transfer (PET)-RAFT polymerization was then performed to provide tailored graft copolymers. Notably, the application of this protocol to a flow process with two spatially segregated unit operations provides a route to independent control of the backbone-forming step (unit operation one) and the subsequent chain extensions (unit operation two). By alternating the light sources in both unit operations between the On and Off states, a range of macromolecular architectures could be prepared from the same starting materials. To demonstrate the power of this divergent approach, a series of graft copolymers with tailored backbone lengths and number and molecular weight characteristics of side chains were synthesized using the same starting materials by a single pass process. Additionally, the polymer architecture was switched between graft and hyperbranched architectures via external manipulation of light sources.

ACS Style

Nathaniel Corrigan; Francisco J. Trujillo; Jiangtao Xu; Graeme Moad; Craig J. Hawker; Cyrille Boyer. Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors. Macromolecules 2021, 54, 3430 -3446.

AMA Style

Nathaniel Corrigan, Francisco J. Trujillo, Jiangtao Xu, Graeme Moad, Craig J. Hawker, Cyrille Boyer. Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors. Macromolecules. 2021; 54 (7):3430-3446.

Chicago/Turabian Style

Nathaniel Corrigan; Francisco J. Trujillo; Jiangtao Xu; Graeme Moad; Craig J. Hawker; Cyrille Boyer. 2021. "Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors." Macromolecules 54, no. 7: 3430-3446.

Research article
Published: 05 January 2021 in Macromolecules
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Synthesis of (multi)block copolymers using reversible addition–fragmentation chain transfer (RAFT) polymerization generally suffers from the limitation that the order of the blocks must be considered. Herein, syntheses of block copolymers by RAFT polymerization using trithiocarbonate RAFT species are conducted as solution, miniemulsion, and emulsion polymerizations to demonstrate that the issue of monomer order for styrene and butyl methacrylate can be largely overcome in emulsion polymerization under carefully chosen conditions. The presence of monomer droplets in emulsion polymerization—in addition to polymer particles that constitute the locus of polymerization—leads to a reduction in the ratio of RAFT end groups to monomer at the locus of polymerization. Consequently, fragmentation of the RAFT adduct radical in the “backward” (“wrong”) direction is associated with fewer monomer additions, thus minimizing the impact of this undesired kinetic event. It is demonstrated that RAFT emulsion polymerization can be exploited to prepare an alternating pentablock copolymer composed of methacrylates (with 10 mol % styrene) and styrene without consideration of monomer order, thereby significantly broadening the scope of RAFT polymerization for multiblock copolymer synthesis.

ACS Style

Murtaza Khan; Thiago R. Guimarães; Kenneth Choong; Graeme Moad; Sébastien Perrier; Per B. Zetterlund. RAFT Emulsion Polymerization for (Multi)block Copolymer Synthesis: Overcoming the Constraints of Monomer Order. Macromolecules 2021, 54, 736 -746.

AMA Style

Murtaza Khan, Thiago R. Guimarães, Kenneth Choong, Graeme Moad, Sébastien Perrier, Per B. Zetterlund. RAFT Emulsion Polymerization for (Multi)block Copolymer Synthesis: Overcoming the Constraints of Monomer Order. Macromolecules. 2021; 54 (2):736-746.

Chicago/Turabian Style

Murtaza Khan; Thiago R. Guimarães; Kenneth Choong; Graeme Moad; Sébastien Perrier; Per B. Zetterlund. 2021. "RAFT Emulsion Polymerization for (Multi)block Copolymer Synthesis: Overcoming the Constraints of Monomer Order." Macromolecules 54, no. 2: 736-746.

Journal article
Published: 01 January 2021 in Australian Journal of Chemistry
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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) amphiphilic 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.

ACS Style

Caroline Bray; Guoxin Li; Almar Postma; Lisa T. Strover; Jade Wang; Graeme Moad. Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers. Australian Journal of Chemistry 2021, 74, 56 .

AMA Style

Caroline Bray, Guoxin Li, Almar Postma, Lisa T. Strover, Jade Wang, Graeme Moad. Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers. Australian Journal of Chemistry. 2021; 74 (1):56.

Chicago/Turabian Style

Caroline Bray; Guoxin Li; Almar Postma; Lisa T. Strover; Jade Wang; Graeme Moad. 2021. "Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers." Australian Journal of Chemistry 74, no. 1: 56.

Journal article
Published: 29 December 2020 in Chemistry Teacher International
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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.

ACS Style

Catherine L. Moad; Graeme Moad. Fundamentals of reversible addition–fragmentation chain transfer (RAFT). Chemistry Teacher International 2020, 3, 3 -17.

AMA Style

Catherine L. Moad, Graeme Moad. Fundamentals of reversible addition–fragmentation chain transfer (RAFT). Chemistry Teacher International. 2020; 3 (2):3-17.

Chicago/Turabian Style

Catherine L. Moad; Graeme Moad. 2020. "Fundamentals of reversible addition–fragmentation chain transfer (RAFT)." Chemistry Teacher International 3, no. 2: 3-17.

Research article
Published: 25 November 2020 in Macromolecules
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A goal in applying electrochemical methods to reversible addition–fragmentation chain transfer (RAFT) polymerization is to use electrochemical reduction to activate RAFT agents (S═C(Z)S-R) to also act as initiators. The use of a mediator can limit side reactions that would otherwise inhibit polymerization. In this work, we present the use of anthraquinone (AQ) to mediate the electrochemical reduction of a trithiocarbonate RAFT agent, 4-cyano-4-(((dodecylthio)carbonothioyl)thio)pentanoic acid, and thereby initiate RAFT polymerization of methyl methacrylate (MMA). In a representative eRAFT reaction conducted in DMSO with a target degree of polymerization (DP) of 100, conversion reached 67% in 24 h at ambient temperature, with Đ = 1.19. The effect of reaction conditions on polymerization was studied—in general, the conversion rate was found to decrease as target DP increases. Dispersity increases as (i) target DP increases and (ii) mediator concentration increases. The livingness of AQ-mediated eRAFT polymerization was confirmed by eRAFT chain extension with MMA and by thermally initiated RAFT with styrene to form a block copolymer. AQ-mediated eRAFT was found to be unsuitable for polymerization of monosubstituted monomers (styrene, butyl acrylate, N,N-dimethylacrylamide, and N-vinylpyrrolidone). These results support the hypothesis that mediated electrochemical reduction of RAFT agents can yield an initiating species (R•), although polymerization is strongly dependent on diffusion and fragmentation kinetics.

ACS Style

Lisa T. Strover; Almar Postma; Michael D. Horne; Graeme Moad. Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible Addition–Fragmentation Chain Transfer Polymerization. Macromolecules 2020, 53, 10315 -10322.

AMA Style

Lisa T. Strover, Almar Postma, Michael D. Horne, Graeme Moad. Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible Addition–Fragmentation Chain Transfer Polymerization. Macromolecules. 2020; 53 (23):10315-10322.

Chicago/Turabian Style

Lisa T. Strover; Almar Postma; Michael D. Horne; Graeme Moad. 2020. "Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible Addition–Fragmentation Chain Transfer Polymerization." Macromolecules 53, no. 23: 10315-10322.

Paper
Published: 16 October 2020 in Polymer Chemistry
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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.

ACS Style

Thiago R. Guimarães; Y. Loong Bong; Steven W. Thompson; Graeme Moad; Sébastien Perrier; Per B. Zetterlund. Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step. Polymer Chemistry 2020, 12, 122 -133.

AMA Style

Thiago R. Guimarães, Y. Loong Bong, Steven W. Thompson, Graeme Moad, Sébastien Perrier, Per B. Zetterlund. Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step. Polymer Chemistry. 2020; 12 (1):122-133.

Chicago/Turabian Style

Thiago R. Guimarães; Y. Loong Bong; Steven W. Thompson; Graeme Moad; Sébastien Perrier; Per B. Zetterlund. 2020. "Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step." Polymer Chemistry 12, no. 1: 122-133.

Review article
Published: 14 October 2020 in Progress in Polymer Science
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Reversible-deactivation radical polymerization (RDRP) processes, such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization and nitroxide mediated polymerization (NMP) have revolutionized polymer synthesis by providing polymer chemists with powerful tools that enable control over architecture, composition and chain length distributions. The user-friendly nature of these procedures have allowed RDRP-derived polymers to be used in the construction of advanced materials with unique and enhanced properties. This review covers the progress of RDRP from its conception to the current state-of-the-art. A brief introduction to the sources of RDRP, general mechanisms, and methodological progressions are presented, and the suite of advanced and highly tailorable materials possible through these techniques is discussed to illustrate the significant potential for even greater impact across multiple disciplines.

ACS Style

Nathaniel Corrigan; Kenward Jung; Graeme Moad; Craig J. Hawker; Krzysztof Matyjaszewski; Cyrille Boyer. Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications. Progress in Polymer Science 2020, 111, 101311 .

AMA Style

Nathaniel Corrigan, Kenward Jung, Graeme Moad, Craig J. Hawker, Krzysztof Matyjaszewski, Cyrille Boyer. Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications. Progress in Polymer Science. 2020; 111 ():101311.

Chicago/Turabian Style

Nathaniel Corrigan; Kenward Jung; Graeme Moad; Craig J. Hawker; Krzysztof Matyjaszewski; Cyrille Boyer. 2020. "Reversible-deactivation radical polymerization (Controlled/living radical polymerization): From discovery to materials design and applications." Progress in Polymer Science 111, no. : 101311.

Research article
Published: 08 October 2020 in Macromolecules
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The molecular weight distribution (MWD) has a significant impact on the properties of polymeric materials; however, the characterization of polymer MWDs has been limited to statistical parameters such as the number average molecular weight (Mn) and dispersity (Đ). These parameters do not fully express the features of polymer MWDs, thus limiting the ability to rationally design complex polymeric materials with tailored MWDs. Herein, a platform for the design and synthesis of arbitrary polymer MWDs is developed and experimentally validated. The platform is based on the description of polymer MWDs as a mathematical function, rather than individual statistical parameters. As such, the complete shape of arbitrary polymer MWDs can be designed using developed software. The software requires only a calibration using model monomodal MWDs directly obtained from GPC to design theoretical MWD. Using this platform in conjunction with a flow-mediated polymerization approach, a range of arbitrarily shaped polymer MWDs were successfully designed and prepared. Finally, complex triblock copolymer mixtures with tailored compositions and overall MWD were fabricated via one-pass flow-mediated polymerization using this computer-guided approach.

ACS Style

Ke Liu; Nathaniel Corrigan; Almar Postma; Graeme Moad; Cyrille Boyer. A Comprehensive Platform for the Design and Synthesis of Polymer Molecular Weight Distributions. Macromolecules 2020, 53, 8867 -8882.

AMA Style

Ke Liu, Nathaniel Corrigan, Almar Postma, Graeme Moad, Cyrille Boyer. A Comprehensive Platform for the Design and Synthesis of Polymer Molecular Weight Distributions. Macromolecules. 2020; 53 (20):8867-8882.

Chicago/Turabian Style

Ke Liu; Nathaniel Corrigan; Almar Postma; Graeme Moad; Cyrille Boyer. 2020. "A Comprehensive Platform for the Design and Synthesis of Polymer Molecular Weight Distributions." Macromolecules 53, no. 20: 8867-8882.

Journal article
Published: 02 October 2020 in Pure and Applied Chemistry
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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’.

ACS Style

Christopher M. Fellows; Karl-Heinz Hellwich; Stefano V. Meille; Graeme Moad; Tamaki Nakano; Michel Vert. Definitions and notations relating to tactic polymers (IUPAC Recommendations 2020). Pure and Applied Chemistry 2020, 92, 1769 -1779.

AMA Style

Christopher M. Fellows, Karl-Heinz Hellwich, Stefano V. Meille, Graeme Moad, Tamaki Nakano, Michel Vert. Definitions and notations relating to tactic polymers (IUPAC Recommendations 2020). Pure and Applied Chemistry. 2020; 92 (11):1769-1779.

Chicago/Turabian Style

Christopher M. Fellows; Karl-Heinz Hellwich; Stefano V. Meille; Graeme Moad; Tamaki Nakano; Michel Vert. 2020. "Definitions and notations relating to tactic polymers (IUPAC Recommendations 2020)." Pure and Applied Chemistry 92, no. 11: 1769-1779.

Research article
Published: 03 September 2020 in Macromolecules
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We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (Đ) ≤1.15) over polymerizations mediated by reversible addition–fragmentation chain transfer (RAFT) agents with relatively low transfer constants (Ctr). An amphiphilic RAFT agent [RSC(═S)Z], based on a hydrophilic methacrylic R-group [Ċ(CH3)2CO2-PEG] and a hydrophobic Z group with Ctr ≈ 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low Ctr, batch miniemulsion or solution polymerizations did not provide polymers with low Đ. The issue of a low Ctr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.

ACS Style

Robert A. E. Richardson; Thiago R. Guimarães; Murtaza Khan; Graeme Moad; Per B. Zetterlund; Sébastien Perrier. Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media. Macromolecules 2020, 53, 7672 -7683.

AMA Style

Robert A. E. Richardson, Thiago R. Guimarães, Murtaza Khan, Graeme Moad, Per B. Zetterlund, Sébastien Perrier. Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media. Macromolecules. 2020; 53 (18):7672-7683.

Chicago/Turabian Style

Robert A. E. Richardson; Thiago R. Guimarães; Murtaza Khan; Graeme Moad; Per B. Zetterlund; Sébastien Perrier. 2020. "Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media." Macromolecules 53, no. 18: 7672-7683.

Research article
Published: 19 May 2020 in Macromolecules
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A versatile approach to the synthesis of migration-resistant poly(vinyl chloride) (PVC) additives is described and a preliminary assessment of their properties is presented. The process involves the synthesis of AB2 3-mikto-arm stars, star-[PVC-block-(polyB);(polyB)2] or star-[PVC;(polyB)2], that contain a reversible addition-fragmentation chain transfer (RAFT)-synthesized PVC segment, to provide compatibility with PVC and good migration resistance, and multiple RAFT-synthesized segments (polyB), where polyB is based on more activated monomer (a styrene or a methacrylate) that contains the functionality required to impart the desired additive properties. The approach to PVC-based stars comprises three steps: (a) synthesis of a hydroxy-functional PVC [X-PVC(OH)n] by RAFT polymerization mediated by a hydroxy-functional xanthate [X-(OH)n], (b) conversion of the X-PVC(OH)n to the corresponding trithiocarbonate, X-PVC-(CDTPA)n, by the Steglich esterification with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (CDTPA), and (c) formation of star polymer additives by RAFT polymerization mediated by X-PVC-(CDTPA)n. The stars prepared include a plasticizer (B = butyl acrylate), a reactive dispersant for use in forming silica nanocomposites (B = 3-methacryloxypropyltrimethoxysilane), UV stabilizers (B = 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate or 2-hydroxy-4-acryloxybenzophenone), and flame retardants (B = 4-vinylbenzyl phosphonate or (diethoxyphosphoryl)methyl methacrylate). Although much optimization remains to be done, our preliminary study shows that the synthesized mikto-arm star additives can be effective in imparting the anticipated properties to PVC.

ACS Style

Zhonghe Sun; Mu Wang; Zhi Li; Bonnie Choi; Roger J. Mulder; Anchao Feng; Graeme Moad; San H. Thang. Versatile Approach for Preparing PVC-Based Mikto-Arm Star Additives Based on RAFT Polymerization. Macromolecules 2020, 53, 4465 -4479.

AMA Style

Zhonghe Sun, Mu Wang, Zhi Li, Bonnie Choi, Roger J. Mulder, Anchao Feng, Graeme Moad, San H. Thang. Versatile Approach for Preparing PVC-Based Mikto-Arm Star Additives Based on RAFT Polymerization. Macromolecules. 2020; 53 (11):4465-4479.

Chicago/Turabian Style

Zhonghe Sun; Mu Wang; Zhi Li; Bonnie Choi; Roger J. Mulder; Anchao Feng; Graeme Moad; San H. Thang. 2020. "Versatile Approach for Preparing PVC-Based Mikto-Arm Star Additives Based on RAFT Polymerization." Macromolecules 53, no. 11: 4465-4479.

Research article
Published: 16 January 2020 in Macromolecules
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The combination of high-throughput (HTP) processes and flow-mediated synthesis allows large data sets to be generated quickly while also permitting large quantities of materials to be prepared in a continuous fashion. In this work, the benefits of well-plate-based HTP polymerization and flow-mediated chemistry are used to streamline the screening and upscaling of value-added biomedical materials through a robust photopolymerization strategy, namely, photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. A library of potential antimicrobial polymers was generated from an initial pool of monomers and tested for their activity against Pseudomonas aeruginosa (PA). The antimicrobial activity of the most promising candidates was then elucidated through structure–property analyses performed via both plate and flow polymerization processes; interestingly, terpolymerization of mixtures of acrylate and acrylamide monomers produced terpolymers with gradient architectures due to their reactivity ratios, which ultimately dictated the resulting antimicrobial activity. Finally, the polymers found to have the highest antimicrobial activity were upscaled in a flow reactor. This workflow provides a general and highly accessible methodology for the discovery and synthetic scaling of optimized polymer structures for biomedical applications such as new antimicrobial agents.

ACS Style

Peter R. Judzewitsch; Nathaniel Corrigan; Francisco Trujillo; Jiangtao Xu; Graeme Moad; Craig J. Hawker; Edgar H. H. Wong; Cyrille Boyer. High-Throughput Process for the Discovery of Antimicrobial Polymers and Their Upscaled Production via Flow Polymerization. Macromolecules 2020, 53, 631 -639.

AMA Style

Peter R. Judzewitsch, Nathaniel Corrigan, Francisco Trujillo, Jiangtao Xu, Graeme Moad, Craig J. Hawker, Edgar H. H. Wong, Cyrille Boyer. High-Throughput Process for the Discovery of Antimicrobial Polymers and Their Upscaled Production via Flow Polymerization. Macromolecules. 2020; 53 (2):631-639.

Chicago/Turabian Style

Peter R. Judzewitsch; Nathaniel Corrigan; Francisco Trujillo; Jiangtao Xu; Graeme Moad; Craig J. Hawker; Edgar H. H. Wong; Cyrille Boyer. 2020. "High-Throughput Process for the Discovery of Antimicrobial Polymers and Their Upscaled Production via Flow Polymerization." Macromolecules 53, no. 2: 631-639.

Journal article
Published: 18 December 2019 in Polymer International
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Graeme Moad; Ezio Rizzardo. A 20th anniversary perspective on the life of RAFT (RAFT coming of age). Polymer International 2019, 69, 658 -661.

AMA Style

Graeme Moad, Ezio Rizzardo. A 20th anniversary perspective on the life of RAFT (RAFT coming of age). Polymer International. 2019; 69 (8):658-661.

Chicago/Turabian Style

Graeme Moad; Ezio Rizzardo. 2019. "A 20th anniversary perspective on the life of RAFT (RAFT coming of age)." Polymer International 69, no. 8: 658-661.

Journal article
Published: 13 November 2019 in Nanomaterials
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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.

ACS Style

Jaleh Mansouri; Vi Khanh Truong; Shane MacLaughlin; David E. Mainwaring; Graeme Moad; Ian J. Dagley; Elena P. Ivanova; Russell J. Crawford; Vicki Chen. 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. Nanomaterials 2019, 9, 1610 .

AMA Style

Jaleh Mansouri, Vi Khanh Truong, Shane MacLaughlin, David E. Mainwaring, Graeme Moad, Ian J. Dagley, Elena P. Ivanova, Russell J. Crawford, Vicki Chen. 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. Nanomaterials. 2019; 9 (11):1610.

Chicago/Turabian Style

Jaleh Mansouri; Vi Khanh Truong; Shane MacLaughlin; David E. Mainwaring; Graeme Moad; Ian J. Dagley; Elena P. Ivanova; Russell J. Crawford; Vicki Chen. 2019. "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." Nanomaterials 9, no. 11: 1610.

Communication
Published: 10 November 2019 in Macromolecular Rapid Communications
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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 (RAFT1), in aqueous solution. Thus, under irradiation with red (633 nm) or yellow (593 nm) light with 50 mpm (moles per million mole of monomer) ZnTPPS at 30 °C, the rate enhancement provided by photoinduced energy or electron transfer (PET) is ≈sevenfold over the rate of direct photoRAFT‐SUMI (without catalyst), which corresponds to achieving full and selective reaction in hours versus days. Importantly, the selectivity, as judged by the absence of oligomers, is retained. Under green light at similar power, higher rates of SUMI are also observed. However, the degree of enhancement provided by PET‐RAFT‐SUMI over direct photoRAFT‐SUMI as a function of catalyst concentration is less and some oligomers are formed.

ACS Style

Yanyan Zhou; Zhengbiao Zhang; Cassandra M. Reese; Derek L. Patton; Jiangtao Xu; Cyrille Boyer; Almar Postma; Graeme Moad. Selective and Rapid Light‐Induced RAFT Single Unit Monomer Insertion in Aqueous Solution. Macromolecular Rapid Communications 2019, 41, e1900478 .

AMA Style

Yanyan Zhou, Zhengbiao Zhang, Cassandra M. Reese, Derek L. Patton, Jiangtao Xu, Cyrille Boyer, Almar Postma, Graeme Moad. Selective and Rapid Light‐Induced RAFT Single Unit Monomer Insertion in Aqueous Solution. Macromolecular Rapid Communications. 2019; 41 (1):e1900478.

Chicago/Turabian Style

Yanyan Zhou; Zhengbiao Zhang; Cassandra M. Reese; Derek L. Patton; Jiangtao Xu; Cyrille Boyer; Almar Postma; Graeme Moad. 2019. "Selective and Rapid Light‐Induced RAFT Single Unit Monomer Insertion in Aqueous Solution." Macromolecular Rapid Communications 41, no. 1: e1900478.