Computer-Aided Design of Agents for Controlling Free-Radical Polymerisation. This project will provide cutting-edge fundamental research of importance to free-radical polymerisation. This process is the basis of a multi-billion dollar industry worldwide, and is very important to the Australian economy. The project will help to expand the applicability of the reversible addition fragmentation chain transfer (RAFT) polymerisation process, which is a significant new CSIRO-invented method for contro ....Computer-Aided Design of Agents for Controlling Free-Radical Polymerisation. This project will provide cutting-edge fundamental research of importance to free-radical polymerisation. This process is the basis of a multi-billion dollar industry worldwide, and is very important to the Australian economy. The project will help to expand the applicability of the reversible addition fragmentation chain transfer (RAFT) polymerisation process, which is a significant new CSIRO-invented method for controlling free-radical polymerisation. In doing this, the project will facilitate the design and development of a range of new polymer products, with applications in biotechnology and nanotechnology. This research will help to keep Australia at the forefront of this important field.Read moreRead less
Polymerization Mechanism and Kinetics of 1,1-Disubstituted Monomers. This project focuses on two exciting research areas: (I) we have found that an oxygen atom b to the double bond activates radical polymerization, making a whole new family of polymeric structures accessible, and (II) we have strong preliminary data that demonstrates a very large solvent effect on propagation and termination reactions for acrylic monomers with an a-CH2OH functionality, suggesting that significant control can be ....Polymerization Mechanism and Kinetics of 1,1-Disubstituted Monomers. This project focuses on two exciting research areas: (I) we have found that an oxygen atom b to the double bond activates radical polymerization, making a whole new family of polymeric structures accessible, and (II) we have strong preliminary data that demonstrates a very large solvent effect on propagation and termination reactions for acrylic monomers with an a-CH2OH functionality, suggesting that significant control can be exerted over the polymerization process using additives. Additionally, we demonstrate that polymers containing repeat units with an a-CH2OH functionality can undergo reversible cyclization, enabling a whole range of novel functional materials.Read moreRead less
Pro-Fluorescent Aryl Nitroxides: New Probes for Polymer Lifetime and Kinetics Research. Internal aryl rings present in novel probes developed for this project impart fluorescence which is efficiently and internally quenched by the presence of a paramagnetic nitroxide group. Scavenging of radicals by the nitroxide however "switches on" the fluorescence and this enables powerful new fluorescence-based detection levels for the technique of nitroxide free radical scavenging. Such sensitivity is a ....Pro-Fluorescent Aryl Nitroxides: New Probes for Polymer Lifetime and Kinetics Research. Internal aryl rings present in novel probes developed for this project impart fluorescence which is efficiently and internally quenched by the presence of a paramagnetic nitroxide group. Scavenging of radicals by the nitroxide however "switches on" the fluorescence and this enables powerful new fluorescence-based detection levels for the technique of nitroxide free radical scavenging. Such sensitivity is applicable to polymerization kinetics studies, as well as providing new means for the determination of materials lifetimes. The development of pro-fluorescent markers as indicators for polymer degradation would be a significant outcome for materials where component failure has a major negative impact.Read moreRead less
Mechanisms in Catalytic Chain Transfer Polymerization. The aim of the proposed research is to gain more insight into the mechanisms underlying catalytic chain transfer polymerization, a relatively recent controlled radical polymerization technique which is finding an increasing number of industrial applications, especially in the paint and coatings industry. An improved understanding of the catalytic chain transfer process, of which some very important features are still poorly understood, will ....Mechanisms in Catalytic Chain Transfer Polymerization. The aim of the proposed research is to gain more insight into the mechanisms underlying catalytic chain transfer polymerization, a relatively recent controlled radical polymerization technique which is finding an increasing number of industrial applications, especially in the paint and coatings industry. An improved understanding of the catalytic chain transfer process, of which some very important features are still poorly understood, will ultimately lead to better catalyst design and improved process and product control. This in turn will lead to novel polymeric materials.Read moreRead less
Defining Polymer Structures in Radical Polymerization Systems: Chain Birth, Chain Growth and Complex Macromolecular Architectures. The project underpins and extends Australia's leading position in the development and application of novel methods to generate advanced polymeric materials. By carefully studying the reaction pathways underpinning the polymerization processes, an in-depth picture of the polymerization is obtained. The research outcomes will strongly benefit the preparation of the com ....Defining Polymer Structures in Radical Polymerization Systems: Chain Birth, Chain Growth and Complex Macromolecular Architectures. The project underpins and extends Australia's leading position in the development and application of novel methods to generate advanced polymeric materials. By carefully studying the reaction pathways underpinning the polymerization processes, an in-depth picture of the polymerization is obtained. The research outcomes will strongly benefit the preparation of the coming generations of intelligent polymer materials of a highly controlled structure, responsive to their environment, with an even broader range of applications than existing polymers. In addition, the project has a substantial educational component providing training embedded in cutting polymer science for several honours and 1 PhD student.Read moreRead less
Reversible Addition Fragmentation Chain Transfer (RAFT) Free Radical Copolymerizations of Various Monomers. The proposed project will investigate the structure and properties of statistical copolymers prepared via living free radical polymerization. We will study the characteristics of a wide variety of Reversible Addition Fragmentation Chain Transfer (RAFT) copolymerizations using a range of monomers, including those interesting for biomedical and material science applications. We expect to gai ....Reversible Addition Fragmentation Chain Transfer (RAFT) Free Radical Copolymerizations of Various Monomers. The proposed project will investigate the structure and properties of statistical copolymers prepared via living free radical polymerization. We will study the characteristics of a wide variety of Reversible Addition Fragmentation Chain Transfer (RAFT) copolymerizations using a range of monomers, including those interesting for biomedical and material science applications. We expect to gain a deeper understanding of the influence of the RAFT process on the kinetics and mechanism of copolymerization and the properties of the resulting polymers in order to tailor specific polymer materials for biomedial applications.Read moreRead less
Accessing Chain Length Dependent Rate Coefficients in Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerisations. The proposed project combines two exciting research areas, namely the chain length dependencies of kinetic coefficients and reversible addition fragmentation chain transfer (RAFT) polymerisations. The starting point of the project will be a novel technique recently invented by our team for termination rate measurement utilizing the RAFT process. Detailed knowledge of cha ....Accessing Chain Length Dependent Rate Coefficients in Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerisations. The proposed project combines two exciting research areas, namely the chain length dependencies of kinetic coefficients and reversible addition fragmentation chain transfer (RAFT) polymerisations. The starting point of the project will be a novel technique recently invented by our team for termination rate measurement utilizing the RAFT process. Detailed knowledge of chain length dependent rate coefficients in both homo- and copolymerisations is essential from both an academic and industrial perspective, because polymerisation kinetics not only govern the reaction rates but influence directly the polymeric material properties.Read moreRead less
Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence suc ....Hydrogen Abstraction in Chemical, Biochemical and Polymerization Processes. Hydrogen-abstraction reactions are of vital importance in the chemical, biochemical and polymerization processes that occur in everyday life. The objective of the proposed research is to improve our understanding of such reactions. State-of-the-art quantum chemistry calculations will be used to examine a broad range of hydrogen-abstraction reactions, and to obtain accurate information about the factors that influence such reactions. Building on this work, more detailed case studies will be performed in two important areas: the hydrogen-abstraction steps in biochemical reactions mediated by coenzyme B12, and chain-transfer processes in conventional and controlled free-radical polymerization.Read moreRead less
Novel network polymers with photoinduced plasticity. The production of crosslinked polymers (thermosets and rubbers) is a multi-billion dollar industry and these polymers are irreplaceable in their use in numerous applications in the household goods, medical, electronics, automotive and construction industries. However, they shrink during solidification causing internal stresses which weaken them and they can not be reshaped, repaired or recycled. This study will develop a novel range of cros ....Novel network polymers with photoinduced plasticity. The production of crosslinked polymers (thermosets and rubbers) is a multi-billion dollar industry and these polymers are irreplaceable in their use in numerous applications in the household goods, medical, electronics, automotive and construction industries. However, they shrink during solidification causing internal stresses which weaken them and they can not be reshaped, repaired or recycled. This study will develop a novel range of crosslinkable polymers which can change shape on irradiation by light (or by heating) for use in applications ranging from repairable composites, stress-free lens, non-shrinking dental filling materials and light-sensitive actuators which will have significant benefit to industry.Read moreRead less
Controlled/living radical polymerization in environmentally friendly miniemulsions induced by compressed carbon dioxide for synthesis of nanoparticles and well-defined polymer. Controlled/living radical polymerization is a technique for precise synthesis of polymer by radical polymerization, which has revolutionized polymer synthesis in terms of accessible polymer structures. However, controlled/living radical polymerization has yet to gain a strong foothold in industry mainly due to problems as ....Controlled/living radical polymerization in environmentally friendly miniemulsions induced by compressed carbon dioxide for synthesis of nanoparticles and well-defined polymer. Controlled/living radical polymerization is a technique for precise synthesis of polymer by radical polymerization, which has revolutionized polymer synthesis in terms of accessible polymer structures. However, controlled/living radical polymerization has yet to gain a strong foothold in industry mainly due to problems associated with its implementation in (aqueous) dispersed systems. The present Proposal addresses this key challenge by a novel environmentally friendly and versatile method for aqueous miniemulsion preparation by use of compressed carbon dioxide. Controlled/living radical polymerization in dispersed systems generates polymeric nanoparticles, which are of importance in many advanced and emerging technologies.Read moreRead less