Novel Complex Architecture Polymers via a Combination of RAFT Chemistry and Pericyclic Reactions: Synthesis and Characterization. The project aims at advancing the synthetic limits and broadening the synthetic scope of living free radical polymerization and thus enhancing the library of polymer structures available for applications ranging from drug delivery to opto-electronics. Current material design for these applications is yet to reach its full potential through innovative synthetic approac ....Novel Complex Architecture Polymers via a Combination of RAFT Chemistry and Pericyclic Reactions: Synthesis and Characterization. The project aims at advancing the synthetic limits and broadening the synthetic scope of living free radical polymerization and thus enhancing the library of polymer structures available for applications ranging from drug delivery to opto-electronics. Current material design for these applications is yet to reach its full potential through innovative synthetic approaches. The proposal critically underpins and further advances Australia's leading position in both breakthrough science as well as advanced materials. Due to its significant scientific breadth and large coverage of both synthetic and physical aspects of polymer science, the project also provides a significant platform for research training at both honours and PhD level.Read moreRead less
Synthesis of oligomers in dense carbon dioxide. The aim of the project is to develop a novel technique for the synthesis of low molecular weight polymers (oligomers) using dense carbon dioxide as a polymerisation solvent. The use of elevated pressure is the major impediment to the commercialisation of such technology. The technique proposed in this project will enable oligomers to be produced at greatly reduced operating pressures and may lead to a more general procedure for conducting other t ....Synthesis of oligomers in dense carbon dioxide. The aim of the project is to develop a novel technique for the synthesis of low molecular weight polymers (oligomers) using dense carbon dioxide as a polymerisation solvent. The use of elevated pressure is the major impediment to the commercialisation of such technology. The technique proposed in this project will enable oligomers to be produced at greatly reduced operating pressures and may lead to a more general procedure for conducting other types of polymer synthesis in dense carbon dioxide.Read moreRead less
Structure-Property Relationships of Polymers with Controlled Architecture. Mechanical properties of a polymer (e.g., how elastic it is and how it dissipates energy when compressed) govern how well it performs as an adhesive, or its behaviour when melted and shaped into a consumer item. This project aims to relate molecular architecture to mechanical properties, using new techniques which permit the creation of polymers wherein each architectural characteristic is separately controlled. This has ....Structure-Property Relationships of Polymers with Controlled Architecture. Mechanical properties of a polymer (e.g., how elastic it is and how it dissipates energy when compressed) govern how well it performs as an adhesive, or its behaviour when melted and shaped into a consumer item. This project aims to relate molecular architecture to mechanical properties, using new techniques which permit the creation of polymers wherein each architectural characteristic is separately controlled. This has the potential to develop fundamental understanding for structure-property relations for the type of branched polymers that are in common use in industry and for which adequate models do not currently exist.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
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
Simulation studies of stick and slip at the solid-liquid boundary. Successful practical application of computational rheology to polymer processing, to adhesion and to the understanding of lubrication at very high shear rates, among other problems, needs both an adequate description of the fluid - a constitutive equation - and the prescription of proper boundary conditions.The constitutive model problem has been extensively studied, and this proposal seeks to address the question of proper bound ....Simulation studies of stick and slip at the solid-liquid boundary. Successful practical application of computational rheology to polymer processing, to adhesion and to the understanding of lubrication at very high shear rates, among other problems, needs both an adequate description of the fluid - a constitutive equation - and the prescription of proper boundary conditions.The constitutive model problem has been extensively studied, and this proposal seeks to address the question of proper boundary conditions for viscoelastic flow at interfaces between a flowing fluid and a solid surface. This vital area has not been thoroughly studied theoretically and computationally, and we seek to clarify the mechanisms by using molecular dynamics.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
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
An Integrated Framework for Optimisation and Control of Key Product Properties in Emulsion Polymerisation. Emulsion polymerization is of major industrial importance. In addition to process efficiency, the use of water as the reactor medium provides environmental benefits. This proposal is aimed at building an integrated framework to analyse, model, control and optimise emulsion polymerisation systems in order to understand, design and operate such complex systems to obtain desired polymer produc ....An Integrated Framework for Optimisation and Control of Key Product Properties in Emulsion Polymerisation. Emulsion polymerization is of major industrial importance. In addition to process efficiency, the use of water as the reactor medium provides environmental benefits. This proposal is aimed at building an integrated framework to analyse, model, control and optimise emulsion polymerisation systems in order to understand, design and operate such complex systems to obtain desired polymer product characteristics. Complex kinetic, transport and evolution equations will be analysed and solved for predicting and controlling key product properties. This project will provide not only a significant advance in fundamental knowledge of polymerisation systems but will also enable production of cost-effective ?designer polymers? for a wide-range of applications.Read moreRead less