New Insights Into Copper-Mediated Polymerization and Polymer Topologies Mikhail Gavrilov Diploma in Chemistry
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New Insights into Copper-Mediated Polymerization and Polymer Topologies Mikhail Gavrilov Diploma in Chemistry A thesis submitted for the degree of Doctor of Philosophy at The University of Queensland in 2017 Australian Institute for Bioengineering and Nanotechnology i Abstract Polymer science has developed new synthetic methods to create complex polymer architectures. The solution and bulk properties of these architectures are influenced by the structure and chemical composition of the original building blocks (e.g. monomers or reactive polymeric blocks). One of the greatest challenges to the field is characterization of these polymers with diverse structures and chemical compositions. Size exclusion chromatography (SEC) has been one of the most used characterization techniques to determine the molecular weight distribution (MWD) of polymers. The information obtained about the polymer from SEC is generally restricted to molecular weight averages and dispersity indexes. However, there is a wealth of valuable information that can be obtained from a deeper analysis of the SEC chromatograms. This information can provide insights into polymerization mechanisms, the amount of unreacted polymer in a coupling reaction, or even the amount of cyclic polymer formed during a ring-closure reaction. The thesis first develops the theory to analyse the SEC chromatograms and provides a methodology to fit the MWDs with a log-normal distribution (LND) model based on a Gaussian function. The LND model was then used to analyse polymers made by a variant of copper-mediated ‗living‘ radical polymerization (LRP) in water. This LRP technique is capable of producing hydrophilic polymers with both narrow MWDs and high chain-end functionality, but the chain-end halide groups were susceptible to hydrolysis upon purification attempts and, therefore, the polymers cannot be further used to create complex polymer architectures. To preserve high chain-end functionality, the terminal halide of the polymers was capped using in situ azidation at the end of aqueous copper- mediated LRP. The azide chain-end fidelity of the purified polymer was tested in a copper- catalyzed azide-alkyne cycloaddition (CuAAC) ‗click‘ reaction. The LND model of MWDs of the resulting products gave an accurate determination of the end-group functionality and insight into the effectiveness of our new polymerization variant. In the final stage of this thesis, the LND model was used to quantify the sequential polymerization of cyclic macromers through successive CuAAC ‗click‘ reactions. The versatility of the LND model was further demonstrated by determining the multicyclic coil conformation as a function of the number of cyclic macromers in the polymer chain. ii Declaration by author This thesis is composed of my original work, and contains no material previously published or written by another person except where due reference has been made in the text. I have clearly stated the contribution by others to jointly-authored works that I have included in my thesis. I have clearly stated the contribution of others to my thesis as a whole, including statistical assistance, survey design, data analysis, significant technical procedures, professional editorial advice, and any other original research work used or reported in my thesis. The content of my thesis is the result of work I have carried out since the commencement of my research higher degree candidature and does not include a substantial part of work that has been submitted to qualify for the award of any other degree or diploma in any university or other tertiary institution. I have clearly stated which parts of my thesis, if any, have been submitted to qualify for another award. I acknowledge that an electronic copy of my thesis must be lodged with the University Library and, subject to the policy and procedures of The University of Queensland, the thesis be made available for research and study in accordance with the Copyright Act 1968 unless a period of embargo has been approved by the Dean of the Graduate School. I acknowledge that copyright of all material contained in my thesis resides with the copyright holder(s) of that material. Where appropriate I have obtained copyright permission from the copyright holder to reproduce material in this thesis. iii Publications during candidature Peer-reviewed papers 1. Monteiro, M. J.; Gavrilov, M., Characterization of hetero-block copolymers by the log-normal distribution model. Polymer Chemistry 2016, 7 (17), 2992-3002. 2. Gavrilov, M.; Jia, Z.; Percec, V.; Monteiro, M. J., Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH4. Polymer Chemistry 2016, 7 (29), 4802-4809. 3. Gavrilov, M.; Zerk, T. J.; Bernhardt, P. V.; Percec, V.; Monteiro, M. J., SET-LRP of NIPAM in water via in situ reduction of Cu(ii) to Cu(0) with NaBH4. Polymer Chemistry 2016, 7 (4), 933-939. 4. Gavrilov, M.; Monteiro, M. J., Derivation of the molecular weight distributions from size exclusion chromatography. European Polymer Journal 2015, 65, 191-196. 5. Sebakhy, K. O.; Gavrilov, M.; Valade, D.; Jia, Z.; Monteiro, M. J., Nanoparticles of Well-Defined 4-Arm Stars made using Nanoreactors in Water. Macromolecular Rapid Communications 2014, 35 (2), 193-197. Publications included in this thesis Gavrilov, M.; Monteiro, M. J., Derivation of the molecular weight distributions from size exclusion chromatography. European Polymer Journal 2015, 65, 191-196. – Incorporated as Chapter 2. Contributor Statement of contribution Mikhail Gavrilov (Candidate) Analysis and data interpretation (40%) Designed experiments (40%) Drafting and writing (40%) Experiments (100%) Michael Monteiro Analysis and data interpretation (60%) Designed experiments (60%) Drafting and writing (60%) Monteiro, M. J.; Gavrilov, M., Characterization of hetero-block copolymers by the log- normal distribution model. Polymer Chemistry 2016, 7 (17), 2992-3002. - Incorporated as Chapter 3. iv Contributor Statement of contribution Mikhail Gavrilov (Candidate) Analysis and data interpretation (40%) Designed experiments (40%) Drafting and writing (40%) Experiments (100%) Michael Monteiro Analysis and data interpretation (60%) Designed experiments (60%) Drafting and writing (60%) Gavrilov, M.; Zerk, T. J.; Bernhardt, P. V.; Percec, V.; Monteiro, M. J., SET-LRP of NIPAM in water via in situ reduction of Cu(ii) to Cu(0) with NaBH4. Polymer Chemistry 2016, 7 (4), 933-939. - Incorporated as Chapter 4. Contributor Statement of contribution Mikhail Gavrilov (Candidate) Analysis and data interpretation (40%) Designed experiments (40%) Drafting and writing (40%) Experiments (90%) Timothy Zerk Analysis and data interpretation (5%) Experiments (10%) Paul Bernhardt Analysis and data interpretation (5%) Designed experiments (10%) Virgil Percec Analysis and data interpretation (10%) Designed experiments (10%) Michael Monteiro Analysis and data interpretation (40%) Designed experiments (40%) Drafting and writing (60%) Gavrilov, M.; Jia, Z.; Percec, V.; Monteiro, M. J., Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH4. Polymer Chemistry 2016, 7 (29), 4802-4809. - Incorporated as Chapter 5. Contributor Statement of contribution Mikhail Gavrilov (Candidate) Analysis and data interpretation (40%) Designed experiments (30%) Drafting and writing (45%) Experiments (100%) Zhongfan Jia Analysis and data interpretation (15%) v Designed experiments (35%) Drafting and writing (10%) Virgil Percec Analysis and data interpretation (5%) Designed experiments (5%) Michael Monteiro Analysis and data interpretation (40%) Designed experiments (30%) Drafting and writing (45%) vi Contributions by others to the thesis The author acknowledges the following individuals who have contributed to this thesis: Prof. Michael J. Monteiro for contributing to drafting and writing, data analysis and interpretation, design and conception of experiments. Dr. Zhongfan Jia for contributing to data analysis and interpretation, design and conception of experiments. Prof. Virgil Percec for contributing to data analysis and interpretation and design and conception of experiments. Prof. Paul Bernhardt for contributing to data analysis and interpretation and design and conception of experiments. Timothy Zerk for UV-vis experiments and data analysis and interpretation. Statement of parts of the thesis submitted to qualify for the award of another degree ―None‖. vii Acknowledgements I primary want to acknowledge my supervisor Prof. Michael J. Monteiro, for his enormous support throughout my PhD candidature. Apart from his strong guidance of my research and funding of the first year of my PhD, he also helped me to develop personally by teaching me to communicate my data properly during both vis-à-vis and weekly group meetings, time management, to pay thorough attention to details and gently support people around me. I will do my best to make his time and effort investments worthy. If we imagine science as a coin with one of its side being theory, models and equations describing laws of nature then another side of the coin must be assigned to experiments, and their reflection of how precisely these models and equations embrace natural phenomena. Michael mostly helped me with first side of the coin — theory, and Dr. Zhongfan Jia was my guide on the other side. He navigated me through the experiment ‖jungles‖ with his colossal ―machete‖ of experience. You would not be reading this thesis without Zhongfan‘s