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Copper (I) mediated Huisgen 1,3 dipolar cycloaddition of 4-(piperidine-1-yl)-N-(prop-1-yne- 3-yl)-1,8-naphtalimide (PN) to poly(αN3εCL-co-εCL) of three different molar ratio of αN3εCL was performed. Reaction was succesfull for poly(αN3εCL-co-εCL) with molar fraction of αN3εCL f = 0,22. No degradation of substituted PCL was observed during the synthetic path, therefore the PN molecule is suitable for click coupling to well defined polyester. New aliphatic polyester based on polycaprolactone was synthesized and characterized by means of 1 HNMR spectra and Gel permeation chromatography calibrated with polystyrene standards. The spectra of other two copolymers coupled with PN were not measured due to their low solubility in common organic solvents. Keywords: living polymerization, α-chloro-ε-caprolactone, click reaction

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19894号 / 工博第4210号 / 新制||工||1651(附属図書館) / 32971 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 秋吉 一成, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Thesis advisor: Jia Niu / Thesis advisor: Jim Morken / Polysaccharides make up one of the largest classes of nature’s macromolecules. However, they are severely understudied relative to other biomolecules such as proteins and DNA sequences. This is because discrete polysaccharides are difficult to isolate from nature or synthesize in laboratories in large enough quantities for thorough research. Polymerization is an efficient route to polysaccharides, yet has historically suffered from harsh conditions and lack of control. Herein, we investigate recent developments in the field of living polymerization as strategies towards synthesis of precision polysaccharides from 1,2- anhydrosugars. We specifically focus on cationic ring opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) ROP polymerization of 1,2-O-Bn-3,4,6-anhydromannose and 1,2-O-Bn-3,4,6-anhydroglucose. Our research screens various catalyst/initiating systems. Our findings demonstrate that cationic ROP and RAFT polymerization are unsuccessful in the living ROP of 1,2-anhydrosugars. / Thesis (MS) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis (PhD (Chemistry and Polymer Science)--University of Stellenbosch, 2008. / Xanthate-mediated polymerization was investigated as a tool for the preparation of well-defined poly(N-vinylpyrrolidone) and copolymers of N-vinylpyrrolidone. Some results regarding the monomer vinyl acetate are included, mostly for comparison purposes. The structure of the leaving/reinitiating group of the xanthate mediating agent was tuned to match the monomer reactivity. This was achieved by studying the initialization behaviour of monomer-xanthate systems via in situ 1H-NMR spectroscopy. Additionally, the latter technique was valuable to identify side reactions affecting the monomer, xanthate and/or polymeric species. Subsequently, experimental conditions were defined, and used to optimize the level of control achieved during polymerization. Block copolymers were prepared from a xanthate end-functional poly(ethylene glycol) with both vinyl acetate and N-vinylpyrrolidone. Finally, the preparation of poly(N-vinylpyrrolidone) with a range of well-defined end groups was achieved via postpolymerization treatment of the xanthate end-functional polymerization product. 3 different routes were investigated, which lead to poly(N-vinylpyrrolidone) with 1) aldehyde or alcohol, 2) thiol or 3) unsaturated ω-chain-end functionality, in high yield, while the α-chain-end functionality is defined by the structure of the xanthate leaving group. The ω-aldehyde end-functional poly(N-vinylpyrrolidone) was successfully conjugated to the lysine residues of the model protein lysozyme via reductive amination. Particular attention was drawn to characterizing the polymerization products. NMR spectroscopy, liquid chromatographic and mass-spectroscopic techniques were used. The major achievements emerging from polymer analysis carried out in this study included the following: - a library of NMR chemical shifts for N-vinylpyrrolidone derivatives; - an estimation of the critical conditions for poly(N-vinylpyrrolidone) relevant for separation according to the polymer chain-ends; - conditions for the separation of block-copolymers comprising a poly(ethylene glycol) segment and a poly(N-vinylpyrrolidone) or poly(vinyl acetate) segment via liquid chromatography; - valuable results on matrix-assisted laser ionization-desorption time-of-flight mass spectroscopy (MALDI-ToF-MS) of poly(N-vinylpyrrolidone).

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

The generalized Langevin equation (GLE) has been used to describe the dynamics of particles in a stationary environment. To better understand the dynamics of polymerization, the GLE has been generalized to the irreversible generalized Langevin equation (iGLE) so as to incorporate the non-stationary response of the solvent. This non-stationary response is manifested in the friction kernel and the behavior of the projected (stochastic) force. A particular polymerizing system, such as living polymerization, is specified both through the parameters of the friction kernel and the potential of mean force (PMF). Equilibrium properties such as extent of polymerization have been obtained and are consistent with Flory-Huggin¡¯s theory. In addition, time-dependent non-equilibrium observables such as polymer length, the polymer length distribution, and polydispersity index (PDI) of living polymerization have been obtained. These have been compared to several experiments so as to validate the models, and to provide additional insight into the thermodynamic and kinetic properties of these systems. In addition to the iGLE, a stochastic model has been used to study the effect of nonequilibrium reactivity on living polymerization. This model can be used to determine whether the reaction is controlled by kinetics or diffusion. A combination of the iGLE and stochastic models may help us obtain more information about living polymerization.

In this work, methylmethacrylate, MMA was polymerized by ATRP method to obtain low molecular weight living polymers. The initiator was p-toluenesulfonylchloride and catalyst ligand complex system were CuCl-4,4&rsquo / dimethyl 2,2&rsquo / bipyridine. Polymers with controlled molecular weight were obtained. The polymer chains were shown by NMR investigation to be mostly syndiotactic. The molecular weight and molecular weight distribution of some polymer samples were measured by GPC method. The K and a constants in [h]=K Ma equation were measured as 9.13x10-5 and 0.74, respectively. FT-IR and X-Ray results showed regularity in polymer chains. The molecular weight-Tg relations were verified from results of molecular weight-DSC results.

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