Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications

Chapter 1 introduced the general concept of living radical polymerization (LRP), three most widely-used LRP methods were introduced, and their advantages and disadvantages were discussed. The mechanism of reversible complexation mediated polymerization (RCMP) was introduced, and its advantages over...

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Main Author: Mao, Weijia
Other Authors: Atsushi Goto
Format: Thesis-Doctor of Philosophy
Language:English
Published: Nanyang Technological University 2022
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Online Access:https://hdl.handle.net/10356/155353
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Institution: Nanyang Technological University
Language: English
id sg-ntu-dr.10356-155353
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institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Science::Chemistry::Organic chemistry::Polymers
spellingShingle Science::Chemistry::Organic chemistry::Polymers
Mao, Weijia
Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
description Chapter 1 introduced the general concept of living radical polymerization (LRP), three most widely-used LRP methods were introduced, and their advantages and disadvantages were discussed. The mechanism of reversible complexation mediated polymerization (RCMP) was introduced, and its advantages over other LRPs have been discussed. The current catalysts and current limitations of RCMP were also introduced. The motivations and aims for the works in this Thesis were explained. In Chapter 2, oxyanions (carboxylate, nitrate, phosphate, and sulfonate) were systematically studied as new RCMP catalysts. The oxyanion-catalyzed RCMP yielded polymers with relatively high conversion in short reaction times, maintaining low dispersity. The high chain-end iodide livingness of the obtained polymers also enabled the synthesis of block copolymers. Oxyanion compounds are inexpensive, little toxic, and amenable to broad molecular structures. These features are attractive for RCMP catalysis. The development of oxyanions as RCMP catalysts also contributed to development of air-tolerant RCMP in Chapter 3. In Chapter 3, air-tolerant RCMP was developed. The air-tolerant RCMP system employed an aldehyde, N-hydroxyphthalimide (NHPI), and an amine for both oxygen consumption and catalysis. The aldehyde (RCHO) consumed oxygen and was converted to a carboxylic acid (RCOOH) catalyzed by NHPI. The carboxylic acid was subsequently converted to a carboxylate anion (RCOO−) in the presence of the amine. The generated RCOO− worked as an RCMP catalyst. This system does not require deoxygenation before polymerization and is amenable to methacrylates and styrene. The development of air-tolerant RCMP enhances the practicality of RCMP. In Chapter 4, RCMP was explored in the emulsion system. We systematically studied the effect of emulsifiers, catalysts, and alkyl iodide initiating dormant species in emulsion RCMP for homopolymerization. The kinetic and mechanistic aspects of emulsion RCMP were also elucidated by partitioning tests of the initiating dormant species and particle number analysis in the course of polymerization. Emulsion RCMP can afford stable polymer latex with relatively high solid contents (up to nearly 50%). The emulsion RCMP combines the advantages of emulsion polymerization such as efficient heat transfer, low viscosity, and high polymerization rate with those of RCMP, such as no use of special capping agents or toxic catalysts. The high solid content, high chain-end fidelity, good monomer versatility achievable in the emulsion RCMP would also be attractive for polymer material design and industrial applications. In Chapter 5, we further explored emulsion RCMP for copolymerization. We carried out block copolymerization exploiting the high iodide chain-end fidelity of poly(methacrylate) −I (PMMA−I) obtained in Chapter 4, successfully yielding block copolymers with high monomer conversions in relatively short reaction times. Random copolymerizations were also carried out in emulsion RCMP, various gradient copolymers were obtained, and monomer sequence can be tuned by the reaction temperature. We also studied using solution RCMP for the synthesis of hydrophilic-amphiphilic block copolymers using monomers with anti-fouling properties and applied the obtained block copolymers for anti-fouling coating on membranes. The accessibility of RCMP in aqueous media to a wide range of monomers was successfully demonstrated.
author2 Atsushi Goto
author_facet Atsushi Goto
Mao, Weijia
format Thesis-Doctor of Philosophy
author Mao, Weijia
author_sort Mao, Weijia
title Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
title_short Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
title_full Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
title_fullStr Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
title_full_unstemmed Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
title_sort synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications
publisher Nanyang Technological University
publishDate 2022
url https://hdl.handle.net/10356/155353
_version_ 1759856154634092544
spelling sg-ntu-dr.10356-1553532023-02-28T23:48:33Z Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications Mao, Weijia Atsushi Goto School of Physical and Mathematical Sciences agoto@ntu.edu.sg Science::Chemistry::Organic chemistry::Polymers Chapter 1 introduced the general concept of living radical polymerization (LRP), three most widely-used LRP methods were introduced, and their advantages and disadvantages were discussed. The mechanism of reversible complexation mediated polymerization (RCMP) was introduced, and its advantages over other LRPs have been discussed. The current catalysts and current limitations of RCMP were also introduced. The motivations and aims for the works in this Thesis were explained. In Chapter 2, oxyanions (carboxylate, nitrate, phosphate, and sulfonate) were systematically studied as new RCMP catalysts. The oxyanion-catalyzed RCMP yielded polymers with relatively high conversion in short reaction times, maintaining low dispersity. The high chain-end iodide livingness of the obtained polymers also enabled the synthesis of block copolymers. Oxyanion compounds are inexpensive, little toxic, and amenable to broad molecular structures. These features are attractive for RCMP catalysis. The development of oxyanions as RCMP catalysts also contributed to development of air-tolerant RCMP in Chapter 3. In Chapter 3, air-tolerant RCMP was developed. The air-tolerant RCMP system employed an aldehyde, N-hydroxyphthalimide (NHPI), and an amine for both oxygen consumption and catalysis. The aldehyde (RCHO) consumed oxygen and was converted to a carboxylic acid (RCOOH) catalyzed by NHPI. The carboxylic acid was subsequently converted to a carboxylate anion (RCOO−) in the presence of the amine. The generated RCOO− worked as an RCMP catalyst. This system does not require deoxygenation before polymerization and is amenable to methacrylates and styrene. The development of air-tolerant RCMP enhances the practicality of RCMP. In Chapter 4, RCMP was explored in the emulsion system. We systematically studied the effect of emulsifiers, catalysts, and alkyl iodide initiating dormant species in emulsion RCMP for homopolymerization. The kinetic and mechanistic aspects of emulsion RCMP were also elucidated by partitioning tests of the initiating dormant species and particle number analysis in the course of polymerization. Emulsion RCMP can afford stable polymer latex with relatively high solid contents (up to nearly 50%). The emulsion RCMP combines the advantages of emulsion polymerization such as efficient heat transfer, low viscosity, and high polymerization rate with those of RCMP, such as no use of special capping agents or toxic catalysts. The high solid content, high chain-end fidelity, good monomer versatility achievable in the emulsion RCMP would also be attractive for polymer material design and industrial applications. In Chapter 5, we further explored emulsion RCMP for copolymerization. We carried out block copolymerization exploiting the high iodide chain-end fidelity of poly(methacrylate) −I (PMMA−I) obtained in Chapter 4, successfully yielding block copolymers with high monomer conversions in relatively short reaction times. Random copolymerizations were also carried out in emulsion RCMP, various gradient copolymers were obtained, and monomer sequence can be tuned by the reaction temperature. We also studied using solution RCMP for the synthesis of hydrophilic-amphiphilic block copolymers using monomers with anti-fouling properties and applied the obtained block copolymers for anti-fouling coating on membranes. The accessibility of RCMP in aqueous media to a wide range of monomers was successfully demonstrated. Doctor of Philosophy 2022-02-18T00:29:37Z 2022-02-18T00:29:37Z 2021 Thesis-Doctor of Philosophy Mao, W. (2021). Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/155353 https://hdl.handle.net/10356/155353 10.32657/10356/155353 en This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0). application/pdf Nanyang Technological University