Precision Synthesis of Conjugated Rod-Coil Block Copolymers for Application to Stretchable Electronic Devices and Reactive Oxygen Generators
- 주제(키워드) polymer , chain-growth , conjugated polymer , stretchable
- 주제(DDC) 621.042
- 발행기관 아주대학교 일반대학원
- 지도교수 In-Hwan Lee
- 발행년도 2026
- 학위수여년월 2026. 2
- 학위명 박사
- 학과 및 전공 일반대학원 에너지시스템학과
- 실제URI http://www.dcollection.net/handler/ajou/000000035629
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
This thesis investigates the precision synthesis of two classes of polymers—conjugated rod–coil block copolymers for application in stretchable electronic devices and reactive oxygen generators, and biodegradable multiblock copolymers—as well as the post-modification of functional polymers. Chapter 1 highlights the development of precision-controlled chain-growth polymerization as a powerful tool for the structural design of conjugated polymers. Suzuki–Miyaura catalyst-transfer polymerization (SCTP) enables narrow dispersity, well-defined end groups, and high reproducibility through its chain-walking mechanism. Compared with traditional step-growth methods, SCTP provides superior molecular precision and functional tunability, facilitating the synthesis of conjugated multiblock and rod–coil copolymers. Moreover, its exceptional moisture stability allows the incorporation of hydrophilic monomers to form self-assembled nanoparticles capable of generating reactive oxygen species (ROS). Overall, SCTP establishes a robust platform for next-generation multifunctional polymer systems through structural and functional sophistication. Chapter 2 presents a versatile dual-polymerization platform integrating photo-ATRP and Suzuki–Miyaura catalyst-transfer polymerization (SCTP) for the precision synthesis of conjugated–vinyl block copolymers. Using a bifunctional initiator strategy, well-defined linear and miktoarm star copolymers were efficiently obtained without post-modification steps. The developed one-pot process achieves high end-group fidelity, narrow dispersity, and structural tunability across diverse vinyl macroinitiators. Systematic variation of linker regiochemistry and block lengths revealed their critical influence on nanoscale self-assembly and thin-film morphology. This streamlined, step-economical protocol establishes an efficient route toward structurally precise and functionally adaptable conjugated block copolymers. Chapter 3 explores the development of an intrinsically non-conjugated polymerization (INCP) platform based on moisture-tolerant Suzuki–Miyaura catalyst-transfer polymerization (SCTP). The approach enables the precise synthesis of diverse conjugated rod–coil block copolymers by integrating a wide range of coil-type polymers, including hydrophobic, hydrophilic, and functional vinyl systems. The resulting polymers exhibit excellent structural definition and tunable assembly behavior in various environments. As a representative application, incorporation of hydrophilic PEG segments led to well-defined micellar nanostructures capable of generating reactive oxygen species (ROS) under photoexcitation, highlighting their potential in photodynamic therapy (PDT). Chapter 4 investigates the precision synthesis of conjugated multiblock copolymers via Suzuki–Miyaura catalyst-transfer polymerization (SCTP) to elucidate structure–property correlations in stretchability and charge transport. By integrating soft and rigid segments in a controlled multiblock architecture, the polymers exhibit enhanced mechanical flexibility without sacrificing electronic performance. Systematic variation of block composition and chain sequence revealed the critical role of molecular ordering in balancing elasticity and conductivity. These findings demonstrate that precision chain-growth polymerization provides a molecular design framework for next-generation stretchable electronic materials. Chapter 5 focuses on the design and synthesis of biodegradable poly(propylene carbonate)-block-poly(L-lactide) (PPC–PLLA) multiblock copolymers through a precision chain-growth polymerization strategy. Controlled incorporation of CO₂-based and lactide segments afforded well-defined architectures with narrow dispersity and tunable mechanical and degradation properties. The systematic modulation of block composition enabled predictable phase separation and enhanced toughness compared with conventional blends. This approach establishes a scalable route toward sustainable, precision-engineered biodegradable polymers. Chapter 6 presents post-polymerization modification techniques to introduce functional moieties into precision-synthesized polymers. Through selective end-group transformation and side-chain substitution, the optical, electronic, and interfacial properties of conjugated backbones were systematically tuned. The methodology allowed the creation of diverse polymer derivatives without compromising molecular integrity, extending the versatility of chain-growth-derived materials. These findings underscore the potential of modular post-functionalization as a tool for tailoring multifunctional polymer systems.
more목차
Chapter 1. Introduction 1.
1.1. Evolution of Polymer Science and the Emergence of Precision Control 1.
1.2. Precision Synthesis in Conjugated Polymers: From Step-Growth Polymerization to Chain-Growth Polymerization 2.
1.3. Advancing Biodegradable Polymers through Chain-Growth Precision Strategies 5.
Chapter 2. Dual Living Polymerization Strategy Using Rationally Designed Bifunctional initiators for the Precision Synthesis of Conjugated Rod-Coil Block Copolymers 8.
2.1. Introduction 8.
2.2. Result and Discussion 11.
2.2.1. Vinyl polymer macroinitiator preparation and block copolymerization using SCTP 11.
2.2.2. One-Pot Photo-ATRP Followed by SCTP: A Streamlined Route to Linear and Star Block Copolymers 17.
2.2.3. Self-Organized Thin Films of Rod–Coil Block Copolymers: Nanostructures and Orientation Governed by Architecture 20.
2.3. Conclusion 21.
2.4. Experimental Section 22.
Chapter 3. Designing Uniform ROS-generating Conjugated Nanoparticles via Crystallization-medicated in situ Nanostructuring of Commodity Polymers 40.
3.1. Introduction 40.
3.2. Result and Discussion 43.
3.2.1. Preparation of core-shell conjugated polymer nanoparticles via CD-INCP 43.
3.2.2. Preparation of core-shell conjugated polymer nanoparticles via CD-INCP using a hydrophilic PEG macroinitiator 51.
3.3. Conclusion 53.
3.4. Experimental Section 54.
Chapter 4. Precision Living Polymerization of Conjugated Multiblock Copolymers: Structure-Property Correlations in Stretchability and Charge Transport 62.
4.1. Introduction 62.
4.2. Result and Discussion 65.
4.2.1. Preparation of telechelic poly(3-hexylthiophene) through living Suzuki–Miyaura catalyst-transfer polymerization (SCTP) 65.
4.2.2. Synthesis of Conjugated Multiblock Copolymers: P3HT-mb-PDMS and P3HT-PU 71.
4.3. Conclusion 86.
4.4. Experimental Section 88.
Chapter 5. Biodegradability of Poly(Propylene carbonate): Synthesis of PPC-based Star/block Copolymers and an Integrated Degradation Study 100.
5.1. Introduction 100.
5.2. Result and Discussion 103.
5.2.1. Preparation of PPC/castor oil star copolymers and GPC, DSC analysis 103.
5.2.2. Preparation and Mechanical Characterization of PPC-mb-PLLA Multiblock Copolymers 106.
5.2.3. Biodegradability of PPC, PLLA, and PPC-mb-PLLA multiblock copolymers 110.
5.3. Conclusion 113.
5.4. Experimental Section 115.
Chapter 6. Streamlined Synthesis of Polymers End-capped with Sulfonyl Azide and Sulfonyl Fluoride: Versatile Building Blocks for Click Functionalization 124.
6.1. Introduction 124.
6.2. Result and Discussion 127.
6.2.1. Preparation of disulfide-functionalized polymers and post-modifications 127.
6.2.2. Synthesis of various polymers via Cu-catalyzed multicomponent reaction 134.
6.3. Conclusion 137.
6.4. Experimental Section 138.
References 152.
