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Large Polymers That Behave Like Small Polymers
Large Polymers That Behave Like Small Polymers
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152807
- ISBN
- 9798384094920
- DDC
- 540
- 서명/저자
- Large Polymers That Behave Like Small Polymers
- 발행사항
- [Sl] : University of Washington, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 179 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
- 주기사항
- Advisor: Golder, Matthew.
- 학위논문주기
- Thesis (Ph.D.)--University of Washington, 2024.
- 초록/해제
- 요약Polymer architecture dictates the physical properties and therefore the function of a material. Consequently, structural changes in the polymer backbone have drastic influences on macromolecular physical properties. For example, rigid monomer units create stiff polymer chains with excellent thermal and mechanical properties, at the expense of processability. Meanwhile, flexible monomer units like ethylenes and siloxanes create soft, flexible plastics at the expense of thermal and mechanical robustness. Synthesizing polymers with novel architectures can overcome these challenges by creating materials with a unique set of properties and thus eliminating the trade-off between chain flexibility and desirable macromolecular physical properties. Detailed within this thesis are our reports of modulating backbone architecture of linear polymers using fluxional monomer units. Additionally, we explore the synthesis of cyclic polymer architectures using ring expansion metathesis polymerization (REMP) through catalyst design and mechanistic studies. First, we demonstrate that small molecule pericyclic rearrangements in bullvalene monomer units creates stochastic kinks in an otherwise rigid polymer backbone. This unique chain architecture results in lower hydrodynamic volumes and decreased thermal transitions. Next, we investigate a different, but also compact, polymer architecture by investigating the REMP mechanism and the role of chain transfer events in molecular weight evolution and size of the cyclic polymer products. Finally, we investigate the structure-function relationship of REMP catalysts by modifying tether length and studying the resulting polymerization profiles. Tether length was found to have a significant effect on REMP rate, providing further understanding on these processes. Through these studies, we elucidate valuable information on REMP polymerization profiles and catalyst behavior, providing insight for future optimization of the synthesis of cyclic polymers.
- 일반주제명
- Chemistry
- 일반주제명
- Engineering
- 일반주제명
- Materials science
- 일반주제명
- Polymer chemistry
- 키워드
- Cyclic polymers
- 키워드
- REMP catalysts
- 기타저자
- University of Washington Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-03B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211152807
■006m o d
■007cr#unu||||||||
■020 ▼a9798384094920
■035 ▼a(MiAaPQ)AAI31557221
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aPomfret, Meredith.
■24510▼aLarge Polymers That Behave Like Small Polymers
■260 ▼a[Sl]▼bUniversity of Washington▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a179 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-03, Section: B.
■500 ▼aAdvisor: Golder, Matthew.
■5021 ▼aThesis (Ph.D.)--University of Washington, 2024.
■520 ▼aPolymer architecture dictates the physical properties and therefore the function of a material. Consequently, structural changes in the polymer backbone have drastic influences on macromolecular physical properties. For example, rigid monomer units create stiff polymer chains with excellent thermal and mechanical properties, at the expense of processability. Meanwhile, flexible monomer units like ethylenes and siloxanes create soft, flexible plastics at the expense of thermal and mechanical robustness. Synthesizing polymers with novel architectures can overcome these challenges by creating materials with a unique set of properties and thus eliminating the trade-off between chain flexibility and desirable macromolecular physical properties. Detailed within this thesis are our reports of modulating backbone architecture of linear polymers using fluxional monomer units. Additionally, we explore the synthesis of cyclic polymer architectures using ring expansion metathesis polymerization (REMP) through catalyst design and mechanistic studies. First, we demonstrate that small molecule pericyclic rearrangements in bullvalene monomer units creates stochastic kinks in an otherwise rigid polymer backbone. This unique chain architecture results in lower hydrodynamic volumes and decreased thermal transitions. Next, we investigate a different, but also compact, polymer architecture by investigating the REMP mechanism and the role of chain transfer events in molecular weight evolution and size of the cyclic polymer products. Finally, we investigate the structure-function relationship of REMP catalysts by modifying tether length and studying the resulting polymerization profiles. Tether length was found to have a significant effect on REMP rate, providing further understanding on these processes. Through these studies, we elucidate valuable information on REMP polymerization profiles and catalyst behavior, providing insight for future optimization of the synthesis of cyclic polymers.
■590 ▼aSchool code: 0250.
■650 4▼aChemistry
■650 4▼aEngineering
■650 4▼aMaterials science
■650 4▼aPolymer chemistry
■653 ▼aCyclic polymers
■653 ▼aPolymer architecture
■653 ▼aPhysical properties
■653 ▼aREMP catalysts
■653 ▼aMechanical properties
■690 ▼a0485
■690 ▼a0794
■690 ▼a0537
■690 ▼a0495
■71020▼aUniversity of Washington▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-03B.
■790 ▼a0250
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163901▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
