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Design and Synthesis of New, Functional Bicontinuous Cubic Lyotropic Liquid Crystal Monomer Systems and Polymer Networks
Design and Synthesis of New, Functional Bicontinuous Cubic Lyotropic Liquid Crystal Monomer Systems and Polymer Networks
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152639
- ISBN
- 9798384051503
- DDC
- 547
- 저자명
- Culley, Keira E.
- 서명/저자
- Design and Synthesis of New, Functional Bicontinuous Cubic Lyotropic Liquid Crystal Monomer Systems and Polymer Networks
- 발행사항
- [Sl] : University of Colorado at Boulder, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 205 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
- 주기사항
- Advisor: Gin, Douglas;Noble, Richard.
- 학위논문주기
- Thesis (Ph.D.)--University of Colorado at Boulder, 2024.
- 초록/해제
- 요약The Gin group has designed and synthesized all but one of the current examples of bicontinuous cubic (Q)-phase-forming, singly polymerizable, lyotropic liquid crystal (LLC) monomers. Although the scope of Q-phase LLC polymer networks developed by our group is very diverse and has effectively tackled a wide range of organic materials problems and research gaps, the task of incorporating advanced functionality into these networks is largely unexplored. Currently, only one example has been reported in the literature demonstrating the incorporation of additional functional properties in a Q-phase polymer network. This thesis aimed to demonstrate a variety of new examples of Q-phase polymer networks with added advanced functionality to expand the usefulness of this class of organic materials. The first chapter of this thesis details the design and synthesis of the first example of a catalytically-active Q-phase LLC polymer network with molecular-size-selective, Bronsted acid catalysis capabilities. This novel sulfonic-acid-based catalytic resin demonstrated excellent size selectivity, rejecting reactants with calculated molecular diameters of ≥1.68 nm due to the uniform size of the periodic Q-phase nanopores. This Q-phase polymer resin could also be recycled and reused as a heterogeneous catalyst with negligible loss of catalytic activity. Building off this initial work, the second chapter of this thesis discusses the design and synthesis of a second example of a catalytic Q-phase LLC network: A 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-based resin capable of molecular-size-selective and class-selective catalytic aerobic oxidation of alcohols to carbonyls. This new Q-phase resin demonstrated significant improvements in catalytic activity and molecular-size-selectivity compared to a previously reported TEMPO-based, inverted hexagonal (HII)-phase LLC polymer network with 1D cylindrical nanopores instead of the 3D-interconnected nanopores of the Q phase. Further, a strong primary (1º) over secondary (2º) alcohol class selectivity was observed for the TEMPO-based Q-phase resin, which is the first time this trend has been seen in the literature under transition-metal-free, acidic conditions. This project worked to expand the existing catalog of Q-phase LLC polymer networks with added functional properties in the hydrophilic nanopores. Finally, the last research chapter of this thesis explores the ability to incorporate other functional entities besides catalytic moieties into the hydrophilic headgroup of novel Q-phase LLC monomers. This work describes the development of five new, ionic LLC monomers with synthetically tethered ethylene oxide (EO) groups for materials property improvements. One of these EO-functionalized monomers was found to form the Q-phase, and the resulting network was studied for improvement of water uptake/hydrophilicity and ion conductivity compared to a non-functionalized gemini analog monomer to demonstrate the impact of the EO functionalization. This final project worked to provide a wider-ranging scope of applicability for this class of nanoporous organic materials and introduce useful property improvements for future functional Q-phase LLC monomer design.
- 일반주제명
- Organic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Polymer chemistry
- 키워드
- Liquid crystals
- 키워드
- Polymer networks
- 기타저자
- University of Colorado at Boulder Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-03B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211152639
■006m o d
■007cr#unu||||||||
■020 ▼a9798384051503
■035 ▼a(MiAaPQ)AAI31484894
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aCulley, Keira E.▼0(orcid)0009-0008-3605-0030
■24510▼aDesign and Synthesis of New, Functional Bicontinuous Cubic Lyotropic Liquid Crystal Monomer Systems and Polymer Networks
■260 ▼a[Sl]▼bUniversity of Colorado at Boulder▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a205 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-03, Section: B.
■500 ▼aAdvisor: Gin, Douglas;Noble, Richard.
■5021 ▼aThesis (Ph.D.)--University of Colorado at Boulder, 2024.
■520 ▼aThe Gin group has designed and synthesized all but one of the current examples of bicontinuous cubic (Q)-phase-forming, singly polymerizable, lyotropic liquid crystal (LLC) monomers. Although the scope of Q-phase LLC polymer networks developed by our group is very diverse and has effectively tackled a wide range of organic materials problems and research gaps, the task of incorporating advanced functionality into these networks is largely unexplored. Currently, only one example has been reported in the literature demonstrating the incorporation of additional functional properties in a Q-phase polymer network. This thesis aimed to demonstrate a variety of new examples of Q-phase polymer networks with added advanced functionality to expand the usefulness of this class of organic materials. The first chapter of this thesis details the design and synthesis of the first example of a catalytically-active Q-phase LLC polymer network with molecular-size-selective, Bronsted acid catalysis capabilities. This novel sulfonic-acid-based catalytic resin demonstrated excellent size selectivity, rejecting reactants with calculated molecular diameters of ≥1.68 nm due to the uniform size of the periodic Q-phase nanopores. This Q-phase polymer resin could also be recycled and reused as a heterogeneous catalyst with negligible loss of catalytic activity. Building off this initial work, the second chapter of this thesis discusses the design and synthesis of a second example of a catalytic Q-phase LLC network: A 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-based resin capable of molecular-size-selective and class-selective catalytic aerobic oxidation of alcohols to carbonyls. This new Q-phase resin demonstrated significant improvements in catalytic activity and molecular-size-selectivity compared to a previously reported TEMPO-based, inverted hexagonal (HII)-phase LLC polymer network with 1D cylindrical nanopores instead of the 3D-interconnected nanopores of the Q phase. Further, a strong primary (1º) over secondary (2º) alcohol class selectivity was observed for the TEMPO-based Q-phase resin, which is the first time this trend has been seen in the literature under transition-metal-free, acidic conditions. This project worked to expand the existing catalog of Q-phase LLC polymer networks with added functional properties in the hydrophilic nanopores. Finally, the last research chapter of this thesis explores the ability to incorporate other functional entities besides catalytic moieties into the hydrophilic headgroup of novel Q-phase LLC monomers. This work describes the development of five new, ionic LLC monomers with synthetically tethered ethylene oxide (EO) groups for materials property improvements. One of these EO-functionalized monomers was found to form the Q-phase, and the resulting network was studied for improvement of water uptake/hydrophilicity and ion conductivity compared to a non-functionalized gemini analog monomer to demonstrate the impact of the EO functionalization. This final project worked to provide a wider-ranging scope of applicability for this class of nanoporous organic materials and introduce useful property improvements for future functional Q-phase LLC monomer design.
■590 ▼aSchool code: 0051.
■650 4▼aOrganic chemistry
■650 4▼aChemistry
■650 4▼aPolymer chemistry
■653 ▼aBicontinuous cubic
■653 ▼aHeterogeneous catalysis
■653 ▼aLiquid crystals
■653 ▼aNanoporous materials
■653 ▼aPolymer networks
■690 ▼a0490
■690 ▼a0485
■690 ▼a0495
■71020▼aUniversity of Colorado at Boulder▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-03B.
■790 ▼a0051
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163211▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
