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Reversible Covalent Bonding for Olefin Polymerization and Separation
Reversible Covalent Bonding for Olefin Polymerization and Separation
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152140
- ISBN
- 9798384051091
- DDC
- 547
- 서명/저자
- Reversible Covalent Bonding for Olefin Polymerization and Separation
- 발행사항
- [Sl] : Cornell University, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 258 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-03, Section: B.
- 주기사항
- Advisor: Lambert, Tristan.
- 학위논문주기
- Thesis (Ph.D.)--Cornell University, 2024.
- 초록/해제
- 요약The formation and breaking of covalent bonds is a fundamental aspect of chemistry. Typical reactions with olefins form or break a bond to produce a desired transformation in an irreversible process in order to drive the reaction to completion. The idea of temporary bonding to activate olefins is a common topic in catalysis, but usually does not result in fully covalent character. Since the advent of organocatalysis, the idea of temporarily and reversibly forming covalent bonds has seen rapid development. The Lambert group has studied organocatalysis for use in both small molecule transformations and more recently polymerization.This dissertation will discuss two projects revolving around the formation and breakage of a covalent bond to an olefin: (1) pentacarboxyclcylopentadiene (PCCP) catalysts for controlled cationic polymerization of vinyl monomers and (2) the separation of olefins and paraffins by chemiselective olefin capture and release.Chapter 1 provides an introduction to cationic polymerization of vinyl monomers, the background and use of PCCP catalysts in polymerization, and previous derivatives of PCCPs. Following is an exploration of various derivatives of PCCPs for the polymerization of vinyl ethers and expansion of the monomer scope to styrenes is detailed. In particular, the use of alkylated PCCP catalysts enabling the polymerization of p-methylstyrene by reversible ionization of a covalent C-C bond is presented for the first time.Chapter 2 discusses the importance of olefin-paraffin separation and the background of nitrone cycloaddition chemistry. A brief investigation of this reactions use in the capture and release of olefins is discussed. This chapter also provides the motivations for the development of the following chapter.Chapter 3 introduces the chemistry of sulfenic acids and their application to olefin capture. The development of a solution phase method of olefin addition to sulfenic acid then elimination from the resulting sulfoxide in a cyclable manner is detailed. Using this reaction system as a proof of concept, attempts at designing a rigid porous material functionalized with sulfenic acid for more efficient gas phase separation are discussed.
- 일반주제명
- Organic chemistry
- 일반주제명
- Polymer chemistry
- 일반주제명
- Chemistry
- 키워드
- Nitrones
- 키워드
- Olefins
- 키워드
- Organocatalysis
- 키워드
- Separations
- 키워드
- Sulfenic acids
- 기타저자
- Cornell University Chemistry and Chemical Biology
- 기본자료저록
- Dissertations Abstracts International. 86-03B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■00520250211152140
■006m o d
■007cr#unu||||||||
■020 ▼a9798384051091
■035 ▼a(MiAaPQ)AAI31484778
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aGalczynski, Jeffrey.▼0(orcid)0009-0005-7382-4208
■24510▼aReversible Covalent Bonding for Olefin Polymerization and Separation
■260 ▼a[Sl]▼bCornell University▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a258 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-03, Section: B.
■500 ▼aAdvisor: Lambert, Tristan.
■5021 ▼aThesis (Ph.D.)--Cornell University, 2024.
■520 ▼aThe formation and breaking of covalent bonds is a fundamental aspect of chemistry. Typical reactions with olefins form or break a bond to produce a desired transformation in an irreversible process in order to drive the reaction to completion. The idea of temporary bonding to activate olefins is a common topic in catalysis, but usually does not result in fully covalent character. Since the advent of organocatalysis, the idea of temporarily and reversibly forming covalent bonds has seen rapid development. The Lambert group has studied organocatalysis for use in both small molecule transformations and more recently polymerization.This dissertation will discuss two projects revolving around the formation and breakage of a covalent bond to an olefin: (1) pentacarboxyclcylopentadiene (PCCP) catalysts for controlled cationic polymerization of vinyl monomers and (2) the separation of olefins and paraffins by chemiselective olefin capture and release.Chapter 1 provides an introduction to cationic polymerization of vinyl monomers, the background and use of PCCP catalysts in polymerization, and previous derivatives of PCCPs. Following is an exploration of various derivatives of PCCPs for the polymerization of vinyl ethers and expansion of the monomer scope to styrenes is detailed. In particular, the use of alkylated PCCP catalysts enabling the polymerization of p-methylstyrene by reversible ionization of a covalent C-C bond is presented for the first time.Chapter 2 discusses the importance of olefin-paraffin separation and the background of nitrone cycloaddition chemistry. A brief investigation of this reactions use in the capture and release of olefins is discussed. This chapter also provides the motivations for the development of the following chapter.Chapter 3 introduces the chemistry of sulfenic acids and their application to olefin capture. The development of a solution phase method of olefin addition to sulfenic acid then elimination from the resulting sulfoxide in a cyclable manner is detailed. Using this reaction system as a proof of concept, attempts at designing a rigid porous material functionalized with sulfenic acid for more efficient gas phase separation are discussed.
■590 ▼aSchool code: 0058.
■650 4▼aOrganic chemistry
■650 4▼aPolymer chemistry
■650 4▼aChemistry
■653 ▼aCationic polymerization
■653 ▼aNitrones
■653 ▼aOlefins
■653 ▼aOrganocatalysis
■653 ▼aSeparations
■653 ▼aSulfenic acids
■690 ▼a0490
■690 ▼a0495
■690 ▼a0485
■71020▼aCornell University▼bChemistry and Chemical Biology.
■7730 ▼tDissertations Abstracts International▼g86-03B.
■790 ▼a0058
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17163144▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.


