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Reversible Covalent Bonding for Olefin Polymerization and Separation
Reversible Covalent Bonding for Olefin Polymerization and Separation
Reversible Covalent Bonding for Olefin Polymerization and Separation

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자료유형  
 학위논문 서양
최종처리일시  
20250211152140
ISBN  
9798384051091
DDC  
547
저자명  
Galczynski, Jeffrey.
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  
Cationic polymerization
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

 008250123s2024        us                              c    eng  d
■001000017163144
■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.

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