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The Development of Chemically Recyclable Polyolefins
The Development of Chemically Recyclable Polyolefins
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202103019
- ISBN
- 9798280746596
- DDC
- 540
- 저자명
- Nie, Cherish.
- 서명/저자
- The Development of Chemically Recyclable Polyolefins
- 발행사항
- [Sl] : Princeton University, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 276 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
- 주기사항
- Advisor: Chirik, Paul J.
- 학위논문주기
- Thesis (Ph.D.)--Princeton University, 2025.
- 초록/해제
- 요약Polyolefins such as polyethylene and polypropylene are attractive and ubiquitous materials due to their low cost of production from abundant feedstock monomers and high thermodynamic stability arising from their hydrocarbon composition. The same attributes severely limit options for sustainable end-of-life treatment as traditional mechanical recycling and incineration are both inefficient and value-reducing processes that are far outpaced by the production of virgin polymer resins. The inherent stability of polyolefins hinders the efficient conversion of waste polymer into valuable products while also contributing to the persistence and accumulation of plastic waste in the environment. The critical need for sustainable alternatives to commodity polyolefins has motivated research efforts to develop new polymer architectures and depolymerization catalysts that enable selective recovery of monomer building blocks from plastic waste. This process is known as chemical recycling and is a key step toward achieving a circular plastics economy.In this dissertation, the development of oligocyclobutane-based polymers derived from butadiene, a feedstock monomer, that undergo clean and selective chemical recycling is described. Through iron-catalyzed [2+2] cycloaddition-oligomerization of butadiene to form (1,n'-divinyl)oligocyclobutane (DVOCB) followed by ruthenium-catalyzed acyclic diene metathesis polymerization, a class of hydrocarbon polyolefins (pDVOCB) featuring a backbone composed of 1,3-enchained cyclobutanes was synthesized, characterized, and demonstrated to be chemically recyclable. pDVOCB exhibited excellent thermal stability, high crystallinity, and promising mechanical performance comparable to commodity polyolefins. Strategies to achieve targeted structural modifications were then explored including post-polymerization modifications, cross-[2+2] copolymerization, and hydrosilylation copolymerization to achieve improved processability and material properties while retaining depolymerizability.The development of robust depolymerization catalysts based on nickel with donating L-type ligands is also described. Specific N-heterocyclic carbenes and phosphines were demonstrated to be effective ligands for nickel-mediated C-C oxidative addition of vinylcyclobutane (VCB), a key elementary step in the depolymerization of DVOCB. The resulting isolable (L)nickel(II) η1,η3-metallacycles were characterized and evaluated as catalysts for VCB activation under thermal and photochemical conditions. Through extensive mechanistic studies, three accessible reaction pathways were identified: retro-[2+2] cycloaddition, β-H elimination, and [2+1] cycloaddition. Ligand design principles governing catalyst activity and selectivity were established, and nickel catalysis was applied toward the retro-[2+2] depolymerization of DVOCB.
- 일반주제명
- Chemistry
- 일반주제명
- Polymer chemistry
- 일반주제명
- Materials science
- 일반주제명
- Analytical chemistry
- 키워드
- Polyolefins
- 키워드
- Polypropylene
- 키워드
- Polyethylene
- 키워드
- Plastic waste
- 키워드
- Nickel
- 기타저자
- Princeton University Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-12B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■006m o d
■007cr#unu||||||||
■020 ▼a9798280746596
■035 ▼a(MiAaPQ)AAI31844319
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aNie, Cherish.▼0(orcid)0000-0002-3758-9950
■24510▼aThe Development of Chemically Recyclable Polyolefins
■260 ▼a[Sl]▼bPrinceton University▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a276 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-12, Section: B.
■500 ▼aAdvisor: Chirik, Paul J.
■5021 ▼aThesis (Ph.D.)--Princeton University, 2025.
■520 ▼aPolyolefins such as polyethylene and polypropylene are attractive and ubiquitous materials due to their low cost of production from abundant feedstock monomers and high thermodynamic stability arising from their hydrocarbon composition. The same attributes severely limit options for sustainable end-of-life treatment as traditional mechanical recycling and incineration are both inefficient and value-reducing processes that are far outpaced by the production of virgin polymer resins. The inherent stability of polyolefins hinders the efficient conversion of waste polymer into valuable products while also contributing to the persistence and accumulation of plastic waste in the environment. The critical need for sustainable alternatives to commodity polyolefins has motivated research efforts to develop new polymer architectures and depolymerization catalysts that enable selective recovery of monomer building blocks from plastic waste. This process is known as chemical recycling and is a key step toward achieving a circular plastics economy.In this dissertation, the development of oligocyclobutane-based polymers derived from butadiene, a feedstock monomer, that undergo clean and selective chemical recycling is described. Through iron-catalyzed [2+2] cycloaddition-oligomerization of butadiene to form (1,n'-divinyl)oligocyclobutane (DVOCB) followed by ruthenium-catalyzed acyclic diene metathesis polymerization, a class of hydrocarbon polyolefins (pDVOCB) featuring a backbone composed of 1,3-enchained cyclobutanes was synthesized, characterized, and demonstrated to be chemically recyclable. pDVOCB exhibited excellent thermal stability, high crystallinity, and promising mechanical performance comparable to commodity polyolefins. Strategies to achieve targeted structural modifications were then explored including post-polymerization modifications, cross-[2+2] copolymerization, and hydrosilylation copolymerization to achieve improved processability and material properties while retaining depolymerizability.The development of robust depolymerization catalysts based on nickel with donating L-type ligands is also described. Specific N-heterocyclic carbenes and phosphines were demonstrated to be effective ligands for nickel-mediated C-C oxidative addition of vinylcyclobutane (VCB), a key elementary step in the depolymerization of DVOCB. The resulting isolable (L)nickel(II) η1,η3-metallacycles were characterized and evaluated as catalysts for VCB activation under thermal and photochemical conditions. Through extensive mechanistic studies, three accessible reaction pathways were identified: retro-[2+2] cycloaddition, β-H elimination, and [2+1] cycloaddition. Ligand design principles governing catalyst activity and selectivity were established, and nickel catalysis was applied toward the retro-[2+2] depolymerization of DVOCB.
■590 ▼aSchool code: 0181.
■650 4▼aChemistry
■650 4▼aPolymer chemistry
■650 4▼aMaterials science
■650 4▼aAnalytical chemistry
■653 ▼aPolyolefins
■653 ▼aPolypropylene
■653 ▼aPolyethylene
■653 ▼aPlastic waste
■653 ▼aNickel
■690 ▼a0485
■690 ▼a0495
■690 ▼a0794
■690 ▼a0486
■71020▼aPrinceton University▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-12B.
■790 ▼a0181
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17356699▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
