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The Development of Chemically Recycl...

Nie, Cherish,

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The Development of Chemically Recyclable Polyolefins /

Record Type:	Electronic resources : Monograph/item
Title/Author:	The Development of Chemically Recyclable Polyolefins // Cherish Nie.
Author:	Nie, Cherish,
Description:	1 electronic resource (276 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
Contained By:	Dissertations Abstracts International86-12B.
Subject:	Chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31844319
ISBN:	9798280746596

The Development of Chemically Recyclable Polyolefins /
Nie, Cherish,

The Development of Chemically Recyclable Polyolefins /Cherish Nie. - 1 electronic resource (276 pages)

Source: Dissertations Abstracts International, Volume: 86-12, Section: B.

Polyolefins 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.

English

ISBN: 9798280746596Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Polyolefins

The Development of Chemically Recyclable Polyolefins /
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500 $a Source: Dissertations Abstracts International, Volume: 86-12, Section: B.
500 $a Advisors: Chirik, Paul J. Committee members: Register, Richard A.; Davidson, Emily C.; Stache, Erin E.
502 $b Ph.D. $c Princeton University $d 2025.
520 $a Polyolefins 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.
546 $a English
590 $a School code: 0181
650 4 $a Chemistry. $3 516420
650 4 $a Polymer chemistry. $3 3173488
650 4 $a Materials science. $3 543314
650 4 $a Analytical chemistry. $3 3168300
653 $a Polyolefins
653 $a Polypropylene
653 $a Polyethylene
653 $a Plastic waste
653 $a Nickel
690 $a 0485
690 $a 0495
690 $a 0794
690 $a 0486
710 2 $a Princeton University. $b Chemistry. $e degree granting institution. $3 3823544
720 1 $a Chirik, Paul J. $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 86-12B.
790 $a 0181
791 $a Ph.D.
792 $a 2025
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31844319