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Designing Sustainable Polymer Networks: Reprocessable Polyurethane-Like Materials and Extrudable Covalent Adaptable Networks /

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Designing Sustainable Polymer Networks: Reprocessable Polyurethane-Like Materials and Extrudable Covalent Adaptable Networks // Nathan Suryajaya Purwanto.
作者:	Purwanto, Nathan Suryajaya,
面頁冊數:	1 electronic resource (517 pages)
附註:	Source: Dissertations Abstracts International, Volume: 86-12, Section: A.
Contained By:	Dissertations Abstracts International86-12A.
標題:	Polymer chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=32039169
ISBN:	9798315798408

Designing Sustainable Polymer Networks: Reprocessable Polyurethane-Like Materials and Extrudable Covalent Adaptable Networks /
Purwanto, Nathan Suryajaya,

Designing Sustainable Polymer Networks: Reprocessable Polyurethane-Like Materials and Extrudable Covalent Adaptable Networks /Nathan Suryajaya Purwanto. - 1 electronic resource (517 pages)

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

Efforts to tackle the recyclability challenges of cross-linked polymers in the last two decades shape the development of covalent adaptable networks (CANs), although continuous reprocessing (e.g., melt-extrusion) of CANs are very rarely demonstrated. A significant portion of commercial network polymers consists of polyurethanes (PUs), with a substantial majority of PUs employed as foams. Sustainability concerns in PUs, namely the use of toxic isocyanates and the lack of recyclability, motivate the development of non-isocyanate polyurethanes (NIPUs). This dissertation aims to address challenges associated with the development of NIPU foam CANs and efforts to achieve recycling of CANs through melt-extrusion.The first part of this dissertation centers on the development of renewable, reprocessable, and recyclable polyhydroxyurethane (PHU) and non-isocyanate polythiourethane (NIPTU) foams. We established a rheological strategy to achieve the swift and rapid synthesis of cross-linked, self-blowing PHU foams. Subsequently, we applied this methodology to produce biobased cross-linked PHU foams with precursors derived from cashew nutshell liquid waste and tall oil waste. We further examined the impact of varying blowing agent concentrations, structure, and functionality on the morphology, mechanical properties, and reprocessability of the foams. We also established the facile synthesis of a new class of cross-linked NIPU foam, i.e., NIPTU foams. Leveraging the rapid and catalyst-free disulfide dynamic chemistry inherent in NIPTU linkages, our NIPTU foams are endowed with excellent melt-extrudability to the bulk state. For the first time for any NIPUs, we also demonstrated foam-to-foam recycling of NIPTU foams.The second part of this dissertation aims to reveal the fundamentals of designing CANs amenable to melt-extrusion. We showed that increasing the cross-link density in a dual dissociative and associative polythiourethane (PTU) CAN hastens the reprocessing, due to a shift in the dominance of associative dynamic chemistry relative to the dissociative character, to the point of extrudability. In another example, we synthesized CANs incorporating a dialkylamino disulfide dynamic cross-linker (BiTEMPS methacrylate or BTMA), capable of dissociative dynamic chemistry, demonstrating that the CAN is melt-extrudable at high temperatures where the dialkylamino disulfide dynamic chemistry is sufficiently rapid. Additionally, we designed internally catalyzed associative siloxane-exchange based CANs by incorporating amide groups as secondary linkages. With increasing siloxane and amide concentrations in our CANs, the siloxane exchange becomes progressively faster. This led to the CAN with the highest cross-link density undergoing facile melt extrusion with full retention of cross-link density.The third part of this dissertation summarizes minor contributions to other published works with a central aim to advance the applications and understanding of CANs. We incorporated a non-piperidine-based dialkylamino disulfide dynamic cross-linker and systematically compared their dynamic properties compared to BTMA. We also incorporated two versions of BTMA: one containing oligosulfides (BTMA-Sn) and one containing purely disulfide (BTMA-S2), into polyethylene (PE) CANs and demonstrated excellent reprocessability and melt-extrudability. We developed a method to depolymerize and recover valuable monomer-like compounds from NIPTU networks via trans(thio)carbamoylation, achieving up to 94 mol% monomer recovery. Additionally, we presented the first chain-growth CAN with thionourethane linkages synthesized from commodity comonomers, showing excellent creep resistance and reprocessability. Lastly, we presented the unusual glass transition (Tg) breadth, facile autonomous self-healing, and elimination of the Tg-confinement effect in styrene/2-propylheptylacrylate random copolymers.

English

ISBN: 9798315798408Subjects--Topical Terms:

3173488
Polymer chemistry.
Subjects--Index Terms:

Covalent adaptable network

Designing Sustainable Polymer Networks: Reprocessable Polyurethane-Like Materials and Extrudable Covalent Adaptable Networks /
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