Alicyclic polyesters from a bicyclic 1,3-dioxane-4-one

Xu, Yaqian; Şucu, Theona; Perry, Mitchell R.; Shaver, Michael P.

doi:10.1039/d0py00448k

Cited by 9 publications

(9 citation statements)

References 34 publications

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“…We further reasoned that the ROP of one ring in the bicyclic BiL will keep the other ring intact, thus leading to an intriguing ring-containing (in-chain) polyester, and that incorporation of the in-chain aliphatic rings could enhance the thermal properties of the resulting polymer because of increased backbone rigidity. 21,60,61 Furthermore, the resulting polymer exhibits two stereogenic centers in a repeat unit, which presents a number of possible stereo-microstructures or tacticities and, thus, the opportunity to use polymer stereochemistry controllable by catalysts or initiators to tune materials properties.…”

Section: The Bigger Picturementioning

confidence: 99%

Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties

Shi

Caporaso

et al. 2021

Chem

111

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Section: The Bigger Picturementioning

confidence: 99%

Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties

Shi

Caporaso

et al. 2021

Chem

111

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“…Among all the five polymer samples, P1 exhibited the highest T g (138 °C) owing to the stiffness in the polymer backbone imparted by the rigid pyrrolidine rings. 52–54 As the n -alkyl side chain length of P2–P4 became longer (methyl, ethyl, and n -butyl), the T g decreased dramatically from 101.0 °C for P2 to 61.8 °C for P3 , and to 61.9 °C for P4 (Fig. 5b), a phenomenon commonly observed in alkyl polymethacrylates.…”

Section: Resultsmentioning

confidence: 87%

Facile synthesis of eight-membered cyclic(ester-amide)s and their organocatalytic ring-opening polymerizations

et al. 2022

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“…Interestingly, this dramatically increased both insertion rates, highlighting the importance of understanding reactivity ratios. 47 …”

Section: Functionalitymentioning

confidence: 99%

Sustainability and Polyesters: Beyond Metals and Monomers to Function and Fate

2022

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Conspectus Poor waste management and unchecked consumption underpin our current paradigm of plastics use, which is demonstrably unsustainable in the long term. Nonetheless, the utility and versatility of plastics suggest that the notion of a plastic-free society is also unsustainable. Responses to this conundrum are increasing, and among these are research efforts focused on the development of more sustainable plastics. This Account, written by trained chemists, reflects an academic research journey culminating in an appreciation of the importance of improving and enabling the overarching systems that plastics exist within. Our primary initial focus was on catalyst development because catalysts are key drivers of sustainability by improving the efficiency and ease of polymerization. Metal catalysts ranging in ligand structure and the incorporated metal(s) were developed for the preparation of traditional polyesters such as poly(lactic acid) and polycaprolactone. The central themes in these works were stereocontrol (tacticity), efficiency (polymerization rate), and versatility (monomer scope). Alongside insights gained by systematically varying catalyst structure came impressive results gained through collaboration, including the remarkably high activity of novel heterometallic zinc catalysts toward various cyclic esters. This catalysis work was complemented by and slowly transitioned to a focus on polymer functionality and monomer design. Several fundamental studies focus on polymer topology, specifically star-shaped polyesters, tuned arm number, length, and tacticity. These reports feature emphases on the end of life (solvolysis) and physical properties of polymers, which were increasingly important themes as work shifted toward new methods of incorporating functionality in polymers produced by ring-opening polymerization. Three key highlights demonstrate this shift: the first two rely upon the exploitation of olefin metathesis (cross- and ring-closing) to functionalize polyesters or polyethers, and the third involves the manipulation of ring-opening polymerization equilibrium to enable selective monomer recovery from a polyester. Our foundational work on 1,3-dioxolan-4-one (DOX) monomers is then discussed because this emerging class of molecules offers a distinct synthetic pathway toward functional polyesters, both conventional and novel. With this DOX framework, polyesters that are usually challenging to synthesize (e.g., poly(mandelic acid)) are accessible because polymerization is driven by the concomitant, controlled extrusion of small molecules (acetone or formaldehyde). After these polyester-focused highlights, the foundation of our ongoing work is presented, namely, that polymer sustainability must be viewed from a systems-level perspective, including economic and social components alongside the environmental considerations. Material design must be driven by practice, and we have to involve key players in academia, industry, and government in a concerted effort t...

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Alicyclic polyesters from a bicyclic 1,3-dioxane-4-one

Abstract: Ring-opening polymerisation of cyclopentyl-decorated dioxaneone rings accesses fully alicyclic polyesters through elimination of formaldehyde.

Cited by 9 publications

References 34 publications

Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties

Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties

Facile synthesis of eight-membered cyclic(ester-amide)s and their organocatalytic ring-opening polymerizations

Sustainability and Polyesters: Beyond Metals and Monomers to Function and Fate

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