Thermal, optical and structural properties of blocks and blends of PLA and P2HEB

MakwanaVishalkumar, A; Lizundia, Erlantz; LarrañagaAitor,; Vilas, José Luis; Shaver, Michael P.

doi:10.1680/jgrma.18.00006

Cited by 10 publications

(6 citation statements)

References 67 publications

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“… 43 We tuned the thermal properties of PHEB by incorporating it into PLA. 44 Copolymerization of 2,3-DHB with l -lactide increased the thermal properties and stability up to those of the triblock copolymer ( T g = 40 °C, T m = 145 °C). Depolymerization does not occur without an accessible chain end, although selectively removing a single block in a block copolymer may facilitate sequential monomer isolation in chemical recycling systems.…”

Section: Functionalitymentioning

confidence: 95%

“…43 We tuned the thermal properties of PHEB by incorporating it into PLA. 44 Copolymerization of 2,3-DHB For each of these polymeric targets, the products are somewhat esoteric and likely to be expensive. In our efforts to consider economic sustainability, we recently explored an underutilized synthetic strategy to expand the scope of conventional polyesters through the polymerization of 1,3dioxolan-4-one (DOX) monomers.…”

Section: ■ Functionalitymentioning

confidence: 99%

“…Thermal degradation of PHEB occurs above 145 °C, limiting applications to low temperature . We tuned the thermal properties of PHEB by incorporating it into PLA . Copolymerization of 2,3-DHB with l -lactide increased the thermal properties and stability up to those of the triblock copolymer ( T g = 40 °C, T m = 145 °C).…”

Section: Functionalitymentioning

confidence: 99%

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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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Section: Functionalitymentioning

confidence: 95%

Section: ■ Functionalitymentioning

confidence: 99%

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

2022

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“…50 Similarly, the degradation rate of di-and triblock copolymers of LLA and 2-(2-hydroxyethoxy)benzoate is slower than that of their respective homopolymers, demonstrating how additional control of the biodegradation rate can be achieved through well-defined block copolymer synthesis. 51 Monomer sequence and distribution also determine the degradation rate of biopolymers, which is highlighted when examining PLGA. The degradation half-life of PLA is reduced from >7 months for the homopolymer to ∼1−2 weeks by copolymerization with 50% glycolic acid.…”

Section: ■ Compostability Of Polymersmentioning

confidence: 99%

“…A recent example of this is the synthesis of poly(ε-CL- block -LLA- block -ε-CL), which showed a reduced crystallinity compared with the poly(ε-CL) homopolymer, and the degradation rate of the block copolymer decreased with increasing l -lactide (LLA) block length . Similarly, the degradation rate of di- and triblock copolymers of LLA and 2-(2-hydroxyethoxy)benzoate is slower than that of their respective homopolymers, demonstrating how additional control of the biodegradation rate can be achieved through well-defined block copolymer synthesis …”

Section: Compostability Of Polymersmentioning

confidence: 99%

Design and Control of Compostability in Synthetic Biopolyesters

Samantaray

Little

Wemyss

et al. 2021

ACS Sustainable Chem. Eng.

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The aerobic composting and anaerobic digestion of plastics is a promising route to recovering the multidimensional value from biodegradable single-use plastics. At present, the collection, separation, and management of biodegradable plastic waste are extremely challenging, and the majority of these plastics still end up in landfills or incineration facilities. This is because not all biodegradable plastics can be treated using organic waste management options (composting). In addition, end-users at a domestic and industrial level are often unaware of the compostability potential of biodegradable plastics, which results in the mismanagement of these types of plastic. A greater understanding of the compostability of biodegradable plastics will generate the required knowledge base for interventions that support their market penetration, use, and proper management. In this review, we clarify the concepts of biodegradability and compostability in bioplastics, in particular commercial synthetic biopolyesters, which have increasing technical and economic importance, and discuss how macromolecular design, blending, and additives can be used to modify their compostability. Future trends on the uptake of compostable and biodegradable bioplastics are also discussed.

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Advances in the Synthesis of Poly(Phenolic Ester)s via Ring‐Opening Polymerization

Lin,

Lu,

Liu

et al. 2024

ChemCatChem

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The poly(phenolic ester)s are attracting growing attention due to their essential role in the application as biodegradable plastics. Thus, extensive efforts have been devoted to the development of methodology that allows facile preparation of poly(phenolic ester)s with controlled molecular weights for widespread utilities. However, it is highly challenging to introduce phenolic ester bond structure into polyesters from ring‐opening polymerization (ROP) to yield aromatic/semiaromatic poly(phenolic ester)s due to severe transesterification reactions. To synthesize poly(phenolic ester)s with desired structures and properties, scientists have developed various ring‐opening polymerization systems with distinct advantages. Here, we have summarized basic features and recent progresses of these methods, including the cyclic phenolic lactone polymerization system, the salicylic acid O‐carboxyanhydride polymerization system, and the dissymmetric cyclic phenolic lactide polymerization system, as well as other copolymerization routes. Furthermore, the advantages and unsettled problems in various synthetic ways are discussed for readers to choose fast and controllable ROP systems for poly(phenolic ester)s.

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Thermal, optical and structural properties of blocks and blends of PLA and P2HEB

Cited by 10 publications

References 67 publications

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

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

Design and Control of Compostability in Synthetic Biopolyesters

Advances in the Synthesis of Poly(Phenolic Ester)s via Ring‐Opening Polymerization

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