Polyoxalates from biorenewable diols via Oxalate Metathesis Polymerization

Garcia, John J.; Miller, Stephen A.

doi:10.1039/c3py01185b

Cited by 36 publications

(43 citation statements)

References 17 publications

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“…P2(2a‐3b) with C8 aliphatic backbone revealed a T m of 45 °C, whereas P3(2a‐3c) with slightly longer chain (C12) aliphatic backbone displayed an enhanced melting temperature ( T m ) of 63 °C. These melting temperatures are considerably lower than those reported for corresponding linear polyoxalates . We reasoned that this is most likely due to the presence of isomannide rings which disrupt the regular arrangement of polymeric chains and becomes relatively more amorphous.…”

Section: Resultsmentioning

confidence: 55%

“…These control experiments imply an oxalate cross metathesis to in situ produce 3a″ during the initial stages of polymerization. Due to the similarity between olefin cross‐metathesis and the reactivity between a dioxalate and a diol to polyoxalate, this intriguing reaction can be named as oxalate cross‐metathesis polymerization (OCMP) . The proposed in situ formation of 2a′ and 3a′ , and polymerization to P1(2a‐3a) is further supported by a control experiment between ex‐situ prepared 2a′ and 3a′ .…”

Section: Resultsmentioning

confidence: 82%

“…Synthesis of oxalates is routinely carried out by treating alcohols with acids or by treating diols with dimethyl oxalate in presence of Lewis acids (Scheme 1, top). 26,27 Our initial attempts to prepare poly(isomannide)oxalates using literature reported method were largely unsuccessful and low molecular weight (450 Da) tar like liquid could be obtained. 28 This is most likely due to the reduced reactivity of sterically encumbered secondary hydroxy groups installed on the rigid isohexides.…”

Section: Synthesis Of Isohexide-dioxalatesmentioning

confidence: 99%

“…After having isolated 2a-2c, their performance in oxalate metathesis polymerization (OMP) was examined. 27 It is anticipated that dioxalates will serve as AA-type monomers and diols will behave as BB type monomers to yield AABB type polymers. The diol selection is based on their bio-renewability and degradability.…”

Section: Polymerization Mechanism and Poly(isohexide-co-alkane)oxalatesmentioning

confidence: 99%

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Cross‐metathesis of biorenewable dioxalates and diols to film‐forming degradable polyoxalates

Rajput

Ram

Menon

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Starting from commonly available sugar derivatives, a single step protocol to access a small family of isohexide‐dioxalates (2a–c) has been established. The synthetic competence of 2a–c has been demonstrated by subjecting them to condensation polymerization. Quite surprisingly, the proton NMR of poly(isomannide‐co‐hexane)oxalate revealed a 1:2 ratio between isomannide‐dioxalate (2a) and 1,6‐hexanediol (3a) in the polymer backbone. This intriguing reactivity was found to be an outcome of a cross metathesis reaction between 2a and 3a. The cross metathesis products 3a”[2‐(2‐methoxyacetoxy)ethyl 2‐(2‐hydroxyethoxy)‐2‐(λ3‐oxydanylidene)acetate] and 2a‘(3R,6R)‐6‐hydroxyhexahydrofuro[3,2‐b]‐furan‐3‐yl methyl oxalate were isolated in a control experiment. Based on direct and indirect evidence, and control experiments, an alternative polymerization mechanism is proposed. Polymerization conditions were optimized to obtain polyoxalates P1(2a‐3a)‐P9(2c‐3c) with molecular weights in the range of 14,000–68,000 g/mol, and narrow polydispersities. The identity of the polyoxalates was unambiguously established using 1‐2D NMR spectroscopy, MALDI‐ToF‐MS, and GPC measurements. The practical implication of these polymers is demonstrated by preparing transparent, mechanically robust films. The environmental footprint of the selected polyoxalates was investigated by subjecting them to solution and solid‐state degradation. The polyoxalates were found to be amenable to degradation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1584–1592

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Section: Resultsmentioning

confidence: 55%

Section: Resultsmentioning

confidence: 82%

Section: Synthesis Of Isohexide-dioxalatesmentioning

confidence: 99%

Section: Polymerization Mechanism and Poly(isohexide-co-alkane)oxalatesmentioning

confidence: 99%

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Cross‐metathesis of biorenewable dioxalates and diols to film‐forming degradable polyoxalates

Rajput

Ram

Menon

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…Aliphatic polyoxalates are mostly prepared by ring‐opening polymerization of cyclic oxalates or polycondensation between diols and oxalyl chloride or dimethyl oxalate. Their facile degradability under aqueous conditions and their biocompatibility have raised interest in medical applications such as absorbable sutures and drugs delivery, but also as eco‐friendly packaging . Interestingly, the use of polyoxalate in chemiluminescence has not been extensively studied and only a few examples have been developed aiming at detecting and imaging H 2 O 2 .…”

Section: Polymer‐supported Chemiluminescencementioning

confidence: 99%

All Eyes on Visible‐Light Peroxyoxalate Chemiluminescence Read‐Out Systems

Delafresnaye

Bloesser

Kockler

et al. 2019

Chemistry A European J

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Chemiluminescence (CL) reactions have been widely employed and explored over the past 50 years because they offer unique light emission upon a defined chemical stimulus. In this Minireview, we focus on peroxyoxalate (PO) compounds because they feature very high quantum yields tuneable over the entire visible spectrum, allowing for visible‐light detection by the naked eye without the necessity for expensive analytical instruments. Although analytical methods have been extensively described, PO‐CL read‐out is a strongly emerging field with ample industrial potential. The state‐of‐the‐art PO‐CL detection read‐out systems for various key analytes is here explored. In particular, structural requirements, recent developments of PO‐CL read‐out probes and current limitations of selected examples are detailed. Furthermore, innovative approaches and synthetic routes to push the boundaries of PO‐CL reactions into biological systems are highlighted. Underpinned by recent contributions, we share perspectives on embedding PO‐CL molecules into polymeric materials, which they consider the next step in designing high performance solid‐phase read‐out systems.

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Seawater‐Degradable Polymers—Fighting the Marine Plastic Pollution

et al. 2020

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Polymers shape human life but they also have been identified as pollutants in the oceans due to their long lifetime and low degradability. Recently, various researchers have studied the impact of (micro)plastics on marine life, biodiversity, and potential toxicity. Even if the consequences are still heavily discussed, prevention of unnecessary waste is desired. Especially, newly designed polymers that degrade in seawater are discussed as potential alternatives to commodity polymers in certain applications. Biodegradable polymers that degrade in vivo (used for biomedical applications) or during composting often exhibit too slow degradation rates in seawater. To date, no comprehensive summary for the degradation performance of polymers in seawater has been reported, nor are the studies for seawater-degradation following uniform standards. This review summarizes concepts, mechanisms, and other factors affecting the degradation process in seawater of several biodegradable polymers or polymer blends. As most of such materials cannot degrade or degrade too slowly, strategies and innovative routes for the preparation of seawater-degradable polymers with rapid degradation in natural environments are reviewed. It is believed that this selection will help to further understand and drive the development of seawater-degradable polymers.

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Polyoxalates from biorenewable diols via Oxalate Metathesis Polymerization

Cited by 36 publications

References 17 publications

Cross‐metathesis of biorenewable dioxalates and diols to film‐forming degradable polyoxalates

Cross‐metathesis of biorenewable dioxalates and diols to film‐forming degradable polyoxalates

All Eyes on Visible‐Light Peroxyoxalate Chemiluminescence Read‐Out Systems

Seawater‐Degradable Polymers—Fighting the Marine Plastic Pollution

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