Cyclic carbonates as monomers for phosgene- and isocyanate-free polyurethanes and polycarbonates

Pyo, Sang‐Hyun; Persson, Per; Mollaahmad, M. Amin; Sörensen, Kent; Lundmark, Stefan; Hatti‐Kaul, Rajni

doi:10.1351/pac-con-11-06-14

Cited by 63 publications

(57 citation statements)

References 6 publications

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“…Finally, the synthesis of small molecule isocyanates often involves the toxic reagent, phosgene . From a green chemistry perspective, an environmentally and biologically friendly replacement for isocyanates in polyurethane remains as an active research area …”

Section: Ion‐containing Biobased Polyols and Waterborne Polyurethane mentioning

confidence: 99%

Synthesis, Properties, and Applications of Ion‐Containing Polyurethane Segmented Copolymers

Nelson

Long

2014

Macro Chemistry & Physics

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Despite the well-established foundation of polyurethane chemistry in both industry and academia, research continues at a vigorous pace to refi ne synthetic processes and discover new functional materials. Incorporating ionic groups into polymers is a synthetic parameter capable of tailoring polymer properties and enabling emerging technologies. This review focuses on recent effort in the fi eld of ion-containing segmented polyurethane copolymers. Multiple synthetic strategies to incorporate both cationic and anionic sites, including a particular focus on waterborne polyurethane dispersions and green synthetic methods, are examined. Fundamental structure-property relationships based on ionic structure, content, and placement are explored and many applications, including biomedical products and polymer electrolytes for energy devices are discussed.(PEG) or poly(tetramethylene oxide) (PTMO), to the polyurethane reaction. The hydrogen bonding, depicted in Figure 1 , between the urethane carbonyl oxygen and urethane hydrogen, coupled with crystallization, constructs the hard segment (HS) domains, while the functionalized fl exible spacers comprise the soft segments (SSs) in an alternating fashion. The microphase-separated morphology of segmented polyurethanes is the foundation for their versatility, with the ability to further tune materials for a specifi c application with other synthetic parameters such as chemical composition and molecular weight. Yilgör and co-workers, [ 5 ] Yurtsever and co-workers, [ 6 ] and Wilkes and co-workers [ 7 ] extensively studied various model segmented polyurethane systems to further understand the morphology and factors infl uencing morphology on a fundamental structure-property level.Many comprehensive reviews and peer-reviewed journal articles focus on fundamental structure-property relationships of segmented polyurethanes.

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Section: Ion‐containing Biobased Polyols and Waterborne Polyurethane mentioning

confidence: 99%

Synthesis, Properties, and Applications of Ion‐Containing Polyurethane Segmented Copolymers

Nelson

Long

2014

Macro Chemistry & Physics

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“…Cyclic carbonates have attracted attention as potential monomers to provide an alternative phosgene‐ and isocyanate‐free route for the production of aliphatic polycarbonates and polyurethanes, the polymers with a broad range of applications (e.g., in engineering, optical devices, seatings, seals, coatings, and high performance adhesives) and with increasing demand in biomedicine due to their features of biocompatibility and low toxicity . Cyclic carbonates are mainly produced by transesterification of polyols with dialkylcarbonate in metal‐ or enzyme (lipase)‐catalyzed reaction, and cycloaddition of CO 2 to epoxides .…”

Section: Introductionmentioning

confidence: 99%

Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction

Bornadel

Ismail

Sayed

et al. 2016

Biotechnology Progress

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Six-membered cyclic carbonates with hydroxyl and methoxycarbonyloxy functional groups were prepared by transesterification of trimethylolpropane (TMP) with dimethylcarbonate (DMC) by solvent-free lipase-mediated flow reaction followed by thermal cyclization. The flow reaction efficiency was evaluated using different configurations of reactor consisting of packed beds of Novozym®435 (immobilized Candida antarctica lipase B-CalB-a.k.a. N435) and molecular sieves, flowrate, and biocatalyst loads. The mixed column of the biocatalyst and molecular sieves, allowing rapid and efficient removal of the by-product-methanol-was the most efficient setup. Higher conversion (81.6%) in the flow reaction compared to batch process (72%) was obtained using same amount of N435 (20% (w/w) N435:TMP) at 12 h, and the undesirable dimer and oligomer formation were suppressed. Moreover, the product was recovered easily without extra separation steps, and the biocatalyst and the molecular sieves remained intact for subsequent regeneration and recycling. The reaction of CalB with DMC and the primary transesterification product, monocarbonated TMP, respectively, as acyl donors was evaluated by in silico modeling and empirically to determine the role of the enzyme in the formation of cyclic carbonates and other side products. DMC was shown to be the preferred acyl donor, suggesting that TMP and its carbonated derivatives serve only as acyl acceptors in the lipase-catalyzed reaction. Subsequent cyclization to cyclic carbonate is catalyzed at increased temperature and not by the enzyme. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:375-382, 2017.

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“…Cyclic alkylene carbonates have attracted attention during the past couple of decades as reactive intermediates for safe, environmentally benign, and chlorine‐free production of polymers 1‐4. They can undergo ring‐opening polymerization (ROP) to produce aliphatic polycarbonates (PC), polyurethanes (PU), and copolymers,3‐5 which are widely used in a range of applications, but are produced from toxic phosgene and/or isocyanate compounds 6, 7. The demand for nontoxic, biocompatible PCs and PUs for medical applications has dramatically increased that require phosgene/isocyanate free routes for production 3, 8.…”

Section: Introductionmentioning

confidence: 99%

Optimization of a two‐step process comprising lipase catalysis and thermal cyclization improves the efficiency of synthesis of six‐membered cyclic carbonate from trimethylolpropane and dimethylcarbonate

Bornadel

Hatti‐Kaul

Sörensen

et al. 2012

Biotechnology Progress

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Six-membered cyclic carbonates are potential monomers for phosgene and/or isocyanate free polycarbonates and polyurethanes via ring-opening polymerization. A two-step process for their synthesis comprising lipase-catalyzed transesterification of a polyol, trimethylolpropane (TMP) with dimethylcarbonate (DMC) in a solvent-free system followed by thermal cyclization was optimized to improve process efficiency and selectivity. Using full factorial designed experiments and partial least squares (PLS) modeling for the reaction catalyzed by Novozym®435 (N435; immobilized Candida antarctica lipase B), the optimum conditions for obtaining either high proportion of monocarbonated TMP and TMP-cyclic-carbonate (3 and 4), or dicarbonated TMP and monocarbonated TMP-cyclic-carbonate (5 and 6) were found. The PLS model predicted that the reactions using 15%-20% (w/w) N435 at DMC:TMP molar ratio of 10-30 can reach about 65% total yield of 3 and 4 within 10 h, and 65%-70% total yield of 5 and 6 within 32-37 h, respectively. High consistency between the predicted results and empirical data was shown with 66.1% yield of 3 and 4 at 7 h and 67.4% yield of 5 and 6 at 35 h, using 18% (w/w) biocatalyst and DMC:TMP molar ratio of 20. Thermal cyclization of the product from 7 h reaction, at 110°C in the presence of acetonitrile increased the overall yield of cyclic carbonate 4 from about 2% to more than 75% within 24 h. N435 was reused for five consecutive batches, 10 h each, to give 3+4 with a yield of about 65% in each run.

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Cyclic carbonates as monomers for phosgene- and isocyanate-free polyurethanes and polycarbonates

Cited by 63 publications

References 6 publications

Synthesis, Properties, and Applications of Ion‐Containing Polyurethane Segmented Copolymers

Synthesis, Properties, and Applications of Ion‐Containing Polyurethane Segmented Copolymers

Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction

Optimization of a two‐step process comprising lipase catalysis and thermal cyclization improves the efficiency of synthesis of six‐membered cyclic carbonate from trimethylolpropane and dimethylcarbonate

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