Reworkable Polyhydroxyurethane Films with Reversible Acetal Networks Obtained from Multifunctional Six-Membered Cyclic Carbonates

Matsukizono, Hiroyuki; Endō, Takeshi

doi:10.1021/jacs.7b11824

Cited by 66 publications

(56 citation statements)

References 36 publications

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“…The reagent CDI was chosen for its ease of handling, low toxicity, low cost, and improved reactivity compared to alternatives such as dimethyl-or diphenylcarbonate, which typically require higher temperatures and prolonged reaction times. 20,33 The phenolic carbonate alternatives also necessitate the removal of super-stochiometric amounts of a phenol byproduct, significantly complicating purification procedures. In contrast, the imidazole byproducts from CDI are easily removed via acidic aqueous extraction.…”

Section: Resultsmentioning

confidence: 99%

Towards Automated Monomer Synthesis: A Streamlined Approach for the Synthesis of Cyclic Carbonates

Tan¹,

Hedrick²,

Arrechea³

et al. 2020

Preprint

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Accessing cyclic carbonate monomers on large scales is critical for development of any new carbonate-based material platform. This is particularly important in the context of using automated experimental systems for materials synthesis, which can often require large inputs of starting materials. However, the synthesis of carbonate monomers can be a challenging and tedious endeavor, requiring multiple synthetic steps and purifications. To address this, we report a drastically improved and scalable process for the synthesis of carbonate monomers via a two-step route that avoids the use of hazardous phosgene or chloroformate reagents. The cyclic carbonate monomers can be obtained in high yields and with minimal need for chromatographic purification. This process enables rapid access to a broad array of functional groups on the carbonate monomer and monomers generated from procedure can readily be polymerized via ring-opening polymerization.<br>

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Section: Resultsmentioning

confidence: 99%

Towards Automated Monomer Synthesis: A Streamlined Approach for the Synthesis of Cyclic Carbonates

Tan¹,

Hedrick²,

Arrechea³

et al. 2020

Preprint

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“…amidation or dehydration leading to the formation of ureas, or oxazolidinones, respectively), and by the hydrogen bonding network arising from the numerous urethane functions throughout the macromolecules. [5][6][7][8]13,19,20,21,22,23,24,25,26 In spite of their relatively high stability, five-membered cyclic carbonates remain the most investigated precursors to NIPUs since they are synthetically more readily available, in particular by carboxylation of epoxides. 21,22,27,28,29,30,31 The objectives are thus to establish a room temperature, ideally catalyst-free and solvent-free, efficient aminolysis of such five-membered ring cyclic carbonates towards NIPUs/PHUs.…”

Section: Ones While Pus Obtained By Transurethanization Display Compmentioning

confidence: 99%

α,ω-Di(vinylene carbonate) telechelic polyolefins: Synthesis by metathesis reactions and studies as potential precursors toward hydroxy-oxazolidone-based polyolefin NIPUs

Chauveau

Fouquay²,

Michaud³

et al. 2019

European Polymer Journal

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Current polyurethane (PU) industrial and academic research aims at developing nonisocyanate PUs, referred to as NIPUs. Within this context, we report herein the synthesis of original vinylene carbonate (VC) compounds, subsequently used as chain-transfer agents (CTAs) towards the preparation of α,ω-di(VC) telechelic (co)polyolefins from the tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins. Thus, (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl acrylate (VC1), bis((5-methyl-2-oxo-1,3dioxol-4-yl)methyl) fumarate (VC2), and bis((5-methyl-2-oxo-1,3-dioxol-4-yl)methyl) (E)hex-3-enedioate (VC3) were synthesized from 4-(hydroxymethyl)-5-methyl-1,3-dioxol-2-one (DMDO-OH). Among these, only VC3 successfully and selectively afforded well-defined ,-di(vinylene carbonate) telechelic polyolefins, namely di(VC3)-PCOE and di(VC3)-P(NB-co-CDT), from the ROMP/CM of COE, and norbonene (NB)/trans,trans,cis-1,5,9cyclododecatriene (CDT), respectively, using Grubbs' 2nd-generation ruthenium catalyst (G2) under mild operating conditions (CH 2 Cl 2 , 40 °C, 3 h). Preliminary investigations on the reactivity of a model VC, namely 4,5-dimethyl-1,3-dioxol-2-one (DMDO), towards nucleophiles such as a primary or secondary amine, promisingly showed the formation of hydroxy-oxazolidone compounds 1 and 2, and oxo-urethane 3 species, respectively. Yet, the ultimate reaction of di(VC3)-PCOE with 2,2′-(ethylenedioxy)bis(ethylamine) (EDR-148) did not give the expected poly(di(hydroxy-oxazolidone)polyolefin) polyaddition type of NIPUs; competing amidation and/or dehydration or urea formation reactions evidenced by detailed NMR, FTIR and MS analyses, were proposed to account for this inefficiency.

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“…In 2018, two interesting works were reported with fascinating reworkable properties on PHUs. 44,45 PHU-containing acetal group undergoes acid-catalyzed reversibility in solvents. 43,44 By using cystamine as comonomer, reprocessable PHUs were achieved at 150 °C.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Poly(hydroxy urethane)s: Folded-Sheet Morphology and Thermoreversible Adhesion

et al. 2019

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Hybrid poly(hydroxy urethane)s (PHUs) are synthesized by copolymerizing aromatic/alicyclic cyclic carbonates with a polyether amine via addition polymerization. They result into polymers with an average molecular weight of 10 kDa and exhibit solubility in common organic solvents. The hybrid PHUs display T g up to 18 °C. PHUs are enriched with multiple H-bonded interactions and they are assessed using temperature-dependent 1 H NMR and Fourier-transform infrared studies. PHUs possess folded-sheet morphology with nanogap between folds and nanowidth between chains. The secondary interactions bestow thermoreversible property to PHUs, and they display good adhesion to both polar (Al–Al) and nonpolar (HDPE–HDPE) substrates. Hybrid PHUs show improved optical transparency compared to homo PHUs. The PHUs are thermally stable up to 250 °C.

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Reworkable Polyhydroxyurethane Films with Reversible Acetal Networks Obtained from Multifunctional Six-Membered Cyclic Carbonates

Cited by 66 publications

References 36 publications

Towards Automated Monomer Synthesis: A Streamlined Approach for the Synthesis of Cyclic Carbonates

Towards Automated Monomer Synthesis: A Streamlined Approach for the Synthesis of Cyclic Carbonates

α,ω-Di(vinylene carbonate) telechelic polyolefins: Synthesis by metathesis reactions and studies as potential precursors toward hydroxy-oxazolidone-based polyolefin NIPUs

Hybrid Poly(hydroxy urethane)s: Folded-Sheet Morphology and Thermoreversible Adhesion

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