Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains

Abstract

Carbon dioxide-based polyoxazolidinones (POxa) are an emerging subclass of non-isocyanate polyurethanes for high temperature applications. Current POxa with rigid linkers suffer from limited solubility that hinders synthesis and characterization. Herein, we report the addition of alkyl and alkoxy solubilizing groups to rigid spirocyclic POxa and their poly(hydroxyoxazolidinone) (PHO) precursors. The modified polymers were soluble in up to six organic solvents, enabling characterization of key properties (e.g., molar mass and polymer structure) using solution-state methods. Dehydration of PHO to POxa changed solubility from highly polar to less polar solvents and improved thermal stability by 76−102 °C. The POxa had relatively high glass transition (85−119 °C) and melting (190−238 °C) temperatures tuned by solubilizing group structure. The improved understanding of factors affecting solubility, structure−property relationships, and degradation pathways gained in this study broadens the scope of soluble POxa and enables more rational design of this promising class of materials.

Facile Access to CO2‐Sourced Polythiocarbonate Dynamic Networks And Their Potential As Solid‐State Electrolytes For Lithium Metal Batteries

“…Lamb et al recently developed new bispropargylic alcohols through the addition of solubilizing groups on the double bond. [22] Although these compounds were characterized by T m ranging from 105 to 200 °C, this approach is an appealing way to potentially access liquid monomers, however total yields starting from the dione were not exceeding 22 %. Schaub et al synthesized monomers starting from 1,4-butynediol and bisepoxides, affording two liquid bisαCCs with overall yields of up to 70 %.…”

“…[10,11] Following studies by us and other research groups have largely expanded the scope of these important families of polymers. [12][13][14][15][16][17][18][19][20][21][22] More specifically, this chemistry allowed to access linear PMTCs through the step-growth copolymerization of bisαCC with dithiols in the presence of a base catalyst under ambient conditions. [11] The versatility of this toolbox was further validated through the one-step synthesis of copolymers containing both urethane and thiocarbonate linkages from the terpolymerization of dithiols and diamines with bisαCC.…”

“…Recently, some of us pioneered the use of CO 2 ‐sourced bis(α‐alkylidene cyclic carbonate)s (bisαCC) monomers to prepare a large palette of new polymers (polycarbonates, polyurethanes, and polythiocarbonates) in unprecedent mild conditions [10,11] . Following studies by us and other research groups have largely expanded the scope of these important families of polymers [12–22] . More specifically, this chemistry allowed to access linear PMTCs through the step‐growth copolymerization of bisαCC with dithiols in the presence of a base catalyst under ambient conditions [11] .…”

Recent Advances in the Synthesis and Polymerization of New CO2‐Based Cyclic†

“…Further targeting the development of new polycarbamates, Lamb and coworkers took advantage from the high reactivity of vinylogues structure such as 36 . [ 52 ] Although prepared in low to moderate yields (36%—50%), tricyclic CO 2 ‐based monomers could be reacted with 1,4‐diamino butane in the presence of DBU at 80 °C delivering appreciable molecular weight polymer ( M n = 9.2—20.9 kg·mol –1 , Ð = 1.42—1.78). Structural modifications of such polymeric cyclic carbamates allowed to modulate their thermal stability as well as their solubility.…”

Covalent Adaptable Networks through Dynamic N,S-Acetal Chemistry: Toward Recyclable CO2-Based Thermosets

“…Overall, this work provides a new tool for the facile preparation of N , S -acetal compounds and recyclable polymer networks from CO 2 . To date, there is no example of oxazolidone-based networks with intrinsic recyclability, and recent contributions on poly­(oxazolidone)­s were focused on linear polymer synthesis. − …”