Enabling Oxygen–Sulfur Exchange Reaction to Produce Semicrystalline Copolymers from Carbon Disulfide and Ethylene Oxide

Abstract

This work describes the first example of semicrystalline poly(thiocarbonate)s from carbon disulfide (CS2) and ethylene oxide (EO), two mass producible low‐cost monomers. Lewis acid/base pairs (LPs) exhibit high activity (EO conversion up to >99%, 8 h) in catalyzing the copolymerization under low Lewis pair/monomer ratio of 1:1500. Oxygen–sulfur exchange reaction (O–S ER) during the copolymerization of CS2 and EO, the generation and mutual copolymerization with COS, CO2, and episulfide, is harnessed to introduce crystallizable segments [SC(O)O and SC(S)S] in the copolymer. The type of Lewis base is found to have a great impact on the chain microstructure and the crystalline properties. The formed copolymers with melting point from 117.7 to 245.3 °C are obtained. The maximum crystallinity is estimated to be 78% based on the powder wide‐angle X‐ray diffraction pattern. This work provides a general method to prepare semicrystalline sulfur‐containing polymers.

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

“…Immersion of solid polymer in 30% H2O2 for 12 h degraded resulted in degradation to oligomers (Mw = 1.8 kg/mol) with formation of sulphones (R2SO2) and sulphonic acids (RSO3H). [184] Figure 28: CS2/thiirane ROCOP forming poly(trithiocarbonate).…”

Polymers from sugars and CS2: ring opening copolymerisation of a d-xylose anhydrosugar oxetane

“…[1][2][3][4][5] For instance, polymers which incorporate pyranose or furanose motifs typically exhibit remarkably high glass transition temperatures (T g ) and the availability of hydroxyl groups of sugar derivatives significantly broadens the scope for prospective material functionalisation. [6][7][8][9] It is known that the replacement of oxygen atoms with sulfur ones in oxygenated polymers can give the resulting polythioethers, polythiocarbonates and polythioesters enhanced physical and thermal properties, [10][11][12][13][14][15][16] as well as additional advanced optical 17 and electrical characteristics. 18 Moreover, sulfur-containing polymers exhibit biocompatibility and have shown potential in metal and bacterial adhesion.…”

Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

“…[183] CS2/EO ROCOP using different degrees of crystallinity. [184] Copyright © 2020 Wiley.…”

“…Another interesting feature of these copolymers is their ability to be degraded by oxidants.T he immersion of solid polymer in 30 %H 2 O 2 for 12 hr esulted in degradation to oligomers (M w = 1.8 kg mol À1 )w ith formation of sulfones (R 2 SO 2 )a nd sulfonic acids (RSO 3 H). [184] Figure 25. CS 2 /epoxide ROCOP and 13 C{ 1 H} NMR spectrum illustrating the polymer functionalities accessible when O/S scrambling occurs.…”

“…XRD data for CS 2 /EO copolymers from bicomponent catalysts show different degrees of crystallinity. [184] Copyright 2020 Wiley.…”