Atom-Exchange Coordination Polymerization of Carbon Disulfide and Propylene Oxide by a Highly Effective Double-Metal Cyanide Complex

An Investigation on the Production of Random Copolymer with Monothiocarbonate and Trithiocarbonate Units over Cyclic Thiocarbonate via Metal‐free Catalysis

“…As summarized in Table , copolymerization of CS 2 and PGE was successfully catalyzed by organic Lewis pairs composed of TEB as LA and various LBs at 40 o C. In most cases, conversion of PGE accomplished in 8 h, resulting in TOF values around 63 h –1 . Rather than a couple of complicated linkages as previously reported in metal catalyst systems (Scheme ), all of the resulted copolymers had only two kinds of alternating linkages, monothiocarbonate [–O(C=S)O–] ( L1 ) and trithiocarbonate linkages [–S(C=S)S–] ( L2 ), confirmed by 1 H NMR and 1 H‐ 13 C HSQC spectra (Figure , Figures S1—S7). As expected, COS was still an intermediate in this copolymerization, confirmed by GC‐MS (Figure S8).…”

“…In 2007, Nozaki and co‐workers conducted the copolymerization of propylene sulfide and CS 2 to yield poly(propylene trithiocarbonate) with high refractive index (RI) of 1.78 . During 2008—2009, various structures produced by Oxygen‐Sulfur Exchange Reaction (O‐S ER) in both the polymer and cyclic byproducts were confirmed by Zhang and Darensbourg, respectively. This process can generate CO 2 , carbonyl sulfide (COS) and episulfide that mix in the reaction system and mutually copolymerize with CS 2 and epoxide, resulting in the copolymers with randomly distributed thiocarbonates [–SC(=O)O–, –OC(=S)O–, –SC(=S)S–], carbonate [–OC(=O)O–] or even (thio)ether units.…”

Alternating and regioregular copolymers with high refractive index from COS and biomass-derived epoxides

“…sulde that participated in the copolymerization mutually, resulting in the production of the mixed units in the chain. 19,25 The peak a at 5.38 ppm and the peak b at 3.33 ppm (covered by the peak f), in Fig. 3A, were ascribed to the protons of methylene (CH 2 ) and methine (CH) connecting with O and S atoms of the monothiocarbonate unit [-SC(]O)O-], respectively.…”

Cooperative catalysis with binary Lewis acid–Lewis base system for the coupling of carbon disulfide and epoxides

“…Based on some mechanistic aspects of Lewis acid/base co‐catalysis, a plausible mechanism for this cycloaddition is proposed, as shown in Scheme . Indeed, in the presence of a Lewis acid or base, the atom exchange reaction between CS 2 and epoxide easily occurs, thus forming various reactive compounds, such as episulfide, COS and CO 2 (Scheme ).…”