One-Pot Synthesis of Organic-Sulfur-Zinc Hybrid Materials via Polycondensation of a Zinc Salt and Thiols Generated in Situ from Cyclic Dithiocarbonates

Abstract

Soluble organic-sulfur-zinc hybrid polymers were prepared via a one-pot reaction consisting of ring-opening addition and subsequent polycondensation. The first reaction is the nucleophilic ring-opening addition of 2-ethylhexylamine to multifunctional cyclic dithiocarbonates giving multiple thiols in situ. The sequential polycondensation of the in situ generated thiols with Zn(OAc)2 gave the target hybrid polymers. This one-pot method enabled the use of a shorter amine than the previous polycondensation of Zn(OAc)2 and purified thiols, which required octadecylamine to obtain a soluble product. The obtained hybrid polymers may be cast as composite films with polystyrene and poly(methyl methacrylate). Owing to the shorter alkyl chain, the calculated nD values of the products (1.60 or 1.61) are higher than that of the previous product bearing octadecyl chains (1.53).

Review—Organic-Inorganic Hybrid Functional Materials: An Integrated Platform for Applied Technologies

“…[41][42][43] Based on the molecular or nanoscale dimensions of the building blocks, light scattering in homogeneous material can be avoided and optically transparent nanocomposite materials suitable for optical applications can be produced. [44][45][46][47] In some cases phase separation of organic and inorganic components is used for the formation of porous materials. 48,49 Smart materials can be fabricated by modification of the composition on the molecular scale.…”

Six-Membered Cyclic Amidines as Efficient Catalysts for the Synthesis of Cyclic Dithiocarbonates from Carbon Disulfide and Epoxides under Mild Conditions

“…Composite films of the resulting hybrid polymers with polystyrene or poly(methyl methacrylate) might be useful as refractive ingredients. 9 Accordingly, reactions of epoxides with carbon disulfide (CS 2 have been developed) for the synthesis of cyclic dithiocarbonates (1,3-oxathiolane-2-thiones); the reactions can be performed in the presence of lithium bromide, 10 lithium tert-butoxide, 11 hydrotalcite, 12 tributylphosphine and lithium perchlorate, 13 a bimetallic aluminum(salen) complex with tetrabutylammonium bromide {[Al(salen)] 2 O•Bu 4 NBr}, 14 triethylamine, 15 aqueous 4-(dimethylamino) pyridine (DMAP), 16 DMAP and 4-methoxyphenol, 17 an N-heterocyclic carbene and potassium carbonate, 18 or triethylamine in nitromethane. 19 However, most of these reactions require high pressures and/or temperatures above the boiling point of CS 2 .…”

Special Issue “Ring-Opening Polymerization”

“…Ochiai et al [6] report on a unique use of the ring-opening reaction of cyclic dithiocarbonates for the synthesis of organic–sulfur–zinc hybrid materials. The reaction gives the corresponding thiols, and these thiols are condensed with zinc acetate to obtain organic–inorganic hybrid polymers.…”