Synthesis of graft terpolymers by addition reaction of amino‐terminated polyether to poly(methacrylate)s bearing five‐membered cyclic dithiocarbonate moieties and application of the graft terpolymers as modifiers for wool

Abstract

Graft terpolymers bearing polyether side chains and poly(methacrylate) stems were synthesized by the graft‐onto reaction of monoamino‐terminated poly(PO9‐co‐EO1) to poly{[5‐(methacryloyloxy)methyl‐1,3‐oxathiolane‐2‐thione]‐co‐n‐butyl methacrylate} [poly(DTCMMA‐co‐BuMA)]. The grafting reaction proceeded via the nucleophilic addition of the terminal amino groups to the five‐membered cyclic dithiocarbonate moieties giving thiol moieties, although the grafting efficiency was low (9–34%) due to the steric hindrance of the side chains. The Tg values of the poly{[DTCMMA‐graft‐poly(PO9‐co‐EO1)]‐co‐BuMA} ranged 27–47 °C, depending on the amounts of flexible poly(PO9‐co‐EO1) chains introduced lowering the Tg values. Poly{[DTCMMA‐graft‐poly(PO9‐co‐EO1)]‐co‐BuMA}s bearing thiol groups were applied for the modification of wool via the disulfide exchange reaction. The modified wool had better dye ability toward a pigment from safflower than the original wool owing to the hydrophilic nature of poly{[DTCMMA‐graft‐poly(PO9‐co‐EO1)]‐co‐BuMA} introduced. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Photoimageable Organic Coating Bearing Cyclic Dithiocarbonate for a Multifunctional Surface

“…We first performed the homopolymerization of DTCMMA via free-radical polymerization; the homopolymers with a modest molecular weight showed extremely poor solubility in common solvents such as THF, DCM, anisole, toluene, ethyl acetate, and cyclopentanone. The solubility issue can be addressed by introducing a comonomer, as it was reported that a copolymer of DTCMMA and n BMA, namely, poly­(DTCMMA- r - n BMA), synthesized by free-radical polymerization, was soluble in common solvents, though dispersity was not well controlled ( Đ > 2.7 at a f DTCMMA of 0.3) . To access soluble copolymers of DTCMMA with narrow molecular weight distribution, we conducted the RAFT copolymerization of DTCMMA and n BMA in anisole.…”

“…Typically, the light-mediated thiol–ene click reaction shows high reaction efficiencies higher than 80%, , while our results exhibited a relatively low DF in the reaction. We first hypothesized that the basic reaction conditions coming from the amine reactant are responsible for the formation of disulfides, which reduce the thiol concentration and limit the reaction. This possibility was investigated with additional experiments in which the polymer film was treated with a DTT reducing agent that can break the disulfide bond before the start of the coupling reaction with AB.…”

“…The solubility issue can be addressed by introducing a comonomer, as it was reported that a copolymer of DTCMMA and nBMA, namely, poly(DTCMMA-r-nBMA), synthesized by free-radical polymerization, was soluble in common solvents, though dispersity was not well controlled (Đ > 2.7 at a f DTCMMA of 0.3). 35 To access soluble copolymers of DTCMMA with narrow app is the apparent propagation rate constant. Figure 1a shows the kinetic plots of copolymerization with the four methacrylates.…”

“…The shape of the SEC traces of the four copolymers with increased conversion (Figure 1c) changes from unimodal to multimodal when Đ exceeds 3, which is in agreement with the results of previous reports on the free-radical copolymerization of DTCMMA with nBMA. 35 These results imply that, at higher conversion, certain but inconsiderable side reactions, such as chain transfer 37 or ringopening, and the coupling reaction of the polymer chains into a disulfide bond, contribute to the increasing dispersity. 38,39 Despite the increase of the Đ, the monomer was consumed with following the linear trend in Figure 1b, implying that the side reactions do not significantly affect the radical-based propagation process based on the RAFT polymerization mechanism.…”

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

“…As a method to avoid the oxidative coupling of thiols, we reported one-pot reactions of in situ generated multiple thiols from dithiocarbonates and amines for fabrication of well-defined polymers [12,13]. This reaction giving thiols is a click reaction [12,13,14,15,16,17,18,19] selective enough to provide a polymer-bearing thiol moieties in the repeating units serving as a polymeric chain transfer agent [12] and dithiols for three-component polyaddition with quantitative atom-economy [13]. We applied this concept to this synthesis of organic-sulfur-zinc hybrid materials.…”