Rapid Hyperbranched Polythioether Synthesis Through Thiol‐Michael Addition Reaction

Abstract

In this study, two types of hyperbranched (HB) polythioether could readily be achieved in a short time at ambient temperature through a thiol‐Michael addition reaction. Dimethyl acetylenedicarboxylate (DMADC) or methyl propiolate (A2) and trimethylolpropane tris(3‐mercaptopropionate) (B3) monomers were reacted using an organobase 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as a catalyst in chloroform at room temperature to provide subsequent HB polythioethers. The effect of TBD concentration on the polymerization was studied for the DMDAC case monitoring the molecular weight evolution against time. HB polythioethers were characterized using spectroscopic (nuclear magnetic resonance) and chromatographic (gel permeation chromatography with refractive index and light‐scattering detectors) techniques. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 824–830

Functional Hyperbranched Polythioamides Synthesized from Catalyst‐free Multicomponent Polymerization of Elemental Sulfur†

“…[ 6,15‐18 ] On the other hand, sulfur‐containing polymers including polythioethers, [ 19‐20 ] polythioesters, [ 21‐22 ] poly(monothiocarbonate)s, [ 23 ] polytrithiocarbonates, [ 24 ] polythioureas, [ 25 ] polythioamides, [ 26 ] polythiophenes, [ 27 ] and others, which generally enjoy high refractive indices, [ 28 ] excellent metal coordination ability, [ 25,29‐30 ] self‐repairing performance, [ 31 ] electrical conductivity, [ 27,32‐33 ] and degradability, [ 34‐36 ] have attracted much attention as advanced materials in the applications including optical materials, [ 37 ] sewage treatment materials, [ 30,38 ] self‐healing materials [ 31 ] and dielectric materials. [ 32,33 ] However, limited examples about sulfur‐containing hyperbranched polymers such as disulfide‐containing hyperbranched poly(amido amine)s with controllable bioreducibility and stimuli‐responsive property were developed, [ 39‐44 ] due to the lack of efficient synthetic approaches, and current methods generally involve sulfur‐bearing smelly and toxic monomers or byproducts.…”

Activated Internal Alkyne‐Based Polymerization†

“…0]dec‐5‐ene (TBD). [ 76‐78 ] A series of polythioethers (PTEs) with high M w values (up to 47400) were obtained in high yields (up to 99%) just for 1 min. Furthermore, different activated alkynes were adopted to polymerize with 1,6‐hexanedithiol, and the results demonstrated that dialkylacetylenedicarboxylates (DAADs) were much more active than alkyl propiolates ( M w up to 8900, yield up to 91%) and methyl phenylpropiolates ( M w up to 1200).…”

Rapid synthesis of polyester based single-chain polymeric nanoparticles via an intra-molecular aza-Michael addition reaction

“…[19][20][21][22][23][24][25][26][27][28] On the other hand, it has been proven that electron-deficient alkyne compounds are also suitable Michael acceptors to react with thiols and amines, and Michael addition reactions of these compounds with thiols and amines have gained much interest in polymer science since the last decade. [29][30][31][32][33][34][35][36][37][38][39] Notably, unlike the double bond analogues mentioned above, the electron-deficient alkyne compounds react more rapidly with thiols and amines, resulting in the formation of polymers and polymeric materials in short durations. 29,30 In this regard, in 2016, our group performed a series of condensation polymerizations between acetylenedicarboxylic acid and a variety of diols to prepare various polyesters containing electron-deficient alkyne units in the main chain.…”