Synthesis of thiourethanes and poly(thiourethane)s bearing carboxylic groups by nucleophilic acylation using cyclic acid anhydrides

Inoue, Yukiko; Matsumoto, Kozo; Endō, Takeshi

doi:10.1007/s00289-015-1567-1

Cited by 2 publications

(1 citation statement)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Polythiourethanes reported in the literature are very scarce and feature different soft segments, making the comparison of thermal characteristics delicate. 65,82,84,85 Thermal properties of known polythiourethanes generally revealed T g values (−29 °C to +57 °C) without any melting or crystallization temperatures being mentioned. The reported thermal stability of these materials was also lower (T d 50 < ca.…”

Section: Macromoleculesmentioning

confidence: 99%

From Epoxide to Cyclodithiocarbonate Telechelic Polycyclooctene through Chain-Transfer Ring-Opening Metathesis Polymerization (ROMP): Precursors to Non-Isocyanate Polyurethanes (NIPUs)

Vanbiervliet

Fouquay²,

Michaud³

et al. 2016

Macromolecules

View full text Add to dashboard Cite

International audienceTelechelic polycyclooctenes (PCOEs) have been successfully synthesized by ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclooctene (COE) using Grubbs' second-generation catalyst (G2) in the presence of epoxide-functionalized chain-transfer agents (CTAs). The monofunctional epoxide oxiran-2-ylmethyl acrylate CTA (1) afforded the isomerized alpha-(glycidyl alkenoate),omega-propenyl functional (IMF) PCOEs. The use of 1,4-benzoquinone (BZQ) as additive completely inhibited the C=C isomerization process, thereby leading selectively to alpha-(glycidyl alkenoate),omega-vinyl telechelic (MF) PCOE. On the other hand, difunctional epoxide CTAs, bis(oxiran-2-ylmethyl) fumarate (3), bis(oxiran-2-ylmethyl) maleate (4), bis(oxiran-2-ylmethyl) (E)-hex-3-enedioate (5), and (Z)-1,4-bis(oxiran-2-ylmethoxy)but-2-ene (6), selectively afforded the corresponding alpha,omega-di(glycidyl alkenoate) telechelic PCOEs (DF) along with minor amounts of cyclic nonfunctional (CNF) PCOE. In the presence of these difunctional symmetric CTAs, the mechanism is proposed to proceed through a tandem one-pot CM/ROMP/ring-closing metathesis (RCM) approach. CM was more effective with Z- than E-configurated CTAs (4 > 6 >> 3 >> 5), regardless of the presence of a methylene group in-between the C=C double bond and the glycidyl moiety. Subsequent dithiocarbonatation of the alpha,omega-diepoxide telechelic PCOEs upon reaction with CS2 in the presence of LiBr quantitatively afforded the first examples of bis(cyclodithiocarbonate) end-functional PCOEs. Ensuing aminolysis of the bis(cyclodithiocarbonate) telechelic PCOEs with the polyether (triethylene glycol) diamine JEFFAMINE EDR-148 quantitatively afforded, at room temperature without any added catalyst, the desired poly(mercaptothiourethane)s NIPUs, as evidenced from FTIR spectroscopy, TGA, and DSC analyses

show abstract