Polymer Bulletin

, Volume 73, Issue 6, pp 1627–1637 | Cite as

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

  • Yukiko Inoue
  • Kozo Matsumoto
  • Takeshi EndoEmail author
Original Paper


A mercapto group generated by addition of 5-phenoxymethyl-1,3-oxathiolane-2-thione and benzylamine could react with cyclic acid anhydrides to give the corresponding carboxylic acids. This method was applied to a polymer modification. Poly(thiourethane)s containing mercapto groups were prepared from difunctional five-membered cyclic dithiocarbonates and diamines could react with succinic or glutaric anhydride to give the corresponding poly(thiourethane)s bearing carboxyl group in the side chains in high yield. Thermal properties of the obtained polymers were examined by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The obtained polymers showed 5 % weight loss temperatures (T d5) at 170 and 216 °C. These polymers exhibited glass transition temperatures (T g) at 52 and 57 °C, respectively. Furthermore, a cross-linked poly(thiourethane) was readily obtained using difunctional cyclic acid anhydride, 1,2,3,4-butanetetracarboxylic dianhydride as a cross linker.


Poly(thiourethane)s Five-membered cyclic dithiocarbonate Diamine Polyaddition Cyclic acid anhydride Carboxylic acid 



High-resolution mass spectra were measured under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”.


  1. 1.
    Kihara N, Nakawaki Y, Endo T (1995) Preparation of 1, 3-Oxathiolane-2-thiones by the reaction of oxirane and cabon disulfide. J Org Chem 60:473–475CrossRefGoogle Scholar
  2. 2.
    Kihara N, Tochigi H, Endo T (1995) Synthesis and reaction of polymers bearing 5-membered cyclic dithiocarbonate group. J Polym Sci Part A Polym Chem 33:1005–1010CrossRefGoogle Scholar
  3. 3.
    Choi W, Sanda F, Endo T (1998) Ring-opening reaction of five-membered dithiocarbonates on cationic catalyst: control of isomerization and polymerization. Macromolecules 31:2454–2460CrossRefGoogle Scholar
  4. 4.
    Moriguchi T, Endo T (1995) Polyaddition of bifunctional dithiocarbonates derived from epoxides and carbon disulfide. synthesis of novel poly(thiourethanes). Macromolecules 28:5386–5387CrossRefGoogle Scholar
  5. 5.
    Inoue Y, Matsumoto K, Endo T (2015) Synthesis and propertied of poly(thiourethane)s having soft oligoether segments. J Polym Sci Part A Polym Chem 53:1076–1081CrossRefGoogle Scholar
  6. 6.
    Ochiai B, Kato Y, Endo T (2009) One-pot synthesis of graft copolymer by combination of free radical polymerization and polyaddition. Macromolecules 42:8001–8002CrossRefGoogle Scholar
  7. 7.
    Besse V, Foyer G, Auvergne R, Caillol S, Boutevin B (2013) Access to nonisocyanate poly(thio)urethanes: a comparative study. J Polym Sci Part A Polym Chem 51:3284–3296CrossRefGoogle Scholar
  8. 8.
    Hirata M, Watanabe T, Ochiai B, Endo T (2012) 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. J Polym Sci Part A Polym Chem 50:3259–3268CrossRefGoogle Scholar
  9. 9.
    Horikiri M, Sudo A, Endo T (2007) Acceleration effect of five-membered cyclic dithiocarbonate on an epoxy-amine curing system. J Polym Sci Part A Polym Chem 45:4606–4611CrossRefGoogle Scholar
  10. 10.
    Choi W, Sanda T, Endo T (1998) Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate. J Polym Sci A Polym Chem 36:1189–1195CrossRefGoogle Scholar
  11. 11.
    Cisneros JA, Björklund E, González-Gil I, Hu Y, Canales Á, Medrano FJ, Romero A, Ortega-Gutiérrez S, Fowler CJ, López-Rodríguez ML (2012) Structure-activity relationship of a new series of reversible dual monoacylglycerol lipase/fatty acid amide hydrolase inhibitors. J Med Chem 55:824–836CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Molecular Engineering InstituteKinki UniversityIizukaJapan
  2. 2.Department of Biological and Environmental ChemistryKinki UniversityIizukaJapan

Personalised recommendations