Skip to main content

New biosourced alternated poly(ether)Ester-Amides (PeEA): synthesis and combined NMR/MALDI ToF MS characterization

Journal of Polymer Research volume 21, Article number: 486 (2014) Cite this article

Abstract

New biosourced alternated poly(ether)Ester-Amides PeEA were prepared by polycondensation in solution or in bulk of unprecedented aminoalcohols based on 1,4:3,6-dianhydrohexitols (DAH) with aromatic and aliphatic diacyl chlorides (sebacoyl, terephtaloyl and isophtaloyl). Optimization of the polymerization in solution has been investigated using MALDI ToF MS and NMR spectroscopy to ascertain the structures and end chain nature of the resulting polymers. The influence of the DAH stereochemistry and the polymerization mode on the structures and thermal properties was demonstrated by MALDI ToF and complementary analytical techniques (DSC and SEC). Isomannide based polymers revealed amorphous but showed higher Tg (around 80 °C for sebacoyl and 180 °C for isophtaloyl) whereas the isosorbide based polymers were semi crystalline. Best properties were obtained in bulk using isomannide based aminoalcohol and sebacoyl chloride (Tg of 82 °C and Mw of 32 kDa, PDI = 1.41).

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

Price includes VAT (USA)
Tax calculation will be finalised during checkout.

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

References

  1. Kricheldorf HR (1997) “Sugar Diols” as building blocks of polycondensates. J Macromol Sci C 37(4):599–631. doi:10.1080/15321799708009650

    Article  Google Scholar 

  2. Wu J, Eduard P, Jasinska-Walc L, Rozanski A, Noordover BAJ, van Es DS, Koning CE (2013) Fully isohexide-based polyesters: synthesis, characterization, and structure-properties relations. Macromolecules 46(2):384–394. doi:10.1021/Ma302209f

    CAS  Article  Google Scholar 

  3. Stoss P, Hemmer R (1991) 1,4:3,6-Dianhydrohexitols. In: Derek H (ed) Advances in Carbohydrate Chemistry and Biochemistry, volume 49. Academic Press, pp 93–173. doi:10.1016/S0065-2318(08)60182-1

  4. Wu J, Eduard P, Thiyagarajan S, van Haveren J, van Es DS, Koning CE, Lutz M, Fonseca Guerra C (2011) Isohexide derivatives from renewable resources as chiral building blocks. Chem Sus Chem 4(5):599–603. doi:10.1002/cssc.201100076

    CAS  Article  Google Scholar 

  5. Medimagh R, Mghirbi S, Saadaoui A, Fildier A, Desloir-Bonjour M, Raffin G, Kricheldorf HR, Chatti S (2013) Synthesis of biosourced polyether-amides from 1,4-3,6-dianhydrohexitols: characterization by NMR and MALDI–ToF mass spectrometry. C R Chim 16(12):1127–1139. doi:10.1016/j.crci.2013.05.004

    CAS  Article  Google Scholar 

  6. Caouthar A, Roger P, Tessier M, Chatti S, Blais JC, Bortolussi M (2007) Synthesis and characterization of new polyamides derived from di(4-cyanophenyl)isosorbide. Eur Polym J 43(1):220–230. doi:10.1016/j.eurpolymj.2006.08.012

    CAS  Article  Google Scholar 

  7. Caouthar AA, Loupy A, Bortolussi M, Blais J-c, Dubreucq L, Meddour A (2005) Synthesis and characterization of new polyamides based on diphenylaminoisosorbide. J Polym Sci A Polym Chem 43(24):2480–2491. doi:10.1002/pola.21116

    Article  Google Scholar 

  8. Sablong R, Duchateau R, Koning CE, de Wit G, va Es D, Koelewijn R, van Haveren J (2008) Incorporation of isosorbide into poly(butylene terephthalate) via solid-state polymerization. Biomacromolecules 9(11):3090–3097. doi:10.1021/bm800627d

    CAS  Article  Google Scholar 

  9. Garaleh M, Yashiro T, Kricheldorf HR, Simon P, Chatti S (2010) (Co-)polyesters derived from isosorbide and 1,4-cyclohexane dicarboxylic acid and succinic acid. Macromol Chem Phys 211(11):1206–1214. doi:10.1002/macp.200900656

    CAS  Article  Google Scholar 

  10. Gopalakrishnan P, Narayan-Sarathy S, Ghosh T, Mahajan K, Belgacem M (2013) Synthesis and characterization of bio-based furanic polyesters. J Polym Res 21(1):1–9. doi:10.1007/s10965-013-0340-0

    Google Scholar 

  11. Beldi M, Medimagh R, Chatti S, Marque S, Prim D, Loupy A, Delolme F (2007) Characterization of cyclic and non-cyclic poly-(ether-urethane)s bio-based sugar diols by a combination of MALDI-TOF and NMR. Eur Polym J 43(8):3415–3433. doi:10.1016/j.eurpolymj.2007.06.003

    CAS  Article  Google Scholar 

  12. Elizabeth C, Sreekumar K (2012) Theoretical and experimental studies of chiral polyurethanes. J Polym Res 19(3):1–10. doi:10.1007/s10965-011-9760-x

    CAS  Article  Google Scholar 

  13. Bennour H, Medimagh R, Fildier A, Raffin G, Hangouet M, Chatti S, Kricheldorf HR (2014) Hyperbranched cyclic and multicyclic poly(etherketone)s by polycondensation of isosorbide and isomannide with 2,6,4′-trifluorobenzophenone and 1,3,5-tris(4-fluorobenzoyl) benzene. High Perform Polym 26(2):144–155. doi:10.1177/0954008313501912

    CAS  Article  Google Scholar 

  14. Abderrazak HB, Fildier A, Romdhane HB, Chatti S, Kricheldorf HR (2013) Synthesis of new poly(ether ketone)s derived from biobased diols. Macromol Chem Phys 214(13):1423–1433. doi:10.1002/macp.201300015

    Article  Google Scholar 

  15. Fenouillot F, Rousseau A, Colomines G, Saint-Loup R, Pascault JP (2010) Polymers from renewable 1,4:3,6-dianhydrohexitols (isosorbide, isomannide and isoidide): a review. Prog Polym Sci 35(5):578–622. doi:10.1016/j.progpolymsci.2009.10.001

    CAS  Article  Google Scholar 

  16. Beghdadi S, Abdelhedi Miladi I, Ben Romdhane H, Bernard J, Drockenmuller E (2012) RAFT polymerization of bio-based 1-vinyl-4-dianhydrohexitol-1,2,3-triazole stereoisomers obtained via click chemistry. Biomacromolecules 13(12):4138–4145. doi:10.1021/bm301435e

    CAS  Google Scholar 

  17. Rusu G, Rusu E (2013) Evaluation of thermal and mechanical behavior of some anionic polyesteramide copolymers. J Polym Res 20(11):1–13. doi:10.1007/s10965-013-0308-0

    CAS  Article  Google Scholar 

  18. Li X, Essawy HA, Pizzi A, Delmotte L, Rode K, Nouen D, Fierro V, Celzard A (2012) Modification of tannin based rigid foams using oligomers of a hyperbranched poly(amine-ester). J Polym Res 19(12):1–9. doi:10.1007/s10965-012-0021-4

    Article  Google Scholar 

  19. Liu C, Jia W, Qian Z, Huang M, Gu Y, Chao G, Gou M, Gong C, Deng H, Lei K, Huang A, Tu M (2007) In vitro degradation behavior of polyesteramide copolymer fiber based on 6-aminocaproic acid, adipic acid, and 1,6-hexane diol. J Polym Res 14(1):31–37. doi:10.1007/s10965-006-9077-3

    CAS  Article  Google Scholar 

  20. Goodman I, Sheahan RJ (1990) Copolyesteramides—V. Hexamethylene adipamide/hexamethylene adipate random and ordered copolymers: preparation and general properties. Eur Polym J 26(10):1081–1088. doi:10.1016/0014-3057(90)90007-Q

    CAS  Article  Google Scholar 

  21. Katsarava R, Beridze V, Arabuli N, Kharadze D, Chu CC, Won CY (1999) Amino acid-based bioanalogous polymers. Synthesis, and study of regular poly(ester amide)s based on bis(α-amino acid) α, ω-alkylene diesters, and aliphatic dicarboxylic acids. J Polym Sci A Polym Chem 37(4):391–407. doi:10.1002/(sici)1099-0518(19990215)37:4<391::aid-pola3>3.0.co;2-e

    CAS  Article  Google Scholar 

  22. Chevallier P, Soutif J-C, Brosse J-C, Grote M (1999) Synthesis of poly(amide-ester)s from 2,6-pyridine dicarboxylic acid and ethanolamine derivatives—investigation of the polymer sorption behaviour towards heavy metal ions. React Funct Polym 42(2):129–146. doi:10.1016/S1381-5148(98)00088-1

    CAS  Article  Google Scholar 

  23. Vera M, Almontassir A, Rodríguez-Galán A, Puiggalí J (2003) Synthesis and characterization of a new degradable poly(ester amide) derived from 6-amino-1-hexanol and glutaric acid. Macromolecules 36(26):9784–9796. doi:10.1021/ma0345652

    CAS  Article  Google Scholar 

  24. Triki R, Abid M, Tessier M, Abid S, El Gharbi R, Fradet A (2013) Furan-based poly(esteramide)s by bulk copolycondensation. Eur Polym J 49(7):1852–1860. doi:10.1016/j.eurpolymj.2013.04.014

    CAS  Article  Google Scholar 

  25. Rodriguez-Galan A, Franco L, Puiggali J (2011) Degradable poly(ester amide)s for biomedical applications. Polymers 3(1):65–99. doi:10.3390/Polym3010065

    CAS  Article  Google Scholar 

  26. Gomurashvili Z, Kricheldorf HR, Katsarava R (2000) Amino acid based bioanalogous polymers. Synthesis and study of new poly(ester amide)s composed of hydrophobic α-amino acids and dianhydrohexitoles. J Macromol Sci Pure Appl Chem 37A(3):215–227

    Article  Google Scholar 

  27. Okada M, Yamada M, Yokoe M, Aoi K (2001) Biodegradable polymers based on renewable resources. V. Synthesis and biodegradation behavior of poly(ester amide)s composed of 1,4:3,6-dianhydro-D-glucitol, α-amino acid, and aliphatic dicarboxylic acid units. J Appl Polym Sci 81(11):2721–2734. doi:10.1002/app.1718

    CAS  Article  Google Scholar 

  28. Abenhaïm D, Loupy A, Munnier L, Tamion R, Marsais F, Quéguiner G (1994) Selective alkylations of 1,4:3,6-dianhydro-d-glucitol (isosorbide). Carbohydr Res 261(2):255–266. doi:10.1016/0008-6215(94)84022-9

    Article  Google Scholar 

  29. Tamion R, Marsais F, Ribereau P, Queguiner G, Abenhaim D, Loupy A, Munnier L (1993) Synthesis of new chiral auxiliaries derived from isosorbide. Tetrahedron Asymmetry 4(8):1879–1890. doi:10.1016/S0957-4166(00)80428-0

    CAS  Article  Google Scholar 

  30. Kricheldorf HR, Rabenstein M, Maskos M, Schmidt M (2001) Macrocycles. 15. The role of cyclization in kinetically controlled polycondensations. 1. Polyester syntheses. Macromolecules 34(4):713–722. doi:10.1021/Ma001099x

    CAS  Article  Google Scholar 

  31. Noordover BAJ, van Staalduinen VG, Duchateau R, Koning CE, van Benthem, Mak M, Heise A, Frissen AE, van Haveren J, van Benthem A, Mak M, Heise A, Frissen AE, van Haveren J (2006) Co- and terpolyesters based on isosorbide and succinic acid for coating applications: synthesis and characterization. Biomacromolecules 7(12):3406–3416. doi:10.1021/bm060713v

    CAS  Article  Google Scholar 

  32. Kricheldorf HR, Weidner SM (2013) High Tg copolyesters of lactide, isosorbide and isophthalic acid. Eur Polym J 49(8):2293–2302. doi:10.1016/j.eurpolymj.2013.05.007

    CAS  Article  Google Scholar 

  33. Armelin E, Paracuellos N, Rodrı́guez-Galán A, Puiggalı́ J (2001) Study on the degradability of poly(ester amide)s derived from the α-amino acids glycine, and l-alanine containing a variable amide/ester ratio. Polymer 42(19):7923–7932. doi:10.1016/S0032-3861(01)00315-9

    CAS  Article  Google Scholar 

  34. Zhao Y, Vaughan AS, Sutton SJ, Swingler SG (2001) On the crystallization, morphology and physical properties of a clarified propylene/ethylene copolymer. Polymer 42(15):6587–6597. doi:10.1016/S0032-3861(01)00031-3

    CAS  Article  Google Scholar 

  35. Garg P, Keul H, Klee D, Möller M (2009) Thermal properties of poly(ester amide)s with isolated, two adjacent and three adjacent amide groups within a polyester chain. Macromol Chem Phys 210(20):1754–1765. doi:10.1002/macp.200900232

    CAS  Article  Google Scholar 

Download references

Acknowledgments

Authors are grateful to Société Roquette Lestrem for a kind gift of Isosorbide and Isomannide. The authors want to thank the Tunisian Ministry of Higher Education and Research and the French Foreign affairs Ministry for Financial support (Project “PHC Utique” 13G/1211). Authors want to thanks all INRAP staff especially (Mr Chaouki Belgacem and Mohamed Mezni, Mrs Saloua Ben Aissa and Monia Elouni) for analysis and helpful discussions.

Author information

Authors and Affiliations

  1. Laboratoire des Substances Naturelles (LSN), LR10 INRAP 02, Institut National de Recherche et d’Analyse Physico-chimique INRAP, Sidi Thabet Biotechpole, 2020, Ariana, Tunisia

    Raouf Medimagh, Asma Saadaoui & Salma Mghirbi

  2. Université de Versailles-St-Quentin (UVSQ), Institut Lavoisier de Versailles (ILV) UMR CNRS 8180, 45 Avenue des Etats-Unis, 78035, Versailles Cedex, France

    Asma Saadaoui, Sylvain Marque & Damien Prim

  3. Université de Lyon, UMR 5280, Institut des Sciences Analytiques (ISA), 5 rue de la Doua, 69100, Villeurbanne, France

    Aurélie Fildier, Audrey Bulete, Guy Raffin & Saber Chatti

Authors
  1. Raouf Medimagh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Asma Saadaoui
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Salma Mghirbi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Sylvain Marque
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Damien Prim
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Aurélie Fildier
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Audrey Bulete
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Guy Raffin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Saber Chatti
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Raouf Medimagh or Saber Chatti.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Medimagh, R., Saadaoui, A., Mghirbi, S. et al. New biosourced alternated poly(ether)Ester-Amides (PeEA): synthesis and combined NMR/MALDI ToF MS characterization. J Polym Res 21, 486 (2014). https://doi.org/10.1007/s10965-014-0486-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0486-4

Keywords

  • 1,4-3,6-dianhydrohexitols
  • Alternated poly(ether)Ester-Amides
  • Biobased
  • MALDI ToF mass spectrometry
  • Polycondensation