Preparation and characterization of poly(lactic acid) composites involving aromatic diboronic acid and organically modified montmorillonite


In this study, composites of polylactide, PLA, involving 1, 2 and 3 mass% 1,4-benzene diboronic acid, BDBA, in the absence and presence of 3 mass% organically modified montmorillonite, Cloisite 30B, C30B, were prepared and characterized. Homogenous dispersion for the composites involving only 1 mass% BDBA and agglomeration for the ones with higher BDBA content were observed. For the composites involving nanoclay, mainly intercalated dispersion was detected. Both TGA and DP-MS results indicated a decrease in thermal stability upon the addition of 1 mass% BDBA. However, as the amount of BDBA incorporated into PLA matrix was increased, thermal stability was also increased. Trans-esterification reactions between BDBA and PLA, although caused decomposition of PLA chains at low concentrations of BDBA to a certain extent, at high concentrations generated a cross-linked structure increasing thermal stability. In the presence of C30B, thermal stability of the composites was increased further. This behavior was associated with enhanced interactions of BDBA and PLA upon diffusion into clay layers.

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 2
Fig. 7
Fig. 8
Fig. 9


  1. 1.

    Krishnamachari P, Zhang J, Lou J, Yan J, Uitenham L. Biodegradable poly(lactic acid)/clay nanocomposites by melt intercalation: a study of morphological, thermal, and mechanical properties. Int J Polym Anal Charact. 2009;14(4):336–50.

  2. 2.

    Paul MA, Delcour C, Alexandre M, Degée P, Monteverde F, Dubois P. Polylactide/montmorillonite nanocomposites: study of the hydrolytic degradation. Polym Degrad Stab. 2005;87:535–42.

  3. 3.

    Kaya H, Ozdemir E, Kaynak C, Hacaloglu J. Effects of nanoparticles on thermal degradation of polylactide/aluminium diethylphosphinate composites. J Anal Appl Pyrol. 2016;118:115–22.

  4. 4.

    Najafi N, Heuzey M, Carreau C, Wood-Adams PJ. Control of thermal degradation of Polylactide (PLA)-clay using chain extenders. Polym Degrad Stab. 2012;97:554–65.

  5. 5.

    Roy PK, Hakkarainen M, Albertsson AC. Nanoclay effects on the degradation process and product patterns of polylactide. Polym Degrad Stab. 2012;97:1254–60.

  6. 6.

    Raquez JM, Habibi Y, Murariu M, Duboi P. Polylactide (PLA)-based nanocomposites. Prog Polym Sci. 2013;10–11:1504–42.

  7. 7.

    Zaidi L, Bruzaud S, Bourmaud A, Médéric P, Kaci M, Grohens Y. Relationship between structure and rheological, mechanical and thermal properties of polylactide/Cloisite 30B nanocomposites. J Appl Polym Sci. 2010;116:1357–65.

  8. 8.

    Zhou Q, Xanthos M. Nanosize and microsize clay effects on the kinetics of the thermal degradation of polylactides. Polym Degrad Stab. 2009;94:327–38.

  9. 9.

    Pochan D, Krikorian V. Poly(l-lactic acid)/layered silicate nanocomposite: fabrication, characterization and properties. Chem Mater. 2003;15:4317–24.

  10. 10.

    Ozdemir E, Lekesiz TO, Hacaloglu J. Polylactide/organically modified montmorillonite composites; effects of organic modifier on thermal characteristics. Polym Deg Stab. 2016;134:87–96.

  11. 11.

    Araújo A, Botelhoa G, Oliveira M, Machado AV. Influence of clay organic modifier on the thermal stability of PLA based nanocomposites. Appl Clay Sci. 2014;88–89:144–50.

  12. 12.

    Liu J, Zhou K, Wen P, Wang B, Hu Y, Gui Z. The influence of multiple modified MMT on the thermal and fire behavior of poly (lactic acid) nanocomposites. Polym Adv Technol. 2015;26(6):626–34.

  13. 13.

    Isitman NA, Dogan M, Bayramli E, Kaynak C. The role of nanoparticle geometry in flame retardancy of polylactide nanocomposites containing aluminium phosphinates. Polym Degrad Stab. 2012;97:1285–96.

  14. 14.

    Fei Cheng, Jaekle F. Boron-containing polymers as versatile building blocks for functional nanostructured materials. Polym Chem. 2011;2:2122–32.

  15. 15.

    Yang HY, Wang X, Yu B, Song L, Hu Y, Yuen RKK. Effect of borates on thermal degradation and flame retardancy of epoxy resins using polyhedral oligomeric silsesquioxane as a curing agent. Thermochim Acta. 2012;535:71–8.

  16. 16.

    Zhu Y, Yuan L, Liang G, Gu A. Green flame retarding bismaleimide resin with simultaneously good processing characteristics, high toughness and outstanding thermal stability based on a multi-functional organic boron compound. Polym Deg Stab. 2015;118:33–44.

  17. 17.

    Ayrilmis N. Combined effects of boron and compatibilizer on dimensional stability and mechanical properties of wood/HDPE composites. Compos Part B Eng. 2013;44:745–9.

  18. 18.

    Tai Q, Song L, Feng H, Tao YJ, Yuen RKK, Hu Y. Investigation of a combination of novel polyphosphoramide and boron-containing compounds on the thermal and flame-retardant properties of polystyrene. J Polym Res. 2013;19:9763–7.

  19. 19.

    Morgan AB, Jurs JL, Tour JM. Synthesis, flame-retardancy testing, and preliminary mechanism studies of nonhalogenated aromatic boronic acids: a new class of condensed-phase polymer flame- retardant additives for acrylonitrile–butadiene–styrene and polycarbonate. J Appl Polym Sci. 2000;76:1257–68.

  20. 20.

    Shih CC, Wu KH, Wang GP, Wu TR, Chang TC. Chain dynamics and thermal stability of boron-tris-containing copolymers. Polym Deg Stab. 2006;91:1658–64.

  21. 21.

    Morishita T, Takahashi N. Highly thermally conductive and electrically insulating polymer nanocomposites with boron nitride nanosheet/ionic liquid complexes RSC. Advances. 2017;7:36450–9.

  22. 22.

    Kumar A, Rao TV, Chowdhury SR, Reddy SVSR. Compatibility confirmation and refinement of thermal and mechanical properties of poly (lactic acid)/poly (ethylene-co-glycidyl methacrylate) blend reinforced by hexagonal boron nitride. React Funct Polym. 2017;117:1–9.

  23. 23.

    Bindhu B, Renisha R, Roberts L, Varghese TO. Boron nitride reinforced polylactic acid composites film for packaging: preparation and properties. Polym Test. 2018;66:172–7.

  24. 24.

    Wootthikanokkhan J, Cheachun T, Sombatsompop N, Thomsorn S, Kaabbuathong N, Wongta N, Wong-On J, Ayutthaya SIN, Kositchaiyong A. Crystallization and thermomechanical properties of PLA composites: effects of additive types and heat treatment. J Appl Polym Sci. 2013;129:215–23.

  25. 25.

    McNeill IC, Leiper HA. Degradation studies of some polyesters and polycarbonates-2. Polylactide: degradation under isothermal conditions, thermal degradation mechanism and photolysis of the polymer. Polym Degrad Stab. 1985;11:309–26.

  26. 26.

    Kopinke D, Remmler M, Mackenzie K, Milder M, Wachsen O. Thermal decomposition of biodegradable polyesters-11. Polylactic acid. Polym Degrad Stab. 1996;43:329–42.

  27. 27.

    Arrieta MP, Parres F, Lopez J. Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products. J Anal Appl Pyrol. 2013;101:150–5.

Download references

Author information

Correspondence to Jale Hacaloglu.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Akar, A.O., Hacaloglu, J. Preparation and characterization of poly(lactic acid) composites involving aromatic diboronic acid and organically modified montmorillonite. J Therm Anal Calorim (2020) doi:10.1007/s10973-019-09236-y

Download citation


  • Polylactide
  • Nanocomposites
  • Aromatic diboronic acid
  • Organoclays
  • Direct pyrolysis mass spectrometry