Skip to main content
SpringerLink
Log in

Synthesis and Characterization of Novel Star-Shaped Itaconic Acid Based Thermosetting Resins

  • Original Paper
  • Published:
Journal of Polymers and the Environment Aims and scope Submit manuscript

Abstract

A star-shaped thermoset resin was synthesized by direct condensation reaction of itaconic acid and glycerol (star-Ita.Gly). In order to decrease the viscosity of the resin, the carboxyl groups of the oligomers were reacted with ethanol (Tstar-Ita.Gly). Chemical structures of the resins were studied by 1H and 13C NMR and Fourier-transform infrared spectroscopy (FT-IR). The curing process was optimized by studying the residual exotherms during the curing process. Thermomechanical properties of the cured samples were studied by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). Thermogravimetric analyses (TGA) were also carried out on both treated and pure resins to study the thermal stability of the cured samples. The viscosity of both resins were measured at different temperatures and different stress levels. Water adsorption tests were also carried out to check the water absorption properties of Tstar-Ita.Gly’s cured samples. The viscosity of the star-Ita.Gly was 154.9 Pa s at room temperature which dropped to 1.8 Pa s upon increasing the temperature to 70 °C. The viscosity of the Tstar-Ita.Gly resin was 0.35 Pa s at room temperature, and 0.04 Pa s at 70 °C. The glass temperature (Tg) of the alcohol-treated resin was 122 °C. Fully biobased content and inexpensive raw materials, biodegradability, very good thermomechanical and comparably very promising rheological properties and processability along with good thermal stability are of advantages of the synthesized resin which make the resin comparable with other thermosetting systems as well as the commercial unsaturated polyester resins.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Alward DB, Kinning DJ, Thomas EL, Fetters LJ (1986) Effect of arm number and arm molecular weight on the solid-state morphology of poly(styrene–isoprene) star block copolymers. Macromolecules 19(1):215–224

    Article  CAS  Google Scholar 

  2. Wang N, Wu XS, Li C, Feng MF (2000) Synthesis, characterization, biodegradation, and drug delivery application of biodegradable lactic/glycolic acid polymers: I. Synthesis and characterization. J Biomater Sci Polym Ed 11(3):301–318

    Article  CAS  Google Scholar 

  3. Lan P, Jia L (2006) Thermal properties of copoly(l-lactic acid/glycolic acid) by direct melt polycondensation. J Macromol Sci A 43(11):1887–1894

    Article  CAS  Google Scholar 

  4. Sawhney AS, Pathak CP, Hubbell JA (1993) Bioerodible hydrogels based on photopolymerized poly(ethylene glycol)-co-poly(. alpha.-hydroxy acid) diacrylate macromers. Macromolecules 26(4):581–587

    Article  CAS  Google Scholar 

  5. Kricheldorf HR, Hachmann-Thiessen H, Schwarz G (2004) Telechelic and star-shaped poly(l-lactide) s by means of bismuth(III) acetate as initiator. Biomacromolecules 5(2):492–496

    Article  CAS  Google Scholar 

  6. Biela T, Duda A, Rode K, Pasch H (2003) Characterization of star-shaped poly(l-lactide) s by liquid chromatography at critical conditions. Polymer 44(6):1851–1860

    Article  CAS  Google Scholar 

  7. Dai J, Ma S, Liu X, Han L, Wu Y, Dai X et al (2015) Synthesis of bio-based unsaturated polyester resins and their application in waterborne UV-curable coatings. Prog Org Coat 78:49–54

    Article  CAS  Google Scholar 

  8. Helminen AO, Korhonen H, Seppälä JV (2002) Structure modification and crosslinking of methacrylated polylactide oligomers. J Appl Polym Sci 86(14):3616–3624

    Article  CAS  Google Scholar 

  9. Wang L, Dong CM (2006) Synthesis, crystallization kinetics, and spherulitic growth of linear and star-shaped poly(l-lactide) s with different numbers of arms. J Polym Sci A 44(7):2226–2236

    Article  CAS  Google Scholar 

  10. Bakare FO, Skrifvars M, Åkesson D, Wang Y, Afshar SJ, Esmaeili N (2014) Synthesis and characterization of bio-based thermosetting resins from lactic acid and glycerol. J Appl Polym Sci 131(13)

  11. Esmaeili N, Bakare FO, Skrifvars M, Afshar SJ, Åkesson D (2015) Mechanical properties for bio-based thermoset composites made from lactic acid, glycerol and viscose fibers. Cellulose 22(1):603–613

    Article  CAS  Google Scholar 

  12. Arvanitoyannis I, Nakayama A, Kawasaki N, Yamamoto N (1995) Novel star-shaped polylactide with glycerol using stannous octoate or tetraphenyl tin as catalyst: 1. Synthesis, characterization and study of their biodegradability. Polymer 36(15):2947–2956

    Article  CAS  Google Scholar 

  13. Perry MR, Shaver MP (2011) Flexible and rigid core molecules in the synthesis of poly(lactic acid) star polymers. Can J Chem 89(4):499–505

    Article  CAS  Google Scholar 

  14. Åkesson D, Skrifvars M, Seppälä J, Turunen M, Martinelli A, Matic A (2010) Synthesis and characterization of a lactic acid-based thermoset resin suitable for structural composites and coatings. J Appl Polym Sci 115(1):480–486

    Article  Google Scholar 

  15. Bakare FO, Ramamoorthy SK, Åkesson D, Skrifvars M (2016) Thermomechanical properties of bio-based composites made from a lactic acid thermoset resin and flax and flax/basalt fibre reinforcements. Compos A 83:176–184

    Article  CAS  Google Scholar 

  16. Åkesson D, Skrifvars M, Seppälä J, Turunen M (2011) Thermoset lactic acid-based resin as a matrix for flax fibers. J Appl Polym Sci 119(5):3004–3009

    Article  Google Scholar 

  17. Kim SH, Han YK, Kim YH, Hong SI (1992) Multifunctional initiation of lactide polymerization by stannous octoate/pentaerythritol. Die Makromol Chem 193(7):1623–1631

    Article  CAS  Google Scholar 

  18. Teng L, Xu X, Nie W, Zhou Y, Song L, Chen P (2015) Synthesis and degradability of a star-shaped polylactide based on l-lactide and xylitol. J Polym Res 22(5):1–7

    Article  CAS  Google Scholar 

  19. Jahandideh A, Muthukumarappan K (2016) Synthesis, characterization and curing optimization of a biobased thermosetting resin from xylitol and lactic acid. Eur Polym J 83:344–358

    Article  CAS  Google Scholar 

  20. Kim SH, Kim YH (eds) (1999) Direct condensation polymerization of lactic acid. Macromolecular symposia. Wiley, New York

    Google Scholar 

  21. Bakare FO, Åkesson D, Skrifvars M, Bashir T, Ingman P, Srivastava R (2015) Synthesis and characterization of unsaturated lactic acid based thermoset bio-resins. Eur Polym J 67:570–582

    Article  CAS  Google Scholar 

  22. Zeng X, Tao W, Mei L, Huang L, Tan C, Feng S-S (2013) Cholic acid-functionalized nanoparticles of star-shaped PLGA-vitamin E TPGS copolymer for docetaxel delivery to cervical cancer. Biomaterials 34(25):6058–6067

    Article  CAS  Google Scholar 

  23. Kim ES, Kim BC, Kim SH (2004) Structural effect of linear and star-shaped poly(l-lactic acid) on physical properties. J Polym Sci B 42(6):939–946

    Article  CAS  Google Scholar 

  24. Park SY, Han BR, Na KM, Han DK, Kim SC (2003) Micellization and gelation of aqueous solutions of star-shaped PLLA-PEO block copolymers. Macromolecules 36(11):4115–4124

    Article  CAS  Google Scholar 

  25. Lin Y, Zhang A (2010) Synthesis and characterization of star-shaped poly(d, l-lactide)-block-poly(ethylene glycol) copolymers. Polym Bull 65(9):883–892

    Article  CAS  Google Scholar 

  26. Lin Y, Zhang A, Wang L (2012) Synthesis and characterization of star-shaped poly(ethylene glycol)-block-poly(l-lactic acid) copolymers by melt polycondensation. J Appl Polym Sci 124(6):4496–4501

    CAS  Google Scholar 

  27. Sakai R, John B, Okamoto M, Seppälä JV, Vaithilingam J, Hussein H et al (2013) Fabrication of polylactide-based biodegradable thermoset scaffolds for tissue engineering applications. Macromol Mater Eng 298(1):45–52

    Article  CAS  Google Scholar 

  28. Finne A, Albertsson A-C (2002) Controlled synthesis of star-shaped l-lactide polymers using new spirocyclic tin initiators. Biomacromolecules 3(4):684–690

    Article  CAS  Google Scholar 

  29. Biela T, Duda A, Pasch H, Rode K (2005) Star-shaped poly(l-lactide) s with variable numbers of hydroxyl groups at polyester arms chain-ends and directly attached to the star-shaped core—controlled synthesis and characterization. J Polym Sci A 43(23):6116–6133

    Article  CAS  Google Scholar 

  30. Qiu LY, Bae YH (2006) Polymer architecture and drug delivery. Pharm Res 23(1):1–30

    Article  CAS  Google Scholar 

  31. Vergnaud J-M, Bouzon J (2012) Cure of thermosetting resins: modelling and experiments. Springer, New York

    Google Scholar 

  32. Jamshidian M, Tehrany EA, Imran M, Jacquot M, Desobry S (2010) Poly-lactic acid: production, applications, nanocomposites, and release studies. Compr Rev Food Sci Food Saf 9(5):552–571

    Article  CAS  Google Scholar 

  33. Chang S, Zeng C, Li J, Ren J (2012) Synthesis of polylactide-based thermoset resin and its curing kinetics. Polym Int 61(10):1492–1502

    Article  CAS  Google Scholar 

  34. Otsu T, Watanabe H, Yang JZ, Yoshioka M, Matsumoto A (eds) (1992) Synthesis and characterization of polymers from itaconic acid derivatives. Makromolekulare chemie Macromolecular symposia. Wiley, New York

    Google Scholar 

  35. Ma S, Liu X, Jiang Y, Tang Z, Zhang C, Zhu J (2013) Bio-based epoxy resin from itaconic acid and its thermosets cured with anhydride and comonomers. Green Chem 15(1):245–254

    Article  CAS  Google Scholar 

  36. Werpy T, Petersen G, Aden A, Bozell J, Holladay J, White J et al (2004) Top value added chemicals from biomass. Volume 1-results of screening for potential candidates from sugars and synthesis gas. DTIC Document

  37. Bakare FO, Skrifvars M, Åkesson D, Wang Y, Afshar SJ, Esmaeili N (2014) Synthesis and characterization of bio-based thermosetting resins from lactic acid and glycerol. J Appl Polym Sci 131(13):1–9

    Article  Google Scholar 

  38. Lv A, Li Z-L, Du F-S, Li Z-C (2014) Synthesis, functionalization, and controlled degradation of high molecular weight polyester from itaconic acid via ADMET polymerization. Macromolecules 47(22):7707–7716

    Article  CAS  Google Scholar 

  39. Avny Y, Saghian N, Zilkha A (1972) Thermally stable polymers derived from itaconic acid. Isr J Chem 10(5):949–957

    Article  CAS  Google Scholar 

  40. Ma S, Liu X, Fan L, Jiang Y, Cao L, Tang Z et al (2014) Synthesis and properties of a bio-based epoxy resin with high epoxy value and low viscosity. ChemSusChem 7(2):555–562

    Article  CAS  Google Scholar 

  41. Li P, Ma S, Dai J, Liu X, Jiang Y, Wang S et al (2016) Itaconic acid as a green alternative to acrylic acid for producing a soybean oil-based thermoset: synthesis and properties. ACS Sustain Chem Eng 5(1):1228–1236

    Article  Google Scholar 

  42. Dai J, Ma S, Wu Y, Zhu J, Liu X (2015) High bio-based content waterborne UV-curable coatings with excellent adhesion and flexibility. Prog Org Coat 87:197–203

    Article  CAS  Google Scholar 

  43. Dai J, Ma S, Teng N, Dai X, Shen X, Wang S et al (2017) 2,5-Furandicarboxylic acid-and itaconic acid-derived fully biobased unsaturated polyesters and their cross-linked networks. Ind Eng Chem Res 56(10):2650–2657

    Article  CAS  Google Scholar 

  44. Jahandideh A, Esmaeili N, Muthukumarappan K (2017) Effect of lactic acid chain lengths on thermomechanical properties of star-LA-xylitol resins and jute reinforced biocomposites. Polym Int 66(7):1021–1030

  45. Jahandideh A, Muthukumarappan K (2017) Star-shaped lactic acid based systems and their thermosetting resins; synthesis, characterization, potential opportunities and drawbacks. Eur Polym J 87:360–379

    Article  CAS  Google Scholar 

  46. Nouri S, Dubois C, Lafleur PG (2015) Synthesis and characterization of polylactides with different branched architectures. J Polym Sci B 53(7):522–531

    Article  CAS  Google Scholar 

  47. Xiong JF, Wang QF, Peng P, Shi J, Wang ZY, Yang Cl (2014) Design, synthesis, and characterization of a potential flame retardant poly(lactic acid-co-pyrimidine-2,4,5,6-tetramine) via direct melt polycondensation. J Appl Polym Sci 131(10):1–10

  48. Murillo EA, Vallejo PP, López BL (2011) Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins. J Appl Polym Sci 120(6):3151–3158

    Article  CAS  Google Scholar 

  49. Xiao L, Mai Y, He F, Yu L, Zhang L, Tang H et al (2012) Bio-based green composites with high performance from poly(lactic acid) and surface-modified microcrystalline cellulose. J Mater Chem 22(31):15732–15739

    Article  CAS  Google Scholar 

  50. Knothe G (2006) Analyzing biodiesel: standards and other methods. J Am Oil Chem Soc 83(10):823–833

    Article  CAS  Google Scholar 

  51. Choi YK, Bae YH, Kim SW (1998) Star-shaped poly(ether–ester) block copolymers: synthesis, characterization, and their physical properties. Macromolecules 31(25):8766–8774

    Article  CAS  Google Scholar 

  52. Abiko A, Yano S-y, Iguchi M (2012) Star-shaped poly(lactic acid) with carboxylic acid terminal groups via poly-condensation. Polymer 53(18):3842–3848

    Article  CAS  Google Scholar 

  53. Barner-Kowollik C, Heuts J, Davis TP (2001) Free-radical copolymerization of styrene and itaconic acid studied by 1H NMR kinetic experiments. J Polym Sci A 39(5):656–664

    Article  CAS  Google Scholar 

  54. Hisham SF, Ahmad I, Daik R, Ramli A (2011) Blends of LNR with unsaturated polyester resin from recycled PET: comparison of mechanical properties and morphological analysis with the optimum blend by commercial resin. Sains Malaysia 40(7):729–735

    CAS  Google Scholar 

  55. Liang G, Chandrashekhara K (2006) Cure kinetics and rheology characterization of soy-based epoxy resin system. J Appl Polym Sci 102(4):3168–3180

    Article  CAS  Google Scholar 

  56. Mohan T, Ramesh Kumar M, Velmurugan R (2005) Rheology and curing characteristics of epoxy–clay nanocomposites. Polym Int 54(12):1653–1659

    Article  CAS  Google Scholar 

  57. Bakare FO, Ramamoorthy SK, Åkesson D, Skrifvars M (2015) Thermomechanical properties of bio-based composites made from a lactic acid thermoset resin and flax and flax/basalt fibre reinforcements. Compos A 83:176–184

  58. Menard KP (2008) Dynamic mechanical analysis: a practical introduction. CRC Press, Boston

    Book  Google Scholar 

  59. Oksman K, Skrifvars M, Selin J-F (2003) Natural fibres as reinforcement in polylactic acid (PLA) composites. Compos Sci Technol 63(9):1317–1324

    Article  CAS  Google Scholar 

  60. Adekunle K, Åkesson D, Skrifvars M (2010) Synthesis of reactive soybean oils for use as a biobased thermoset resins in structural natural fiber composites. J Appl Polym Sci 115(6):3137–3145

    Article  CAS  Google Scholar 

  61. Li WH, Wong A, Leach D (eds) (2010) Advances in benzoxazine resins for aerospace applications. Proceedings of 2010 SAMPE international symposium, Seattle WA, SAMPE Covina CA

  62. Corneillie S, Smet M (2015) PLA architectures: the role of branching. Polym Chem 6(6):850–867

    Article  CAS  Google Scholar 

  63. ASTM D570-98(2010)e1 (2010) Standard test method for water absorption of plastics. ASTM International, West Conshohocken, PA. http://www.astmorg.

Download references

Acknowledgements

The authors would like to acknowledge the funds provided by Agricultural Experiment Station, South Dakota State University and US Department of Agriculture, Washington, DC in support of this research work.

Author information

Author notes

  1. Arash Jahandideh

    Present address: Agricultural, Biosystems & Mechanical Engineering Department, 1400 North Campus Drive Box 2120, P. O. Box 2120, Brookings, SD, 57007, USA

Authors and Affiliations

  1. Agricultural and Biosystems Engineering Department, South Dakota State University, P. O. Box 2120, Brookings, SD, 57007, USA

    Arash Jahandideh & Kasiviswanathan Muthukumarappan

  2. Institute for Materials Research and Innovation, University of Bolton, Deane Road, Bolton, BL3 5AB, UK

    Nima Esmaeili

Authors
  1. Arash Jahandideh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nima Esmaeili
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kasiviswanathan Muthukumarappan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Arash Jahandideh.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jahandideh, A., Esmaeili, N. & Muthukumarappan, K. Synthesis and Characterization of Novel Star-Shaped Itaconic Acid Based Thermosetting Resins. J Polym Environ 26, 2072–2085 (2018). https://doi.org/10.1007/s10924-017-1112-4

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10924-017-1112-4

Keywords

Search

Navigation