Skip to main content
SpringerLink
Log in

Fully bio-based, highly toughened and heat-resistant poly(L-lactide) ternary blends via dynamic vulcanization with poly(D-lactide) and unsaturated bioelastomer

通过动态硫化制备的全生物基、高韧性与高耐热聚乳酸三元共混物

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Inherent brittleness and low heat resistance are the two major obstacles that hinder the wide applications of poly(L-lactide) (PLLA). In this study, we report a fully biobased, highly toughened and heat-resistant PLLA ternary blend, which was prepared by dynamic vulcanization of PLLA with poly(D-lactide) (PDLA) and an unsaturated bioelastomer (UBE). The results indicated that during dynamic vulcanization PDLA cocrystallized with PLLA to form stereocomplex (SC) crystallites, which not only enhanced the molecular entanglement but also accelerated the crystallization rate of PLLA matrix. With increase in the content of PDLA, the matrix molecular entanglement increased while phase-separation was enhanced, which enabled the impact strength to increase first and then decrease. The ternary blends containing 10 wt.% PDLA showed the highest impact strength. The presence of SC crystallites makes it possible to achieve a fully sustainable PLLA/VUB/PDLA ternary blend with highly crystalline matrix under conventional injection molding, due to the high nucleation efficiency of SC towards crystallization of PLLA. The highly crystalline ternary blend showed excellent heat resistance and better impact toughness than high impact polystyrene.

摘要

随着环境污染的加剧以及不可再生石油资源的逐渐枯竭, 生物基高分子材料受到了越来越多的关注. 聚乳酸作为一种可再生的高 分子材料, 由于具有良好的生物降解性、生物相容性和机械强度, 在众多领域都具有巨大应用潜力. 然而聚乳酸也存在一些缺陷限制着它 的应用领域, 如冲击韧性差、耐热形变温度低等. 基于此, 我们利用动态硫化技术, 将左旋聚乳酸(PLLA), 右旋聚乳酸(PDLA)以及不饱和 生物基弹性体(UBE)通过自由基引发动态硫化成功制备了冲击韧性优于高抗冲聚苯乙烯、耐热性突出的全生物基PLLA/VUB/PDLA三元 共混物, 在不降低生物质含量、不影响其降解性能的情况下, 实现了PLLA的高性能化.

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

Similar content being viewed by others

References

  1. Zhu Y, Romain C, Williams CK. Sustainable polymers from renewable resources. Nature, 2016, 540: 354–362

    Article  Google Scholar 

  2. Liu Y, Zheng Y, Hayes B. Degradable, absorbable or resorbable—what is the best grammatical modifier for an implant that is eventually absorbed by the body? Sci China Mater, 2017, 60: 377–391

    Article  Google Scholar 

  3. Nagarajan V, Mohanty AK, Misra M. Perspective on polylactic acid (PLA) based sustainable materials for durable applications: focus on toughness and heat resistance. ACS Sustain Chem Eng, 2016, 4: 2899–2916

    Article  Google Scholar 

  4. Tan BH, Muiruri JK, Li Z, et al. Recent progress in using stereocomplexation for enhancement of thermal and mechanical property of polylactide. ACS Sustain Chem Eng, 2016, 4: 5370–5391

    Article  Google Scholar 

  5. Zhang L, Li Y, Wang H, et al. Strong and ductile poly(lactic acid) nanocomposite films reinforced with alkylated graphene nanosheets. Chem Eng J, 2015, 264: 538–546

    Article  Google Scholar 

  6. Liu H, Zhang J. Research progress in toughening modification of poly(lactic acid). J Polym Sci B Polym Phys, 2011, 49: 1051–1083

    Article  Google Scholar 

  7. Zolali AM, Heshmati V, Favis BD. Ultratough co-continuous PLA/ PA11 by interfacially percolated poly(ether-b-amide). Macromolecules, 2017, 50: 264–274

    Article  Google Scholar 

  8. Shi Y, Li M, Wang N, et al. Para-amino benzoic acid doped microgrooved carbon fibers to improve strength and biocompatibility of PLA-PEG. Sci China Mater, 2016, 59: 911–920

    Article  Google Scholar 

  9. Lebarbé T, Grau E, Gadenne B, et al. Synthesis of fatty acid-based polyesters and their blends with poly(L-lactide) as a way to tailor PLLA toughness. ACS Sustain Chem Eng, 2015, 3: 283–292

    Article  Google Scholar 

  10. Hao X, Kaschta J, Liu X, et al. Entanglement network formed in miscible PLA/PMMA blends and its role in rheological and thermo- mechanical properties of the blends. Polymer, 2015, 80: 38–45

    Article  Google Scholar 

  11. Sun Y, Yang L, Lu X, et al. Biodegradable and renewable poly (lactide)–lignin composites: synthesis, interface and toughening mechanism. J Mater Chem A, 2015, 3: 3699–3709

    Article  Google Scholar 

  12. Ojijo V, Ray SS. Super toughened biodegradable polylactide blends with non-linear copolymer interfacial architecture obtained via facile in-situ reactive compatibilization. Polymer, 2015, 80: 1–17

    Article  Google Scholar 

  13. Liu GC, He YS, Zeng JB, et al. In situ formed crosslinked polyurethane toughened polylactide. Polym Chem, 2014, 5: 2530–2539

    Article  Google Scholar 

  14. Hassouna F, Raquez JM, Addiego F, et al. New development on plasticized poly(lactide): Chemical grafting of citrate on PLA by reactive extrusion. Eur Polymer J, 2012, 48: 404–415

    Article  Google Scholar 

  15. Zeng JB, Li YD, Zhu QY, et al. A novel biodegradable multiblock poly(ester urethane) containing poly(l-lactic acid) and poly(butylene succinate) blocks. Polymer, 2009, 50: 1178–1186

    Article  Google Scholar 

  16. Anderson K, Schreck K, Hillmyer M. Toughening polylactide. Polymer Revs, 2008, 48: 85–108

    Article  Google Scholar 

  17. Zeng JB, Li KA, Du AK. Compatibilization strategies in poly(lactic acid)-based blends. RSC Adv, 2015, 5: 32546–32565

    Article  Google Scholar 

  18. Imre B, Pukánszky B. Compatibilization in bio-based and biodegradable polymer blends. Eur Polymer J, 2013, 49: 1215–1233

    Article  Google Scholar 

  19. Liu H, Song W, Chen F, et al. Interaction of microstructure and interfacial adhesion on impact performance of polylactide (PLA) ternary blends. Macromolecules, 2011, 44: 1513–1522

    Article  Google Scholar 

  20. Zhao TH, Wu Y, Li YD, et al. High performance and thermal processable dicarboxylic acid cured epoxidized plant oil resins through dynamic vulcanization with poly(lactic acid). ACS Sustain Chem Eng, 2017, 5: 1938–1947

    Article  Google Scholar 

  21. Zhao TH, He Y, Li YD, et al. Dynamic vulcanization of castor oil in a polylactide matrix for toughening. RSC Adv, 2016, 6: 79542–79553

    Article  Google Scholar 

  22. Wang Y, Chen K, Xu C, et al. Supertoughened biobased poly(lactic acid)–epoxidized natural rubber thermoplastic vulcanizates: fabrication, co-continuous phase structure, interfacial in situ compatibilization, and toughening mechanism. J Phys Chem B, 2015, 119: 12138–12146

    Article  Google Scholar 

  23. Yuan D, Chen Z, Xu C, et al. Fully biobased shape memory material based on novel cocontinuous structure in poly(lactic acid)/ natural rubber TPVs fabricated via peroxide-induced dynamic vulcanization and in situ interfacial compatibilization. ACS Sustain Chem Eng, 2015, 3: 2856–2865

    Article  Google Scholar 

  24. Chen Y, Yuan D, Xu C. Dynamically vulcanized biobased polylactide/ natural rubber blend material with continuous cross-linked rubber phase. ACS Appl Mater Interfaces, 2014, 6: 3811–3816

    Article  Google Scholar 

  25. Liu H, Chen F, Liu B, et al. Super toughened poly(lactic acid) ternary blends by simultaneous dynamic vulcanization and interfacial compatibilization. Macromolecules, 2010, 43: 6058–6066

    Article  Google Scholar 

  26. Zhang K, Nagarajan V, Misra M, et al. Supertoughened renewable PLA reactive multiphase blends system: phase morphology and performance. ACS Appl Mater Interfaces, 2014, 6: 12436–12448

    Article  Google Scholar 

  27. Li X, Kang H, Shen J, et al. Highly toughened polylactide with novel sliding graft copolymer by in situ reactive compatibilization, crosslinking and chain extension. Polymer, 2014, 55: 4313–4323

    Article  Google Scholar 

  28. Fang H, Jiang F, Wu Q, et al. Supertough polylactide materials prepared through in situ reactive blending with peg-based diacrylate monomer. ACS Appl Mater Interfaces, 2014, 6: 13552–13563

    Article  Google Scholar 

  29. Song W, Liu H, Chen F, et al. Effects of ionomer characteristics on reactions and properties of poly(lactic acid) ternary blends prepared by reactive blending. Polymer, 2012, 53: 2476–2484

    Article  Google Scholar 

  30. Liu GC, He YS, Zeng JB, et al. Fully biobased and supertough polylactide-based thermoplastic vulcanizates fabricated by peroxide- induced dynamic vulcanization and interfacial compatibilization. Biomacromolecules, 2014, 15: 4260–4271

    Article  Google Scholar 

  31. Odent J, Raquez JM, Duquesne E, et al. Random aliphatic copolyesters as new biodegradable impact modifiers for polylactide materials. Eur Polymer J, 2012, 48: 331–340

    Article  Google Scholar 

  32. Guo X, Zhang J, Huang J. Poly(lactic acid)/polyoxymethylene blends: morphology, crystallization, rheology, and thermal mechanical properties. Polymer, 2015, 69: 103–109

    Article  Google Scholar 

  33. Han Q, Wang Y, Shao C, et al. Nonisothermal crystallization kinetics of biodegradable poly(lactic acid)/zinc phenylphosphonate composites. J Composite Mater, 2014, 48: 2737–2746

    Article  Google Scholar 

  34. Tang Z, Zhang C, Liu X, et al. The crystallization behavior and mechanical properties of polylactic acid in the presence of a crystal nucleating agent. J Appl Polym Sci, 2012, 125: 1108–1115

    Article  Google Scholar 

  35. Yin HY, Wei XF, Bao RY, et al. Enhancing thermomechanical properties and heat distortion resistance of poly(L-lactide) with high crystallinity under high cooling rate. ACS Sustain Chem Eng, 2015, 3: 654–661

    Article  Google Scholar 

  36. Srithep Y, Nealey P, Turng LS. Effects of annealing time and temperature on the crystallinity and heat resistance behavior of injection-molded poly(lactic acid). Polym Eng Sci, 2013, 53: 580–588

    Article  Google Scholar 

  37. Yin HY, Wei XF, Bao RY, et al. High-melting-point crystals of poly (L-lactic acid) (PLLA): the most efficient nucleating agent to enhance the crystallization of PLLA. CrystEngComm, 2015, 17: 2310–2320

    Article  Google Scholar 

  38. Yu F, Liu T, Zhao X, et al. Effects of talc on the mechanical and thermal properties of polylactide. J Appl Polym Sci, 2012, 125: E99–E109

    Article  Google Scholar 

  39. Xu Z, Niu Y, Yang L, et al. Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes. Polymer, 2010, 51: 730–737

    Article  Google Scholar 

  40. Tsuji H, Takai H, Saha SK. Isothermal and non-isothermal crystallization behavior of poly(l-lactic acid): effects of stereocomplex as nucleating agent. Polymer, 2006, 47: 3826–3837

    Article  Google Scholar 

  41. Krikorian V, Pochan DJ. Unusual crystallization behavior of organoclay reinforced poly(L-lactic acid) nanocomposites. Macromolecules, 2004, 37: 6480–6491

    Article  Google Scholar 

  42. Nam JY,Sinha Ray S, Okamoto M. Crystallization behavior and morphology of biodegradable polylactide/layered silicate nanocomposite. Macromolecules, 2003, 36: 7126–7131

    Article  Google Scholar 

  43. Tsuji H, Takai H, Fukuda N, et al. Non-isothermal crystallization behavior of poly(L-lactic acid) in the presence of various additives. Macromol Mater Eng, 2006, 291: 325–335

    Article  Google Scholar 

  44. Wei XF, Bao RY, Cao ZQ, et al. Stereocomplex crystallite network in asymmetric PLLA/PDLA blends: formation, structure, and confining effect on the crystallization rate of homocrystallites. Macromolecules, 2014, 47: 1439–1448

    Article  Google Scholar 

  45. Saeidlou S, Huneault MA, Li H, et al. Poly(lactic acid) stereocomplex formation: application to PLA rheological property modification. J Appl Polym Sci, 2014, 131

    Google Scholar 

  46. Zhang K, Yu HO, Shi YD, et al. Morphological regulation improved electrical conductivity and electromagnetic interference shielding in poly(L-lactide)/poly(e-caprolactone)/carbon nanotube nanocomposites via constructing stereocomplex crystallites. J Mater Chem C, 2017, 5: 2807–2817

    Article  Google Scholar 

  47. Wang M, Wu Y, Li YD, et al. Progress in toughening poly(lactic acid) with renewable polymers. Polymer Rev, 2017, 57: 557–593

    Article  Google Scholar 

  48. Liu Z, Luo Y, Bai H, et al. Remarkably enhanced impact toughness and heat resistance of poly(L-lactide)/thermoplastic polyurethane blends by constructing stereocomplex crystallites in the matrix. ACS Sustain Chem Eng, 2016, 4: 111–120

    Article  Google Scholar 

  49. Lin L, Deng C, Lin GP, et al. Super toughened and high heatresistant poly(lactic acid) (PLA)-based blends by enhancing interfacial bonding and PLA phase crystallization. Ind Eng Chem Res, 2015, 54: 5643–5655

    Article  Google Scholar 

  50. Signori F, Coltelli MB, Bronco S. Thermal degradation of poly (lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing. Polymer Degradation Stability, 2009, 94: 74–82

    Article  Google Scholar 

  51. Lin S, Yu W, Wang X, et al. Study on the thermal degradation kinetics of biodegradable poly(propylene carbonate) during melt processing by population balance model and rheology. Ind Eng Chem Res, 2014, 53: 18411–18419

    Article  Google Scholar 

  52. Gupta A, Simmons W, Schueneman GT, et al. Rheological and thermo-mechanical properties of poly(lactic acid)/lignin-coated cellulose nanocrystal composites. ACS Sustain Chem Eng, 2017, 5: 1711–1720

    Article  Google Scholar 

  53. Bai J, Wang J, Wang W, et al. Stereocomplex crystallite-assisted shear-induced crystallization kinetics at a high temperature for asymmetric biodegradable PLLA/PDLA blends. ACS Sustain Chem Eng, 2016, 4: 273–283

    Article  Google Scholar 

  54. Tsuji H. Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications. Macromol Biosci, 2005, 5: 569–597

    Article  Google Scholar 

  55. Sakai F, Nishikawa K, Inoue Y, et al. Nucleation enhancement effect in poly(L-lactide) (PLLA)/poly(e-caprolactone) (PCL) blend induced by locally activated chain mobility resulting from limited miscibility. Macromolecules, 2009, 42: 8335–8342

    Article  Google Scholar 

  56. Han L, Xie Q, Bao J, et al. Click chemistry synthesis, stereocomplex formation, and enhanced thermal properties of well-defined poly (L-lactic acid)-b-poly(D-lactic acid) stereo diblock copolymers. Polym Chem, 2017, 8: 1006–1016

    Article  Google Scholar 

  57. Bai H, Huang C, Xiu H, et al. Toughening of poly(l-lactide) with poly(e-caprolactone): Combined effects of matrix crystallization and impact modifier particle size. Polymer, 2013, 54: 5257–5266

    Article  Google Scholar 

  58. Bai H, Xiu H, Gao J, et al. Tailoring impact toughness of poly(Llactide)/poly(e-caprolactone) (PLLA/PCL) blends by controlling crystallization of PLLA matrix. ACS Appl Mater Interfaces, 2012, 4: 897–905

    Article  Google Scholar 

  59. Zhu LD, Yang HY, Cai GD, et al. Submicrometer-sized rubber particles as “craze-bridge” for toughening polystyrene/high-impact polystyrene. J Appl Polym Sci, 2013, 129: 224–229

    Article  Google Scholar 

Download references

Acknowledgements

Si WJ and An XP carried out the experiments, analyzed the data and wrote the draft of manuscript; Zeng JB and Chen YK proposed the project and critical comments on the writing of the manuscript; Wang YZ provided some additional suggestions and comments on the design and writing of the manuscript. All the authors checked and approved the manuscript.

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China

    Wan-Jie Si  (司万杰), Xu-Pei An  (安许沛) & Jian-Bing Zeng  (曾建兵)

  2. Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou, 510641, China

    Jian-Bing Zeng  (曾建兵) & Yu-Kun Chen  (陈玉坤)

  3. Center for Degradable and Flame-Retardant Polymeric Materials, College of Chemistry, State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), Sichuan University, Chengdu, 610064, China

    Yu-Zhong Wang  (王玉忠)

Authors
  1. Wan-Jie Si  (司万杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xu-Pei An  (安许沛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jian-Bing Zeng  (曾建兵)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yu-Kun Chen  (陈玉坤)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yu-Zhong Wang  (王玉忠)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jian-Bing Zeng  (曾建兵).

Additional information

Wan-Jie Si is a postgraduate student majoring in polymer chemistry and physics at Southwest University and his research project is high-performance modification of poly(lactic acid).

Jian-Bing Zeng received his PhD degree in 2009 from Sichuan University under the supervision of Prof. Yu-Zhong Wang. He worked as a lecturer and associate professor at Sichuan University (2009–2014) and has been working as a professor at southwest university since 2014. His research interests focus on biobased/biodegradable polymers and high performance reprocessible polymer networks.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Si, WJ., An, XP., Zeng, JB. et al. Fully bio-based, highly toughened and heat-resistant poly(L-lactide) ternary blends via dynamic vulcanization with poly(D-lactide) and unsaturated bioelastomer. Sci. China Mater. 60, 1008–1022 (2017). https://doi.org/10.1007/s40843-017-9111-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-017-9111-1

Keywords

Search

Navigation