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Biodegradable multiblock copolymers containing poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)], poly(ε-caprolactone), and polyhedral oligomeric silsesquioxane: synthesis, characterization, and tensile property

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Abstract

Biodegradable multiblock copolymers based on poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV), poly(ε-caprolactone) (PCL), and polyhedral oligomeric silsesquioxane (POSS) were synthesized by one-step copolymerization with 1,6-hexamethylene diisocyanate (HDI) as a coupling agent. The chemical structures, molecular weight, and polydispersity index of the PHBV/PCL/POSS multiblock copolymers were confirmed by 1H NMR, FTIR, and gel permeation chromatography (GPC). XRD analysis illustrated that PHBV and POSS blocks in multiblock copolymers with high content of PHBV and POSS could crystallize to form separate crystalline phases. DSC analysis indicated that the mutual interference of crystallization of PHBV, PCL, and POSS blocks existed. Compared with the crystallinity of PHBV-diol and original PHBV, the crystallinity of PHBV block decreased from 54.8 (original PHBV) and 49.5 (PHBV-diol) to 25.5%. TG measurement revealed that thermal degradation of the multiblock copolymers proceeded by a four-step degradation process and the thermal degradation behavior of PHBV block was similar to that of the original PHBV. The melt processing window of multiblock copolymers was much wider than that of the original PHBV. The results of tensile testing showed that the tensile strength at break of the fibrous membranes of multiblock copolymers increased by 37.5% from 0.8 to 1.1 MPa and the elongation at break reached 307.8%.

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References

  1. Shan GF, Gong X, Chen WP, Chen L, Zhu MF (2011) Effect of multi-walled carbon nanotubes on crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Colloid Polym Sci 289:1005–1014

    Article  CAS  Google Scholar 

  2. Qiang Z, Cheng G (2004) Preparation of biodegradable poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers. J Mater Sci 39:3829–3831

    Article  Google Scholar 

  3. Liu QS, Zhang HX, Deng BY, Zhao XY (2014) Poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate): structure, property, and fiber. Int J Polym Sci 374368

  4. Sato H, Nakamura M, Padermshoke A, Yamaguchi H, Terauchi H, Ekgasit S, Noda I, Ozaki Y (2004) Thermal behavior and molecular interaction of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) studied by wide-angle x-ray diffraction. Macromolecules 37:3763–3769

    Article  CAS  Google Scholar 

  5. Liu QS, Zhu MF, Chen YM (2010) Synthesis and characterization of multi-block copolymers containing poly [(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] and poly(ethylene glycol). Polym Int 59:842–850

    CAS  Google Scholar 

  6. Li J, Lai MF, Liu JJ (2004) Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(β-hydroxybutyrate-co-β-hydroxyvalerate). J Appl Polym Sci 92:2514–2521

    Article  CAS  Google Scholar 

  7. Liu Q, Shyr TW, Tung CH, Deng BY, Zhu MF (2011) Block copolymers containing poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and poly (ɛ-caprolactone) units: synthesis, characterization and thermal degradation. Fiber Polym 12:848–856

    Article  CAS  Google Scholar 

  8. Naguib HF, Aziz MSA, Sherif SM, Saad GR (2011) Synthesis and thermal characterization of poly(ester-ether urethane)s based on PHB and PCL-PEG-PCL blocks. J Polym Res 18:1217–1227

    Article  CAS  Google Scholar 

  9. Hirt TD, Neuenschwander P, Suter UW (1996) Synthesis of degradable, biocompatible, and tough block-copolyesterurethanes. Macromol Chem Phys 197:4253–4268

    Article  CAS  Google Scholar 

  10. Li J, Li X, Ni X, Wang H, Li H, Leong KW (2006) Self-assembled supramolecular hydrogels formed by biodegradable PEO-PHB-PEO triblock copolymers and alpha-cyclodextrin for controlled drug delivery. Biomaterials 27:4132–4140

    Article  CAS  PubMed  Google Scholar 

  11. Wu L, Chen S, Li Z, Xu K, Chen GQ (2008) Synthesis, characterization and biocompatibility of novel biodegradable poly[(( R )-3-hydroxybutyrate)- block -( D, L -lactide)- block -(ε-caprolactone)] triblock copolymers. Polym Int 57:939–949

    Article  CAS  Google Scholar 

  12. Reeve MS, McCarthy SP, Gross RA (1993) Preparation and characterization of (R)-poly(β-hydroxybutyrate)-poly(ε-caprolactone) and (R)-poly(β-hydroxybutyrate)-poly(lactide) degradable diblock copolymers. Macromolecules 26:888–894

    Article  CAS  Google Scholar 

  13. Chen C, Fei B, Peng S, Wu H, Zhuang Y, Cheng X, Dong L, Feng Z (2002) Synthesis and characterization of poly(β-hydroxybutyrate) and poly(ε-caprolactone) copolyester by transesterification. J Polym Sci B Polym Phys 40:1893–1903

    Article  CAS  Google Scholar 

  14. Saad GR, Lee YJ, Seliger H (2002) Synthesis and characterization of biodegradable poly(ester-urethanes) based on bacterial poly(R-3-hydroxybutyrate). J Appl Polym Sci 83:703–718

    Article  CAS  Google Scholar 

  15. Liu Q, Shyr TW, Tung CH, Zhu M, Deng B (2011) Peculiar spherulitic morphologies and melting behavior of block copolymer containing poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(ɛ-caprolactone) units. Macromol Res 19:1220–1223

    Article  CAS  Google Scholar 

  16. Lee KM, Knight PT, Chung T, Mather PT (2008) Polycaprolactone−POSS chemical/physical double networks. Macromolecules 41:4730–4738

    Article  CAS  Google Scholar 

  17. Mirmohammadi SA, Imani M, Uyama H, Atai M, Bagher MT, Bahri-Lale N (2014) The effects of solvent and initiator on anionic ring opening polymerization of ε-caprolactone: synthesis and characterization. Polym Int 63:479–485

    Article  CAS  Google Scholar 

  18. Huitron-Rattinger E, Ishida K, Romo-Uribe A, Mather PT (2013) Thermally modulated nanostructure of poly(ε-caprolactone)-POSS multiblock thermoplastic polyurethanes. Polymer 54:3350–3362

    Article  CAS  Google Scholar 

  19. Yuan WZ, Liu X, Zou H, Ren J (2013) Environment-induced nanostructural dynamical-change based on supramolecular self-assembly of cyclodextrin and star-shaped poly(ethylene oxide) with polyhedral oligomeric silsesquioxane core. Polymer 54:5374–5381

    Article  CAS  Google Scholar 

  20. Wang W, Guo YL, Otaigbe JU (2009) The synthesis, characterization and biocompatibility of poly(ester urethane)/polyhedral oligomeric silesquioxane nanocomposites. Polymer 50:5749–5757

    Article  CAS  Google Scholar 

  21. Ni Y, Zheng S (2007) Melting and crystallization behavior of polyhedral oligomeric silsesquioxane-capped poly(ε-caprolactone). J Polym Sci B Polym Phys 45:2201–2214

    Article  CAS  Google Scholar 

  22. Hirt TD, Neuenschwander P, Suter UW (1996) Telechelic diols from poly[(R)-3-hydroxybutyric acid] and poly{[(R)-3-hydroxybutyric acid]-co-[(R)-3-hydroxyvaleric acid]. Macromol Chem Phys 197: 1609–1614

  23. Zou H, Yuan WZ, Lu YQ, Wang SF (2017) UV light- and thermo-responsive supramolecular aggregates with tunable morphologies from the inclusion complexation of dendritic/linear polymers. Chem Commun 53:2463–2466

    Article  CAS  Google Scholar 

  24. Zou H, Yuan WZ (2015) Temperature- and redox-responsive magnetic complex micelles for controlled drug release. J Mater Chem B 3:260–269

    Article  CAS  Google Scholar 

  25. Zheng L, Kasi RM, Farris RJ, Coughlin EB (2002) Synthesis and thermal properties of hybrid copolymers of syndiotactic polystyrene and polyhedral oligomeric silsesquioxane. J Polym Sci A Polym Chem 40:885–891

    Article  CAS  Google Scholar 

  26. Lee ES, Lei D, Devarayan K, Kim BS (2015) High strength poly(vinyl alcohol)/poly(acrylic acid) cross-linked nanofibrous hybrid composites incorporating nanohybrid POSS. Compos Sci Technol 110:111–117

    Article  CAS  Google Scholar 

  27. Sun ZG, Qiao XJ, Ren QG, Gou XD, Wei L, Liu PZ, Li WC (2016) Synthesis of SiC/SiO2 nanochains by carbon thermal reduction process and its optimization. Adv Powder Technol 27:1552–1559

    Article  CAS  Google Scholar 

  28. Gu X, Jian W, Mather PT (2011) Polyhedral oligomeric silsesquioxane (POSS) suppresses enzymatic degradation of PCL-based polyurethanes. Biomacromolecules 12:3066–3077

    Article  CAS  PubMed  Google Scholar 

  29. Liu QS, Zhu MF, Wu WH, Qin ZY (2009) Reducing the formation of six-membered ring ester during thermal degradation of biodegradable PHBV to enhance its thermal stability. Polym Degrad Stab 94:18–24

    Article  CAS  Google Scholar 

  30. Orozco-Castellanos LM, Marcos-Fernández A, Martínez-Richa A (2001) Mechanisms and kinetics of thermal degradation of poly(ε-caprolactone). Biomacromolecules 2:288–294

    Article  CAS  Google Scholar 

  31. Xia S, Liu Q, Shen Y, Yao P, Deng B (2016) Poly(ɛ-caprolactone)/polyhedral oligomeric silsesquioxane hybrids: crystallization behavior and thermal degradation. J Appl Polym Sci 133:11517–11527

    Google Scholar 

Download references

Funding

This research was supported by the National Natural Science Foundation of China (51403084), the Key Research and Development Program (Industry Forward and Common Key Technology) Project of Suqian City (H201708), the Jiangsu Overseas Research Training Program for University Prominent Young and Middle-Aged Teachers and Presidents, the Natural Science Foundation of Jiangsu Province (BK20130142), the Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education/Shandong Province of China (KF201714), the 111 Project (B17021), the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (PPZY2015B147).

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Authors and Affiliations

  1. Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi, 214122, China

    Sainan Xia, Ying Shen, Yuqi Zhou, Pengfei Yao, Qingsheng Liu & Bingyao Deng

  2. Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education/Shandong Province, Qilu University of Technology, Jinan, 250353, China

    Qingsheng Liu

  3. The School of Materials, The University of Manchester, Manchester, UK

    Qingsheng Liu

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  1. Sainan Xia
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  2. Ying Shen
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  3. Yuqi Zhou
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  4. Pengfei Yao
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  5. Qingsheng Liu
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Correspondence to Qingsheng Liu or Bingyao Deng.

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Xia, S., Shen, Y., Zhou, Y. et al. Biodegradable multiblock copolymers containing poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)], poly(ε-caprolactone), and polyhedral oligomeric silsesquioxane: synthesis, characterization, and tensile property. Colloid Polym Sci 296, 1667–1677 (2018). https://doi.org/10.1007/s00396-018-4389-5

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  • DOI: https://doi.org/10.1007/s00396-018-4389-5

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