Skip to main content

Advertisement

Log in

Effects of soft segment characteristics on the properties of biodegradable amphiphilic waterborne polyurethane prepared by a green process

  • Polymers & biopolymers
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Traditional 3D printing materials are not suitable for tissue engineering due to their toxicity, low degradability and poor biocompatibility. In this study, a new amphiphilic biodegradable waterborne polyurethane (WBPU) was developed by a green and sustainable process without any organic solvents, catalysts or cross-linkers. The soft segments of this kind of WBPU were formed by replacing hydrophobic poly(ε-caprolactone) diol with hydrophilic poly(ethylene glycol) (PEG). Different block lengths of PEG were used for this purpose. The combination of ester and ether groups endowed WBPU with amphiphilic characteristics, which is important for regeneration and maintenance of tissue. The effects of composition and content of soft segments on the phase separation, thermal properties, mechanical properties, water absorption, biodegradability and cytotoxicity of WBPU were investigated. The results showed that the desired properties of WBPU could be achieved by tuning the block length of PEG and content of soft segments. The present work provided a new approach to prepare WBPUs with amphiphilic and biodegradable characteristics, which are promising candidates for 3D printing materials for tissue engineering scaffolds.

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

Access this article

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

Instant access to the full article PDF.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12

Similar content being viewed by others

References

  1. Inzana JA, Olvera D, Fuller SM, Kelly JP, Graeve OA, Schwarz EM (2014) 3D printing of composite calcium phosphate and collagen scaffolds for bone regeneration. Biomaterials 35:4026–4034

    CAS  Google Scholar 

  2. Tarafder S, Balla VK, Davies NM, Bandyopadhyay A, Bose S (2013) Microwave-sintered 3D printed tricalcium phosphate scaffolds for bone tissue engineering. J Tissue Eng Regen Med 7:631–641

    CAS  Google Scholar 

  3. Wu G-H, Hsu S-h (2015) Review: polymeric-based 3D printing for tissue engineering. J Med Biol Eng 35:285–292

    Google Scholar 

  4. Han LH, Yu S, Wang T, Behn AW, Yang F (2013) Microribbon-like elastomers for fabricating macroporous and highly flexible scaffolds that support cell proliferation in 3D. Adv Funct Mater 23:346–358

    CAS  Google Scholar 

  5. Yen HJ, Hsu SH, Tseng CS, Huang JP, Tsai CL (2009) Fabrication of precision scaffolds using liquid-frozen deposition manufacturing for cartilage tissue engineering. Tissue Eng Part A 15:965–975

    CAS  Google Scholar 

  6. Chen Q, Liang S, Thouas GA (2013) Elastomeric biomaterials for tissue engineering. Prog Polym Sci 38:584–671

    CAS  Google Scholar 

  7. Suri S, Han LH, Zhang W, Singh A, Chen S, Schmidt CE (2011) Solid freeform fabrication of designer scaffolds of hyaluronic acid for nerve tissue engineering. Biomed Microdevices 13:983–993

    CAS  Google Scholar 

  8. Ovsianikov A, Malinauskas M, Schlie S, Chichkov B, Gittard S, Narayan R et al (2011) Three-dimensional laser micro- and nano-structuring of acrylated poly(-ethylene glycol) materials and evaluation of their cytoxicity for tissue engineering applications. Acta Biomater 7:967–974

    CAS  Google Scholar 

  9. Reininghaus W, Koestner A, Klimisch HJ (1991) Chronic toxicity and oncogenicity of inhaled methyl acrylate and n-butyl acrylate in Sprague-Dawley rats. Food Chem Toxicol 29:329–339

    CAS  Google Scholar 

  10. Kligerman AD, Atwater AL, Bryant MF, Erexson GL, Kwanyuen P, Dearfield KL (1991) Cytogenetic studies of ethyl acrylate using C57BL/6 mice. Mutagenesis 6:137–141

    CAS  Google Scholar 

  11. Lin ZF, Wu MM, He HM, Liang QF, Hu CS, Zeng ZW et al (2019) 3D Printing of mechanically stable calcium-free alginate-based scaffolds with tunable surface charge to enable cell adhesion and facile biofunctionalization. Adv Funct Mater 29:1808439

    Google Scholar 

  12. Hao HY, Shao JY, Deng Y, He S, Luo F, Wu YK et al (2016) Synthesis and characterization of biodegradable lysine-based waterborne polyurethane for soft tissue engineering applications. Biomater Sci 4:1682–1690

    CAS  Google Scholar 

  13. Hung KC, Tseng CS, Dai LG, Hsu SH (2016) Water-based polyurethane 3D printed scaffolds with controlled release function for customized cartilage tissue engineering. Biomaterials 83:156–168

    CAS  Google Scholar 

  14. Sartori S, Chiono V, Tonda-Turo C, Mattu C, Gianluca C (2014) Biomimetic polyurethanes in nano and regenerative medicine. J Mater Chem B 2:5128–5144

    CAS  Google Scholar 

  15. Wang Y-J, Jeng US, Hsu S-h (2018) Biodegradable water-Based polyurethane shape memory elastomers for bone tissue engineering. Acs Biomater Sci Eng 4:1397–1406

    CAS  Google Scholar 

  16. Nair LS, Laurencin CT (2007) Biodegradable polymers as biomaterials. Prog Polym Sci 32:762–798

    CAS  Google Scholar 

  17. Cai L, Heilshorn SC (2014) Designing ECM-mimetic materials using protein engineering. Acta Biomater 10:1751–1760

    CAS  Google Scholar 

  18. Cui H, Webber MJ, Stupp SI (2010) Self-assembly of peptide amphiphiles: from molecules to nanostructures to biomaterials. Pept Sci 94:1–18

    CAS  Google Scholar 

  19. Han DK, Park KD, Hubbell JA, Kim YH (1998) Surface characteristics and biocompatibility of lactide-based poly (ethylene glycol) scaffolds for tissue engineering. J Biomater Sci Polym Ed 9:667–680

    CAS  Google Scholar 

  20. Kutikov AB, Song J (2015) Biodegradable PEG-based amphiphilic block copolymers for tissue engineering applications. ACS Biomater Sci Eng 1:463–480

    CAS  Google Scholar 

  21. Veronese FM, Pasut G (2005) PEGylation successful approach to drug delivery. Drug Discov Today 10:1451–1458

    CAS  Google Scholar 

  22. Jiang X, Yu F, Wang Z, Li J, Tan H, Ding M, Fu Q (2010) Fabrication and characterization of waterborne biodegradable polyurethanes 3-dimensional porous scaffolds for vascular tissue engineering. J Biomater Sci Polym Ed 21:1637–1652

    CAS  Google Scholar 

  23. Wang Z, Yu L, Ding M, Tan H, Li J, Fu Q (2011) Preparation and rapid degradation of nontoxic biodegradable polyurethanes based on poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) and l-lysine diisocyanate. Polym Chem 2:601–607

    CAS  Google Scholar 

  24. Ma Z, Hong Y, Nelson DM, Pichamuthu JE, Leeson CE, Wagner WR (2011) Biodegradable polyurethane ureas with variable polyester or polycarbonate soft segments: effects of crystallinity, molecular weight, and composition on mechanical properties. Biomacromol 12:3265–3274

    CAS  Google Scholar 

  25. Hung K-C, Tseng C-S, Hsu S-H (2014) Synthesis and 3D printing of biodegradable polyurethane elastomer by a water-based process for cartilage tissue engineering applications. Adv Healthcare Mater 3:1578–1587

    CAS  Google Scholar 

  26. Yeong W-Y, Chua C-K, Leong K-F, Chandrasekaran M (2004) Rapid prototyping in tissue engineering: challenges and potential. Trends Biotechnol 22:643–652

    CAS  Google Scholar 

  27. Yen H-J, Hsu S, Tseng C-S, Huang J-P, Tsai C-L (2009) Fabrication of precision scaffolds using liquid-frozen deposition manufacturing for cartilage tissue engineering. Tissue Eng Part A 15:965–975

    CAS  Google Scholar 

  28. Hsu SH, Hung KC, Lin YY, Su CH, Yeh HY, Jeng US et al (2014) Water-based synthesis and processing of novel biodegradable elastomers for medical applications. J Mater Chem B 2:5083–5092

    CAS  Google Scholar 

  29. Guo M, Wyss HM (2011) Micromechanics of Soft Particles. Macromol Mater Eng 296:223–229

    CAS  Google Scholar 

  30. Fang CQ, Zhou X, Yu Q, Liu SL, Guo DG, Yu RE, Hu JB (2014) Synthesis and characterization of low crystalline water borne polyurethane for potential application in water-based ink. Prog Org Coat 77:61–71

    CAS  Google Scholar 

  31. Tao C, Luo Z, Bao J, Cheng Q, Huang Y, Xu G (2018) Effects of macromolecular diol containing different carbamate content on the micro-phase separation of waterborne polyurethane. J Mater Sci 53:8639–8652. https://doi.org/10.1007/s10853-017-1908-6

    Article  CAS  Google Scholar 

  32. García-Pacios V, Jofre-Reche JA, Costa V, Colera M, Martín-Martínez JM (2013) Coatings prepared from waterborne polyurethane dispersions obtained with polycarbonates of 1,6-hexanediol of different molecular weights. Prog Org Coat 76:1484–1493

    Google Scholar 

  33. Princi E, Vicini S, Castro K, Capitani D, Proietti N, Mannina L (2009) On the micro-phase separation in waterborne polyurethanes. Macromol Chem Phys 210:879–889

    CAS  Google Scholar 

  34. Cakić SM, Ristić IS, Marinović-Cincović M, Špírková M (2013) The effects of the structure and molecular weight of the macrodiol on the properties polyurethane anionic adhesives. Int J Adhes Adhes 41:132–139

    Google Scholar 

  35. Yu L, Zhou L, Ding M, Li J, Tan H, Fu Q (2011) Synthesis and characterization of novel biodegradable folate conjugated polyurethanes. J Colloid Interface Sci 358:376–383

    CAS  Google Scholar 

  36. Ayres E, Oréfice RL, Yoshida MI (2007) Phase morphology of hydrolysable polyurethanes derived from aqueous dispersions. Eur Polym J 43:3510–3521

    CAS  Google Scholar 

  37. Mondal S, Martin D (2012) Hydrolytic degradation of segmented polyurethane copolymers for biomedical applications. Polym Degrad Stabil 97:1553–1561

    CAS  Google Scholar 

  38. Bogdanov B, Toncheva V, Schacht E, Finelli L, Sarti B, Scandola M (1999) Physical properties of poly(ester-urethanes) prepared from different molar mass polycaprolactone-diols. Polymer 40:3171–3182

    CAS  Google Scholar 

  39. Mondal S, Hu JL (2006) Structural characterization and mass transfer properties of nonporous-segmented polyurethane membrane: influence of the hydrophilic segment content and soft segment melting temperature. J Membr Sci 276:16–22

    CAS  Google Scholar 

  40. Mondal S, Hu JL (2006) Structural characterization and mass transfer properties of polyurethane block copolymer: influence of mixed soft segment block and crystal melting temperature. Polym Int 55:1013–1020

    CAS  Google Scholar 

  41. O’Sickey MJ, Lawrey BD, Wilkes GL (2002) Structure–property relationships of poly(urethane urea)s with ultra-low monol content poly(propylene glycol) soft segments. I. Influence of soft segment molecular weight and hard segment content. J Appl Polym Sci 84:229–243

    Google Scholar 

  42. Li F, Hou J, Zhu W, Zhang X, Xu M, Luo X (1996) Crystallinity and morphology of segmented polyurethanes with different soft-segment length. J Appl Polym Sci 62:631–638

    CAS  Google Scholar 

  43. Mondal S, Hu JL (2008) Structural characterization and mass transfer properties of dense segmented polyurethane membrane: influence of hard segment and soft segment crystal melting temperature. Polym Eng Sci 48:233–239

    CAS  Google Scholar 

  44. Wang T-L, Hsieh T-H (1997) Effect of polyol structure and molecular weight on the thermal stability of segmented poly(urethaneureas). Polym Degrad Stabil 55:95–102

    CAS  Google Scholar 

  45. Yashima E, Noguchi J, Okamoto Y (1994) Enantiomer enrichment of oxprenolol through cellulose tris(3,5-dimethylphenylcarbamate) membrane. J Appl Polym Sci 54:1087–1091

    CAS  Google Scholar 

  46. Coutinho FMB, Delpech MC (2000) Degradation profile of films cast from aqueous polyurethane dispersions. Polym Degrad Stabil 70:49–57

    CAS  Google Scholar 

  47. Pielichowski K, Pielichowski J, Altenburg H, Balloff H-J (1996) Thermische degradation von MDI-basierenden polyurethanen: charakteristische abhängigkeiten zwischen den zersetzungsparametern. Thermochim Acta 284:419–428

    CAS  Google Scholar 

  48. Chattopadhyay DK, Webster DC (2009) Thermal stability and flame retardancy of polyurethanes. Prog Polym Sci 34:1068–1133

    CAS  Google Scholar 

  49. Król P (2007) Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers. Prog Mater Sci 52:915–1015

    Google Scholar 

  50. Migneco F, Huang YC, Birla RK, Hollister SJ (2009) Poly(glycerol-dodecanoate), a biodegradable polyester for medical devices and tissue engineering scaffolds. Biomaterials 33:6479–6484

    Google Scholar 

  51. Liu N, Zhao Y, Kang M, Wang J, Wang X, Feng Y (2015) The effects of the molecular weight and structure of polycarbonatediols on the properties of waterborne polyurethanes. Prog Org Coat 82:46–56

    CAS  Google Scholar 

  52. Hou LJ, Ding YT, Zhang ZL, Sun ZS, Shan ZH (2015) Synergistic effect of anionic and nonionic monomers on the synthesis of high solid content waterborne polyurethane. Colloid Surface A 467:46–56

    CAS  Google Scholar 

  53. Zhang T, Zhang HF, Zhang LQ, Jia SJ, Liu J, Xiong Z, Sun W (2017) Biomimetic design and fabrication of multilayered osteochondral scaffolds by low-temperature deposition manufacturing and thermal-induced phase-separation techniques. Biofabrication 9:025021

    Google Scholar 

  54. Tokiwa Y, Suzuki T, Takeda K (1988) Two types of lipases in hydrolysis of polyester. Agric Biol Chem 52:1937–1943

    CAS  Google Scholar 

  55. Kamath KR, Park K (1993) Biodegradable hydrogels in drug delivery. Adv Drug Deliv Rev 11:59–84

    CAS  Google Scholar 

  56. Hao HY, Deng Y, Wu YK, Liu SY, Lin WW, Li JH et al (2018) Synthesis of biodegradable waterborne phosphatidylcholine polyurethanes for soft tissue engineering applications. Regen Biomater 4:69–79

    Google Scholar 

  57. Wang C, Zheng YD, Sun Y, Fan JS, Qin Q, Zhao Z (2016) A novel biodegradable polyurethane based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(ethylene glycol) as promising biomaterials with the improvement of mechanical properties and hemocompatibility. Polym Chem 7:6120–6132

    CAS  Google Scholar 

Download references

Funding

This study was funded by science and technology project from Jilin Province Ministry of Education (Grant No. JJKH20191304KJ).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Guangfeng Wu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

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

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, Z., Wu, G. Effects of soft segment characteristics on the properties of biodegradable amphiphilic waterborne polyurethane prepared by a green process. J Mater Sci 55, 3139–3156 (2020). https://doi.org/10.1007/s10853-019-04237-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-019-04237-6

Navigation