Hostname: page-component-7479d7b7d-wxhwt Total loading time: 0 Render date: 2024-07-12T12:07:02.290Z Has data issue: false hasContentIssue false
  • English
  • Français

A latent crosslinkable PCL-based polyurethane: Synthesis, shape memory, and enzymatic degradation

Published online by Cambridge University Press:  17 July 2018

Wenbin Kuang  and
Patrick T. Mather
Wenbin Kuang
Affiliation:
Syracuse Biomaterials Institute and Biomedical and Chemical Engineering Department, Syracuse University, Syracuse, New York 13244, USA
Patrick T. Mather*
Affiliation:
Syracuse Biomaterials Institute and Biomedical and Chemical Engineering Department, Syracuse University, Syracuse, New York 13244, USA
*
a)Address all correspondence to this author. e-mail: patrick.mather@bucknell.edu
Get access

Abstract

Seeking a latent-crosslinkable, mechanically flexible, fully thermoplastic shape memory polymer, we have developed a simple but effective macromolecular design that includes pendent crosslinking sites via the chain extender of a polyurethane architecture bearing semicrystalline poly(ε-caprolactone) (PCL) soft segments. This new composition was used to prepare fibrous mats by electrospinning and films by solvent casting, each containing thermal initiators for chemical crosslinking. The one-step synthesis strategy proved successful, and the crosslinking sites within PCL segments resulted in two-way (reversible) shape memory: repeatable elongation (cooling) and contraction (heating) under constant tensile stress. Being fully characterized, the crosslinked fiber mats revealed promising one-way and two-way (reversible) shape memory phenomena, with lower storage moduli though, compared to uncrosslinked films. We observed for both fibrous mats and films that increasing the applied tensile stress led to greater crystallization-induced elongation upon cooling as well as smaller strain hysteresis, particularly for covalently crosslinked samples. Relevant to medical applications, the materials were observed to feature unique, two-stage enzymatic degradation that was sensitive to differences in crystallinity and microstructure among samples.

Keywords

chemical synthesispolymermemory
Type
Invited Paper
Information
Journal of Materials Research , Volume 33 , Issue 17 , 14 September 2018 , pp. 2463 - 2476
Copyright
Copyright © Materials Research Society 2018 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Lendlein, A. and Kelch, S.: Shape memory polymers. Angew. Chem., Int. Ed. 41, 2034 (2002).3.0.CO;2-M>CrossRefGoogle ScholarPubMed
Ratna, D. and Karger-Kocsis, J.: Recent advances in shape memory polymers and composite: A review. J. Mater. Sci. 43, 254 (2008).CrossRefGoogle Scholar
Liu, C., Qin, H., and Mather, P.T.: Review of progress in shape memory polymers. J. Mater. Chem. 17, 1543 (2007).CrossRefGoogle Scholar
Xie, T.: Tunable polymer multi-shape memory effect. Nature 464, 267 (2010).CrossRefGoogle ScholarPubMed
Yu, K., Xie, T., Leng, J., Ding, Y., and Qi, H.J.: Mechanisms of multi-shape memory effects and associated energy release in shape memory polymers. Soft Matter 8, 5687 (2012).CrossRefGoogle Scholar
Mather, P.T., Luo, X., and Rousseau, I.A.: Shape memory polymer research. Annu. Rev. Mater. Res. 39, 445 (2009).CrossRefGoogle Scholar
Li, J., Rodgers, W.R., and Xie, T.: Semi-crystalline two-way shape memory elastomer. Polymer 52, 5320 (2011).CrossRefGoogle Scholar
Westbrook, K.K., Mather, P.T., Parakh, V., Dunn, M.L., Qi, Q., Lee, B.M., and Qi, H.J.: Two-way reversible shape memory effects in a free-standing polymer composite. Smart Mater. Struct. 20, 065010 (2011).CrossRefGoogle Scholar
Shenoy, D.K., Thomsen, D.L. III, Srinivasan, A., Keller, P., and Ratna, B.R.: Carbon coated liquid crystal elastomer film for artificial muscle applications. Sens. Actuators, A 96, 184 (2002).CrossRefGoogle Scholar
Leng, J., Lan, X., Liu, Y., and Du, S.: Shape memory polymers and their composites: Stimulus methods and applications. Prog. Mater. Sci. 56, 1077 (2011).CrossRefGoogle Scholar
Yu, Y. and Ikeda, T.: Soft actuators based on liquid-crystalline elastomers. Angew. Chem., Int. Ed. 45, 5416 (2006).CrossRefGoogle ScholarPubMed
Ohm, C., Brehmer, M., and Zentel, R.: Liquid crystalline elastomers as actuators and sensors. Adv. Mater. 22, 3366 (2010).CrossRefGoogle ScholarPubMed
Krause, S., Zander, F., Bergmann, G., Brandt, H., Wertmer, H., and Finkelmann, H.: Nematic main-chain elastomers: Coupling and orientational behavior. C. R. Chim. 12, 85 (2009).CrossRefGoogle Scholar
Chung, T., Romo-Uribe, A., and Mather, P.T.: Two-way reversible shape memory in a semicrystalline network. Macromolecules 41, 184 (2008).CrossRefGoogle Scholar
Baker, R.M., Henderson, J.H., and Mather, P.T.: Shape memory poly(ε-caprolactone)-co-poly(ethylene glycol) foams with body temperature triggering and two-way actuation. J. Mater. Chem. B 1, 4916 (2013).CrossRefGoogle Scholar
Behl, M., Kratz, K., Zotzmann, J., Nőchel, U., and Lendlein, A.: Reversible bidirectional shape memory polymers. Adv. Mater. 25, 4466 (2013).CrossRefGoogle ScholarPubMed
Zhou, J., Turner, S.A., Brosnan, S.M., Li, Q., Carrilo, J.Y., Nykypanchuk, D., Gang, O., Ashby, V.S., Dobrynin, A.V., and Sheiko, S.S.: Shape-shifting: Reversible shape memory in semicrystalline elastomers. Macromolecules 47, 1768 (2014).CrossRefGoogle Scholar
Teramoto, N., Kogure, H., Kimura, Y., and Shibata, M.: Thermal properties and biodegradability of the copolymers of L-lactide, ε-caprolactone, and ethylene glycol oligomer with maleate units and their crosslinked products. Polymer 45, 7927 (2004).CrossRefGoogle Scholar
Ping, P., Wang, W., Chen, X., and Jing, X.: The influence of hard-segments on two-phase structure and shape memory properties of PCL-based segmented polyurethanes. J. Polym. Sci., Part B: Polym. Phys. 45, 557 (2007).CrossRefGoogle Scholar
Kim, B.K. and Lee, S.Y.: Polyurethanes having shape memory effects. Polymer 37, 5781 (1996).CrossRefGoogle Scholar
Senador, A.E. Jr., Shaw, M.T., and Mather, P.T.: Electrospinning of polymeric nanofibers: Analysis of jet formation. Mater. Res. Soc. Symp. Proc. 661, 5.9.1 (2001).Google Scholar
Greiner, A. and Wendorff, J.H.: Electrospinning: A fascinating method for the preparation of ultrathin fibers. Angew. Chem., Int. Ed. 46, 5670 (2007).CrossRefGoogle ScholarPubMed
Demir, M.M., Yilgor, I., Yilgor, E., and Erman, B.: Electrospinning of polyurethane fibers. Polymer 43, 3303 (2002).CrossRefGoogle Scholar
Odian, G.: Principles of Polymerization, 4th ed. (A John Wiley & Sons, Inc., New Jersey, 2004); p. 619.CrossRefGoogle Scholar
Gȕven, O.: Crosslinking and Scission in Polymers (Springer, Netherlands, 1990); p. 1.CrossRefGoogle Scholar
Boire, P.C., Gupta, M.K., Zachman, A.I.L., Lee, S.H., Balikov, D.A., Kim, K., Bellan, L.M., and Sung, H.: Pendant allyl crosslinking as a tunable shape memory actuator for vascular applications. Acta Biomater. 24, 53 (2015).CrossRefGoogle ScholarPubMed
Lawton, M.I., Tillman, K.R., Mohammed, H.S., Kuang, W., Shipp, D.A., and Mather, P.T.: Anhydride-based reconfigurable shape memory elastomers. ACS Macro Lett. 5, 203 (2016).CrossRefGoogle Scholar
Gan, Z., Liang, Q., Zhang, J., and Jing, X.: Enzymatic degradation of poly(ε-caprolactone) film in phosphate buffer solution containing lipases. Polym. Degrad. Stab. 56, 209 (1997).CrossRefGoogle Scholar
Zeng, J., Chen, X., Liang, Q., Xu, X., and Jing, X.: Enzymatic degradation of poly(L-lactide) and poly(ε-caprolactone) electrospun fibers. Macromol. Biosci. 4, 1118 (2004).CrossRefGoogle ScholarPubMed
Gu, X., Wu, J., and Mather, P.T.: Polyhedral oligomeric silsesquioxane (POSS) suppresses enzymatic degradation of PCL-based polyurethanes. Biomacromolecules 12, 3066 (2011).CrossRefGoogle ScholarPubMed
Luo, X. and Mather, P.T.: Preparation and characterization of shape memory elastomeric composites. Macromolecules 42, 7251 (2009).CrossRefGoogle Scholar
Robertson, J.M., Nejad, H.B., and Mather, P.T.: Dual-spun shape memory elastomeric composites. ACS Macro Lett. 4, 436 (2015).CrossRefGoogle Scholar
Burke, K.A., Rousseau, I.A., and Mather, P.T.: Reversible actuation in main-chain liquid crystalline elastomers with varying crosslink densities. Polymer 55, 5897 (2014).CrossRefGoogle Scholar
Rice, M.A., Samchez-Adams, J., and Anseth, K.S.: Exogenously triggered, enzymatic degradation of photopolymerized hydrogels with polycaprolactone subunits: Experimental observation and modeling of mass loss behavior. Biomacromolecules 7, 1968 (2006).CrossRefGoogle ScholarPubMed
Saraf, V.P., Glasser, W.G., Wilkes, G.L., and McGrath, J.E.: Structure-property relationships of PEG-containing polyurethane networks. J. Appl. Polym. Sci. 30, 2207 (1985).CrossRefGoogle Scholar
McMullin, E., Rebar, H.T., and Mather, P.T.: Biodegradable thermoplastic elastomers incorporating POSS: Synthesis, microstructure, and mechanical properties. Macromolecules 49, 3769 (2016).CrossRefGoogle Scholar
Valério, A., Conti, D.S., Araújo, P.H.H., Sayer, C., and da Rocha, S.R.P.: Synthesis of PEG-PCL-based polyurethane nanoparticles by miniemulsion polymerization. Colloids Surf., B 135, 35 (2015).CrossRefGoogle ScholarPubMed
Lee, B.S., Chun, B.C., Chung, Y.C., Sul, K.I., and Cho, J.W.: Structure and thermomechanical properties of polyurethane block copolymers with shape memory effect. Macromolecules 34, 6431 (2001).CrossRefGoogle Scholar
Ahmad, M., Xu, B., Purnawali, H., Fu, Y., Huang, W., Miraftab, M., and Luo, J.: High performance shape memory polyurethane synthesized with high molecular weight polyol as the soft segment. Appl. Sci. 2, 535 (2012).CrossRefGoogle Scholar
Barkoula, N., Peijs, T., Schimanski, T., and Loos, J.: Processing of single polymer composites using the concept of constrained fibers. Polym. Compos. 26, 114 (2005).CrossRefGoogle Scholar
Kim, N.K., Fakirov, S., and Bhattacharyya, D.: Polymer–polymer and single polymer composites involving nanofibrillar poly(vinylidene fluoride): Manufacturing and mechanical properties. J. Macromol. Sci., Part B: Phys. 53, 1168 (2014).CrossRefGoogle Scholar
Jiang, S., He, C., Men, Y., Chen, X., An, L., Funari, S.S., and Chan, C.: Study of temperature dependence of crystallization transitions of a symmetric PEO–PCL diblock copolymer using simultaneous SAXS and WAXS measurements with synchrotron radiation. Eur. Phys. J. E: Soft Matter Biol. Phys. 27, 357 (2008).CrossRefGoogle Scholar
Krumova, M., López, D., Benavente, R., Mijangos, C., and Pereňa, J.M.: Effect of crosslinking on the mechanical and thermal properties of poly(vinyl alcohol). Polymer 41, 9265 (2000).CrossRefGoogle Scholar
Park, J., Ye, Q., Topp, E.M., Lee, C.H., Kostoryz, E.L., Misra, A., and Spencer, P.: Dynamic mechanical analysis and esterase degradation of dentin adhesives containing a branched methacrylate. J. Biomed. Mater. Res., Part B 91, 61 (2009).CrossRefGoogle ScholarPubMed
Song, L., Ye, Q., Ge, X., Misra, A., Laurence, J.S., Berrie, C.L., and Spencer, P.: Synthesis and evaluation of novel dental monomer with branched carboxyl acid group. J. Biomed. Mater. Res., Part B 102, 1473 (2014).CrossRefGoogle ScholarPubMed
Liu, C., Chun, S.B., and Mather, P.T.: Chemically cross-linked polycyclooctene: Synthesis, characterization, and shape memory behavior. Macromolecules 35, 9868 (2002).CrossRefGoogle Scholar
Nair, L.S. and Laurencin, C.T.: Biodegradable polymers as biomaterials. Prog. Polym. Sci. 32, 762 (2007).CrossRefGoogle Scholar
Christenson, E.M., Patel, S., Anderson, J.M., and Hiltner, A.: Enzymatic degradation of poly(ether urethane) and poly(carbonate urethane) by cholesterol esterase. Biomaterials 27, 3920 (2006).CrossRefGoogle ScholarPubMed
Supplementary material: File

Kuang and Mather supplementary material

Kuang and Mather supplementary material 1

Download Kuang and Mather supplementary material(File)
File 3.4 MB