Abstract
Stereocomplex crystallite (SC) between enantiomeric poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA), with largely improved thermal resistance and mechanical properties compared with PLLA and PDLA, is a good nucleating agent for poly(lactic acid) (PLA). The effects of SC and/or polyethylene glycol (PEG) on the crystallization behaviors of PLA were investigated. The non-isothermal and isothermal crystallization kinetics revealed that SC and PEG can separately promote the crystallization rate of PLA by heterogeneous nucleation and increasing crystal growth rate, respectively. However, their promoting effect is limited when used alone, and the modified PLA cannot crystallize completely under a cooling rate of 20 °C/min. When SC and PEG are both present, the crystallization rate of PLA is greatly accelerated, and even under a cooling rate of 40 °C/min, PLA can crystallize completely and get a high crystallinity owing to the excellent balance between simultaneously improved nucleation and crystal growth rate.
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References
Lim L-T, Auras R, Rubino M (2008) Processing technologies for poly(lactic acid). Prog Polym Sci 33(8):820–852
Gilding D, Reed A (1979) Biodegradable polymers for use in surgery—polyglycolic/poly(actic acid) homo- and copolymers: 1. Polymer 20(12):1459–1464
Athanasiou KA, Niederauer GG, Agrawal C (1996) Sterilization, toxicity, biocompatibility and clinical applications of polylactic acid/polyglycolic acid copolymers. Biomaterials 17(2):93–102
Trimaille T, Pichot C, Elaissari A, Fessi H, Briancon S, Delair T (2003) Poly(d, l-lactic acid) nanoparticle preparation and colloidal characterization. Colloid Polym Sci 281(12):1184–1190
Wang C-F, Xie H-Y, Cheng Y-P, Chen L, Hu MZ, Chen S (2011) Chemical synthesis and optical properties of CdS-poly(lactic acid) nanocomposites and their transparent fluorescent films. Colloid Polym Sci 289(4):395–400
Li HB, Huneault MA (2007) Effect of nucleation and plasticization on the crystallization of poly(lactic acid). Polymer 48(23):6855–6866
Kulinski Z, Piorkowska E (2005) Crystallization, structure and properties of plasticized poly(l-lactide). Polymer 46(23):10290–10300
Saeidlou S, Huneault MA, Li H, Sammut P, Park CB (2012) Evidence of a dual network/spherulitic crystalline morphology in PLA stereocomplexes. Polymer 53(25):5816–5824
Barrau S, Vanmansart C, Moreau M, Addad A, Stoclet G, Lefebvre J-M, Seguela R (2011) Crystallization behavior of carbon nanotube–polylactide nanocomposites. Macromolecules 44(16):6496–6502
Xu Z, Niu Y, Yang L, Xie W, Li H, Gan Z, Wang Z (2010) Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes. Polymer 51(3):730–737
Xu Z, Niu Y, Wang Z, Li H, Yang L, Qiu J, Wang H (2011) Enhanced nucleation rate of polylactide in composites assisted by surface acid oxidized carbon nanotubes of different aspect ratios. ACS Appl Mater Interfaces 3(9):3744–3753
Na B, Zou S, Lv R, Luo M, Pan H, Yin Q (2011) Unusual cold crystallization behavior in physically aged poly(l-lactide). J Phys Chem B 115(37):10844–10848
Zhong Y, Zhang Y, Yang J, Li W, Wang Z, Xu D, Chen S, Ding Y (2013) Exponentially increased nucleation ability for poly(l-lactide) by adding acid-oxidized multiwalled carbon nanotubes with reduced aspect ratios. Sci China-Chem 56(2):181–194
Yamane H, Sasai K (2003) Effect of the addition of poly(d-lactic acid) on the thermal property of poly(l-lactic acid). Polymer 44(8):2569–2575
Tsuji H, Takai H, Saha SK (2006) Isothermal and non-isothermal crystallization behavior of poly(l-lactic acid): effects of stereocomplex as nucleating agent. Polymer 47(11):3826–3837
Rahman N, Kawai T, Matsuba G, Nishida K, Kanaya T, Watanabe H, Okamoto H, Kato M, Usuki A, Matsuda M, Nakajima K, Honma N (2009) Effect of polylactide stereocomplex on the crystallization behavior of poly(l-lactic acid). Macromolecules 42(13):4739–4745
Narita J, Katagiri M, Tsuji H (2011) Highly enhanced nucleating effect of melt-recrystallized stereocomplex crystallites on poly(l-lactic acid) crystallization. Macromol Mater Eng 296(10):887–893
Narita J, Katagiri M, Tsuji H (2013) Highly enhanced accelerating effect of melt-recrystallized stereocomplex crystallites on poly(l-lactic acid) crystallization, 2—effects of poly(d-lactic acid) concentration. Macromol Mater Eng 298(3):270–282
Sun J, Yu H, Zhuang X, Chen X, Jing X (2011) Crystallization behavior of asymmetric PLLA/PDLA blends. J Phys Chem B 115(12):2864–2869
Ikada Y, Jamshidi K, Tsuji H, Hyon SH (1987) Stereocomplex formation between enantiomeric poly(lactides). Macromolecules 20(4):904–906
Tsuji H, Horii F, Hyon SH, Ikada Y (1991) Stereocomplex formation between enantiomeric poly(lactic acid)s. 2. Stereocomplex formation in concentrated solutions. Macromolecules 24(10):2719–2724
Tsuji H, Hyon SH, Ikada Y (1991) Stereocomplex formation between enantiomeric poly(lactic acid)s. 3. Calorimetric studies on blend films cast from dilute solution. Macromolecules 24(20):5651–5656
Tsuji H, Hyon SH, Ikada Y (1992) Stereocomplex formation between enantiomeric poly(lactic acids). 5. Calorimetric and morphological studies on the stereocomplex formed in acetonitrile solution. Macromolecules 25(11):2940–2946
Tsuji H, Ikada Y (1999) Stereocomplex formation between enantiomeric poly(lactic acid)s. XI. Mechanical properties and morphology of solution-cast films. Polymer 40(24):6699–6708
Tsuji H, Tezuka Y (2004) Stereocomplex formation between enantiomeric poly(lactic acid)s. 12. Spherulite growth of low-molecular-weight poly(lactic acid)s from the melt. Biomacromolecules 5(4):1181–1186
Tsuji H (2005) Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications. Macromol Biosci 5(7):569–597
He Y, Xu Y, Wei J, Fan Z, Li S (2008) Unique crystallization behavior of poly(l-lactide)/poly(d-lactide) stereocomplex depending on initial melt states. Polymer 49(26):5670–5675
Purnama P, Kim SH (2009) Stereocomplex formation of high-molecular-weight polylactide using supercritical fluid. Macromolecules 43(2):1137–1142
Sun J, Shao J, Huang S, Zhang B, Li G, Wang X, Chen X (2012) Thermostimulated crystallization of polylactide stereocomplex. Mater Lett 89:169–171
Bao R-Y, Yang W, Jiang W-R, Liu Z-Y, Xie B-H, Yang M-B (2013) Polymorphism of racemic poly(l-lactide)/poly(d-lactide) blend: effect of melt and cold crystallization. J Phys Chem B 117(13):3667–3674
Bao R-Y, Yang W, Jiang W-R, Liu Z-Y, Xie B-H, Yang M-B, Fu Q (2012) Stereocomplex formation of high-molecular-weight polylactide: a low temperature approach. Polymer 53(24):5449–5454
Zou S, Na B, Lv R, Pan H (2012) The plasticizer-assisted formation of a percolating multiwalled carbon nanotube network in biodegradable poly(l-lactide). J Appl Polym Sci 123(3):1843–1847
Yang JM, Chen HL, You JW, Hwang JC (1997) Miscibility and crystallization of poly(l-lactide) poly(ethylene glycol) and poly(l-lactide)/poly(epsilon-caprolactone) blends. Polym J 29(8):657–662
Martin O, Averous L (2001) Poly(lactic acid): plasticization and properties of biodegradable multiphase systems. Polymer 42(14):6209–6219
Li Y, Wu H, Wang Y, Liu L, Han L, Wu J, Xiang F (2010) Synergistic effects of PEG and MWCNTs on crystallization behavior of PLLA. J Polym Sci B Polym Phys 48(5):520–528
Zhang Y, Zhang QH, Zha LS, Yang WL, Wang CC, Jiang XG, Fu SK (2004) Preparation, characterization and application of pyrene-loaded methoxy poly(ethylene glycol)–poly(lactic acid) copolymer nanoparticles. Colloid Polym Sci 282(12):1323–1328
Nakafuku C, Takehisa SY (2004) Glass transition and mechanical properties of PLLA and PDLLA–PGA copolymer blends. J Appl Polym Sci 93(5):2164–2173
Nakafuku C (1996) Effects of molecular weight on the melting and crystallization of poly(l-lactic acid) in a mixture with poly(ethylene oxide). Polym J 28(7):568–575
Hu Y, Hu Y, Topolkaraev V, Hiltner A, Baer E (2003) Crystallization and phase separation in blends of high stereoregular poly(lactide) with poly(ethylene glycol). Polymer 44(19):5681–5689
Jia ZY, Zhang KY, Tan JJ, Han CY, Dong LS, Yang YM (2009) Crystallization behavior and mechanical properties of crosslinked plasticized poly(l-lactic acid). J Appl Polym Sci 111(3):1530–1539
Zhang Y, Xu H, Yang J, Chen S, Ding Y, Wang Z (2013) Significantly accelerated spherulitic growth rates for semicrystalline polymers through the layer-by-layer film method. J Phys Chem C 117(11):5882–5893
Yasuniwa M, Tsubakihara S, Sugimoto Y, Nakafuku C (2004) Thermal analysis of the double-melting behavior of poly(l-lactic acid). J Polym Sci B Polym Phys 42(1):25–32
Hoogsteen W, Postema A, Pennings A, Ten Brinke G, Zugenmaier P (1990) Crystal structure, conformation and morphology of solution-spun poly(l-lactide) fibers. Macromolecules 23(2):634–642
Cartier L, Okihara T, Lotz B (1997) Triangular polymer single crystals: stereocomplexes, twins, and frustrated structures. Macromolecules 30(20):6313–6322
Cebe P, Hong S-D (1986) Crystallization behaviour of poly(ether-ether-ketone). Polymer 27(8):1183–1192
Zhang Y, Wang Z, Jiang F, Bai J, Wang Z (2013) Effect of miscibility on spherulitic growth rate for double-layer polymer films. Soft Matter 9(24):5771–5778
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The authors gratefully acknowledge the financial support of the Special Funds for Major Basic Research (nos. 2011CB606006 and 2012CB025902), the National Natural Science Foundation of China (nos. 51033003 and 51073109), and the Fundamental Research Funds for the Central Universities (no. 2011SCU04A03).
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Wei, XF., Bao, RY., Cao, ZQ. et al. Greatly accelerated crystallization of poly(lactic acid): cooperative effect of stereocomplex crystallites and polyethylene glycol. Colloid Polym Sci 292, 163–172 (2014). https://doi.org/10.1007/s00396-013-3067-x
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DOI: https://doi.org/10.1007/s00396-013-3067-x