Toughening modification of PLLA with PCL in the presence of PCL-b-PLLA diblock copolymers as compatibilizer
Sheng Xiang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
University of the Chinese Academy of Sciences, Beijing, China
Search for more papers by this authorLidong Feng
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorXinchao Bian
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorBao Zhang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorBin Sun
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorYanlong Liu
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorCorresponding Author
Gao Li
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Correspondence
Gao Li and Xuesi Chen, Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
Email: [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Xuesi Chen
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Correspondence
Gao Li and Xuesi Chen, Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
Email: [email protected]; [email protected]
Search for more papers by this authorSheng Xiang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
University of the Chinese Academy of Sciences, Beijing, China
Search for more papers by this authorLidong Feng
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorXinchao Bian
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorBao Zhang
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorBin Sun
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorYanlong Liu
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Search for more papers by this authorCorresponding Author
Gao Li
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Correspondence
Gao Li and Xuesi Chen, Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
Email: [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Xuesi Chen
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Jilin Biomedical Polymers Engineering Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China
Correspondence
Gao Li and Xuesi Chen, Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
Email: [email protected]; [email protected]
Search for more papers by this authorAbstract
To obtain an effective compatibilizer for the blends of poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL), the diblock copolymers PCL-b-PLLA with different ratios of PCL/PLLA (CL/LA) and different molecular weights (Mn) were synthesized by ring-opening polymerization (ROP) of L-lactide with monohydric poly(ε-caprolactone) (PCL-OH) as a macro-initiator. These copolymers were melt blended with PLLA/PCL (80/20) blend at contents between 3.0 and 20 phr (parts per hundred resin), and the effects of added PCL-b-PLLA on the mechanical, morphological, rheological, and thermodynamic properties of the PLLA/PCL/PCL-b-PLLA blends were investigated. The compatibility between PLLA matrix and PCL phase was enhanced with decreasing in CL/LA ratios or increasing in Mn for the added PCL-b-PLLA. Moreover, the crystallinity of PLLA matrix increased because of the added compatibilizers. The PCL-b-PLLA with the ratio of CL/LA (50/50) and Mn ≥ 39.0 kg/mol were effective compatibilizers for PLLA/PCL blends. When the content of PCL-b-PLLA is greater than or equal to 5 phr, the elongations at break of the PLLA/PCL/PCL-b-PLLA blends all reached approximately 180%, about 25 times more than the pristine PLLA/PCL(80/20) blend.
Supporting Information
Filename | Description |
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pat4530-sup-0001-Supporting Information.docxWord 2007 document , 1.2 MB |
Figure S1. GPC profiles of monohydric poly(ε-capro1actone)(PCL-OH). Figure S2. GPC profiles of PCL-b-PLLA diblock copolymer. Figure S3. Plots of rheological properties: (a) storage modulus (G') vs. ω, and (b) loss modulus (G") vs. ω for PLLA/PCL (80/20) and PLLA/PCL/19k-CLxLAy (80/20/10). Figure S4. Plots of rheological properties: (a) storage modulus (G') vs. ω, and (b) loss modulus (G") vs. ω for PLLA/PCL/m-CL50LA50 (80/20/10). Figure S5. PLLA and PCL curves of stress versus strain. Table S1. Non-isothermal properties of samples obtained from cooling and second heating DSC thermograms. |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
REFERENCES
- 1Sajjad Saeidloua MAH, Li HB, Chul BP. Poly (lactic acid) crystallization. Prog Polym Sci. 2012; 37(12): 1657-1677.
- 2Maharana T, Mohanty B, Negi YS. Melt-solid polycondensation of lactic acid and its biodegradability. Prog Polym Sci. 2009; 34(1): 99-124.
- 3Xiang S, Shao J, Li G, et al. Effects of molecular weight on the crystallization and melting behaviors of poly(L-lactide). Chin J Polym Sci. 2016; 34(1): 69-76.
- 4Hamad K, Kaseem M, Ayyoob M, Joo J, Deri F. Polylactic acid blends: The future of green, light and tough. Prog Poly Sci. 2018; 85: 83-127.
- 5Tang Z, He C, Tian H, et al. Polymeric nanostructured materials for biomedical applications. Prog Polym Sci. 2016; 60: 86-128.
- 6Ramot Y, Haim-Zada M, Domb AJ, Nyska A. Biocompatibility and safety of PLA and its copolymers. Adv Drug Deliv Rev. 2016; 107: 153-162.
- 7Ghasri M, Jahandideh A, Kabiri K, Bouhendi H, Zohuriaan-Mehr MJ, Moini N. Glycerol-lactic acid star-shaped oligomers as efficient biobased surface modifiers for improving superabsorbent polymer hydrogels. Polym. Advan. Technol. 2018. in press
- 8Pavelkova A, Kucharczyk P, Stloukal P, Koutny M, Sedlarik V. Novel poly (lactic acid)–poly (ethylene oxide) chain-linked copolymer and its application in nano-encapsulation. Polym Advan Technol. 2014; 25(6): 595-604.
- 9Liu P, Zhen W. Structure-property relationship, rheological behavior, and thermal degradability of poly (lactic acid)/fulvic acid amide composites. Polym Advan Technol. 2018; 29(8): 2192-2203.
- 10Luo Y, Ju Y, Bai H, Liu Z, Zhang Q, Fu Q. Tailor-made dispersion and distribution of stereocomplex crystallites in poly(l-lactide)/elastomer blends toward largely enhanced crystallization rate and impact toughness. J Phys Chem B. 2017; 121(25): 6271-6279.
- 11Drumright RE, Gruber PR, Henton DE. Polylactic acid technology. Adv Mater. 2000; 12(23): 1841-1846.
- 12Su JJ, Meng Y, Zhu F, Han J, Wang K, Fu Q. Simultaneously reinforce and toughen polypropylene by in-situ introducing polylactic acid microfibrils. Polym Advan Technol. 2018; 29(5): 1469-1477.
- 13Lima LT, Aurasb R, Rubinob M. Processing technologies for poly (lactic acid). Prog Polym Sci. 2008; 33(8): 820-852.
- 14Rasal RM, Janorkar AV, Hirt DE. Poly (lactic acid) modifications. Prog Polym Sci. 2010; 35(3): 338-356.
- 15Guo Y, Zuo X, Xue Y, et al. Enhancing impact resistance of polymer blends via self-assembled nanoscale interfacial structures. Macromolecules. 2018; 51(11): 3897-3910.
- 16Martino VP, Jiménez A, Ruseckaite RA, Avérous L. Structure and properties of clay nano-biocomposites based on poly (lactic acid) plasticized with polyadipates. Polym Advan Technol. 2011; 22(12): 2206-2213.
- 17Ding Y, Feng W, Lu B, Wang P, Wang G, Ji J. PLA-PEG-PLA tri-block copolymers: effective compatibilizers for promotion of the interfacial structure and mechanical properties of PLA/PBAT blends. Polymer. 2018; 146: 179-187.
- 18Li X, Ai X, Pan H, et al. The morphological, mechanical, rheological, and thermal properties of PLA/PBAT blown films with chain extender. Polym Advan Technol. 2018; 29(6): 1706-1717.
- 19Phetwarotai W, Maneechot H, Kalkornsurapranee E, Phusunti N. Thermal behaviors and characteristics of polylactide/poly (butylene succinate) blend films via reactive compatibilization and plasticization. Polym Advan Technol. 2018; 29(7): 2121-2133.
- 20Kelnar I, Fortelný I, Kaprálková L, Kratochvíl J, Angelov B, Nevoralová M. Effect of layered silicates on fibril formation and properties of PCL/PLA microfibrillar composites. J Appl Polym Sci. 2016; 133(8).
- 21Sakai F, Nishikawa K, Inoue Y, Yazawa K. Nucleation enhancement effect in poly(l-lactide) (PLLA)/poly(ϵ-caprolactone) (PCL) blend induced by locally activated chain mobility resulting from limited miscibility. Macromolecules. 2009; 42(21): 8335-8342.
- 22Noroozi N, Schafer LL, Hatzikiriakos SG. Thermorheological properties of poly (ε-caprolactone)/polylactide blends. Polym Eng Sci. 2012; 52(11): 2348-2359.
- 23Urquijo J, Guerrica-Echevarría G, Eguiazábal JI. Melt processed PLA/PCL blends: effect of processing method on phase structure, morphology, and mechanical properties. J Appl Polym Sci. 2015; 132(41).
- 24Wu D, Zhang Y, Zhang M, Yu W. Selective localization of multiwalled carbon nanotubes in poly(ε-caprolactone)/polylactide blend. Biomacromolecules. 2009; 10(2): 417-424.
- 25Derakhshandeh M, Noroozi N, Schafer LL, Vlassopoulos D, Hatzikiriakos SG. Dynamics of partially miscible polylactide-poly(ε-caprolactone) blends in the presence of cold crystallization. Rheol Acta. 2016; 55(8): 657-671.
- 26Cayuela J, Da Cruz-Boisson F, Michel A, Cassagnau P. Synthesis of bisphenol-a polycarbonate-poly(ε-caprolactone) copolymers by reactive extrusion through in situ ε-caprolactone polymerization. Polymer. 2016; 104: 156-169.
- 27Harada M, Iida K, Okamoto K, Hayashi H, Hirano K. Reactive compatibilization of biodegradable poly (lactic acid)/poly(ε-caprolactone) blends with reactive processing agents. Polym Eng Sci. 2008; 48(7): 1359-1368.
- 28Deokar MD, Idage SB, Idage BB, Sivaram S. Synthesis and characterization of well-defined random and block copolymers of ε-caprolactone with l-lactide as an additive for toughening polylactide: influence of the molecular architecture. J Appl Polym Sci. 2016; 133(14).
- 29Kellersztein I, Amir E, Dotan A. Grafting of wheat straw fibers with poly (ε-caprolactone) via ring-opening polymerization for poly (lactic acid) reinforcement. Polym Advan Technol. 2016; 27(5): 657-664.
- 30Zhou D, Sun JR, Shao J, et al. Unusual crystallization and melting behavior induced by microphase separation in MPEG-b-PLLA diblock copolymer. Polymer. 2015; 80(47): 123-129.
- 31Li T, Zhang J, Schneiderman DK, Francis LF, Bates FS. Toughening glassy poly (lactide) with block copolymer micelles. ACS Macro Lett. 2016; 5(3): 359-364.
- 32Zhang C, Zhai T, Turng LS, Dan Y. Morphological, mechanical, and crystallization behavior of polylactide/polycaprolactone blends compatibilized by L-lactide/caprolactone copolymer. Ind Eng Chem Res. 2015; 54(38): 9505-9511.
- 33Rizzuto M, Mugica A, Zubitur M, Caretti D, Müller AJ. Plasticization and anti-plasticization effects caused by poly (lactide-ran-caprolactone) addition to double crystalline poly(l-lactide)/poly(ε-caprolactone) blends. CrstEngComm. 2016; 18(11): 2014-2023.
- 34Dell Erba R, Groeninckx G, Maglio G, Malinconico M, Migliozzi A. Immiscible polymer blends of semicrystalline biocompatible components: thermal properties and phase morphology analysis of PLLA/PCL blends. Polymer. 2001; 42(18): 7831-7840.
- 35Wu D, Zhang Y, Yuan L, Zhang M, Zhou W. Viscoelastic interfacial properties of compatibilized poly(ε-caprolactone)/polylactide blend. J Polym Sci B. 2010; 48(7): 756-765.
- 36Choi NS, Kim CH, Cho KY, Park JK. Morphology and hydrolysis of PCL/PLLA blends compatibilized with P (LLA-co-CL) or P (LLA-b-CL). J Appl Polym Sci. 2002; 86(8): 1892-1898.
- 37Leng X, Ren Y, Wei Z, Bian Y, Li Y. Synthesis of star-comb double crystalline diblock copolymer of poly(ε-caprolactone)-block-poly(l-lactide): effect of chain topology on crystallization behavior. Macromol Chem Phys. 2017; 218(16):1700178.
- 38Han W, Liao X, Yang Q, et al. Crystallization and morphological transition of poly(l-lactide)-poly(ε-caprolactone) diblock copolymers with different block length ratios. RSC Adv. 2017; 7(36): 22515-22523.
- 39Michell RM, Blaszczyk-Lezak I, Mijangos C, Müller AJ. Confinement effects on polymer crystallization: from droplets to alumina nanopores. Polymer. 2013; 54(16): 4059-4077.
- 40Wang Y, Hillmyer MA. Polyethylene-poly(L-lactide) diblock copolymers: synthesis and compatibilization of poly(L-lactide)/polyethylene blends. J Polym Sci, Part A: Polym Chem. 2001; 39(16): 2755-2766.