Oxygen Barrier Properties of LDHs/PCL Nanocomposite Films Synthesized by In-situ Graft Polymerization
MAO Long1,2, LIU Yuejun1,2, BAI Yongkang2, LIU Xiaochao1
1 Key Laboratory of Advanced Packaging Materials and Technology of Hunan Province, Hunan University of Technology, Zhuzhou 412007; 2 School of Materials Science and Engineering, Xiamen University of Technology, Xiamen 361024
Abstract: In this work, layered double hydroxides-g-poly(ε-caprolactone) (LDHs-g-PCL) were prepared by in-situ ring-opening polymerization at low LDHs loadings. Then LDHs/PCL nanocomposites were prepared by blending LDHs-g-PCL and pure PCL via solution casting method, and the nanocomposites' chemical structures were investigated. And crystallization behavior, mechanical properties and barrier properties of nanocomposites were also deeply studied. It was shown that LDHs-g-PCL were prepared successfully by in-situ polymerization. And results showed that with the increase of LDHs-g-PCL in LDHs/PCL nanocomposites, the crystallization of LDHs/PCL nanocomposites gradually increased. However, the efficiency of heterogeneous nucleation of LDHs-g-PCL decreased to a certain extent. Tensile strength and elongation at break of LDHs/PCL nanocomposites containing 10% (mass fraction) LDHs-g-PCL increased by 31% and 37%, respectively. Compared to pure PCL, the O2 permeability of LDHs/PCL nanocomposites containing 50% (mass fraction) LDHs-g-PCL was reduced by nearly 78%. And the reduction of the O2 permeability arised from the longer diffusion path that the pentrants must travel in the presence of LDHs. The relative permeability model of nanocomposites based on Nielsen's theory was optimized. According to the optimized model, the key parameters to improve the barrier properties of LDHs/PCL nanocomposites are not only the barrier effect of the LDHs (or LDHs-g-PCL) but also the bulk effect that they develop in the polymer matrix.
毛龙, 刘跃军, 白永康, 刘小超. 原位接枝聚合改性LDHs/PCL纳米复合薄膜的制备及氧气阻隔性能*[J]. 《材料导报》期刊社, 2017, 31(18): 43-48.
MAO Long, LIU Yuejun, BAI Yongkang, LIU Xiaochao. Oxygen Barrier Properties of LDHs/PCL Nanocomposite Films Synthesized by In-situ Graft Polymerization. Materials Reports, 2017, 31(18): 43-48.
1 Zhang Y, Liu Q, Zhang S, et al. Gas barrier properties and mechanism of kaolin/styrene-butadiene rubber nanocomposites[J]. Appl Clay Sci, 2015,111:37. 2 Paul D R, Robeson L M. Polymer nanotechnology: Nanocomposites[J]. Polymer, 2008,49(15):3187. 3 Yi S, Yang Z, Wang S, et al. Effects of MgAlCe-CO3 layered double hydroxides on the thermal stability of PVC resin[J]. J Appl Polym Sci, 2011,119(5):2620. 4 Wang S, Huang J, Chen F. Study on Mg-Al hydrotalcites in flame retardant paper preparation[J]. Bio Resources, 2012,7(1):997. 5 Wang D, Leuteritz A, Kutlu B, et al. Preparation and investigation of the combustion behavior of polypropylene/organomodified MgAl-LDH micro-nanocomposite[J]. J Alloys Compd, 2011,509(8):3497. 6 Gain O, Espuche E, Pollet E, et al. Gas barrier properties of poly(ε-caprolactone)/clay nanocomposites: Influence of the morphology and polymer/clay interactions[J]. J Polym Sci Part B: Polym Phys, 2005,43(2):205. 7 Liu L, Yu T, Wang P, et al. In situ polymerization and characte-rization of poly(ε-caprolactone)/layered double hydroxide nanocomposites[J]. Adv Mater Res, 2012,557-559:371. 8 Pucciariello R, Tammaro L, Villani V, et al. New nanohybrids of poly(ε-caprolactone) and a modified Mg/Al hydrotalcite: Mechanical and thermal properties[J]. J Polym Sci Part B: Polym Phys, 2007,45(8):945. 9 Ludueña L N, Alvarez V A, Vazquez A. Processing and microstructure of PCL/clay nanocomposites[J]. Mater Sci Eng A, 2007,460-461:121. 10Su H, Xue J, Cai P, et al. Structure and oxygen-barrier properties of (linear low-density polyethylene/ethylene-vinyl alcohol copolymer)/linear low-density polyethylene composite films prepared by microlayer coextrusion[J]. J Appl Polym Sci, 2015,132(27):34. 11Gorrasi G, Tortora M, Vittoria V, et al. Vapor barrier properties of polycaprolactone montmorillonite nanocomposites: Effect of clay dispersion[J]. Polymer, 2003,44(8):2271. 12Xu B, Zheng Q, Song Y, et al. Calculating barrier properties of po-lymer/clay nanocomposites: Effects of clay layers[J]. Polymer, 2006,47(8):2904. 13Bharadwaj R K. Modeling the barrier properties of polymer-layered silicate nanocomposites[J]. Macromolecules, 2001,34(26):9189. 14Liu Y J, Mao L, Fan S H. Preparation and study of intumescent flame retardant poly(butylene succinate) using MgAlZnFe-CO3 la-yered double hydroxide as a synergistic agent[J]. J Appl Polym Sci, 2014,131(17):8964. 15Liu Yuejun, Mao Long. Effect of MgAlZnFe-CO3 LDHs on fire retardancy and mechanical properties of intumescent flame retardant poly(butylene succinate) composites[J]. Chem J Chin Universities, 2013,34(12):2903(in Chinese). 刘跃军, 毛龙. MgAlZnFe-CO3 LDHs对PBS膨胀阻燃体系性能的影响[J]. 高等学校化学学报, 2013,34(12):2903. 16Messersmith P B, Giannells E P. Synthesis and barrier properties of poly(ε-caprolactone)-layered silicate nanocomposites[J]. J Polym Sci Part A: Polym Chem, 1995,7(33):1047. 17Yan M, Yang H, Xing X. Synthesis and enzymatic degradation of poly(ε-caprolactone-co-ethylene carbonate-co-ethylene oxide) copolymer[J]. Polym Bull, 2013,70(2):467. 18Bach L G, Islam M R, Cao X T, et al. A novel photoluminescent nanohybrid of poly(ε-caprolactone) grafted Mg/Al layered double hydroxides and Tb3+ ions: Synthesis and characterization[J]. J Alloys Compd, 2014,582:22. 19Katiyar V, Gerds N, Koch C B, et al. Poly l-lactide-layered double hydroxide nanocomposites via in situ polymerization of L-lactide[J]. Polym Degrad Stab, 2010,95(12):2563. 20Layek R K, Das A K, Park M J, et al. Enhancement of physical, mechanical, and gas barrier properties in noncovalently functiona-lized graphene oxide/poly(vinylidene fluoride) composites[J]. Carbon, 2015,81(1):329. 21Nielsen L E. Models for the permeability of filled polymer systems[J]. J Macromol Sci: Part A: Chem, 1967,1(5):929. 22Klute C H. Diffusion of small molecules in semicrystalline polymers: Water in polyethylene[J]. J Appl Polym Sci, 1959,1(3):340. 23Lape N K, Nuxoll E E, Cussler E L. Polydisperse flakes in barrier films[J]. J Membr Sci, 2004,236(1-2):29.
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2017, Vol. 31 
