Abstract: The functionalized carbon nanotubes (CNT) were prepared by grafting toluene-2,4-diisocyanate (TDI) onto the surface of CNT. Then a series of TDI functionalized carbon nanotubes (CNT-TDI)/thermoplastic polyurethane elastomer (TPU) composites containing various weight percents of CNT-TDI were prepared by prepolymer method via in-situ polymerization. The structure of CNT-TDI was characterized by Fourier-transformed infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TG); and the influences of the dosage of CNT-TDI on the rheological properties of CNT-TDI/TPU composites were studied by a rotational rheometer. The results demonstrate that, TDI successfully grafts onto CNT via the reaction between the groups of -NCO and -COOH, and its content is about 17%. The dynamic rheological studies show that the storage modulus (G′), loss modulus (G″) and the complex viscosity (η*) of pristine TPU increase significantly with the incorporation of CNT-TDI loading. The crossover of G′ and G″ and the tanδ move to low frequency with CNT-TDI contents increasing, which indicates the existence of a network structure in CNT-TDI/TPU composites. Han plots shift upward and gradually close to the diagonal line, and the van Gurp-Palmen plots shift downward, which implies that the elastic response exhibits an increasing trend. Cole-Cole curves show that the phase separation of composites decrease due to the presence of CNT-TDI.
1 Seyed Ismail Seyed Shahabadi, Junhua Kong, Xuehong Lu. Aqueous-only, green route to self-healable, UV-resistant, and electrically conductive polyurethane/graphene/lignin nanocomposite coatings[J].ACS Sustainable Chemistry & Engineering,2017,5(4):3148. 2 Yang R, Cheng B W, Kang W M, et al. Review on the functionalization and application of carbon nanotubes in composites materials[J].Materials Review A: Review Papers,2015,29(4):47(in Chinese). 杨蕊,程博闻,康卫民,等.碳纳米管的功能化及其在复合材料中的应用[J].材料导报:研究篇,2015,29(4):47. 3 Wei J W, Pu L C, Hu N, et al. The electronic properties of B/N co-doped single-walled nanotubes[J].Journal of Chongqing Institute of Technology,2011(9):94. 韦建卫,蒲利春,胡南,等.硼氮共掺杂单壁碳纳米管电子特性研究[J].重庆理工大学学报(自然科学版),2011(9):94. 4 Wei J W. Effect of gas absorption and decomposition on nanotube-graphene complex defects[J].Journal of Chongqing Institute of Technology,2015(12):48. 韦建卫.纳米管-石墨烯复合缺陷结构的几种气体吸附分解效应[J].Journal of Chongqing Institute of Technology,2015(12):48. 5 Wu G H, Liu S Q, Wu X Y, et al. The effect of carbon nanotubes-grafted lactide on the mechanical and thermal properties of poly (lactic acid) biocomposites[J].Journal of Reinforced Plastics and Composites,2017,36(9):655. 6 Ou Z X, Zheng Y Y, Xiao D S, et al. Preparation and properties of functional graphene-carbon nanotube/thermoplastic polyurethane composite film[J].Acta Materiae Compositae Sinica,2016,33(3):486(in Chinese). 欧忠星,郑玉婴,肖东升,等.功能化改性还原氧化石墨烯-碳纳米管/热塑性聚氨酯复合材料膜的制备及性能[J].复合材料学报,2016,33(3):486. 7 Hyunwoo Kim, Yutaka Miura, Christopher W. Macosko. Graphene/polyurethane nanocomposites for improved gas barrier and electrical conductivity[J].Chemistry of materials,2010,22(11):3441. 8 Zheng Q, Yang B B, Wu G, et al. A study of dynamie rheology for multicomponent polymers[J].Chemical Journal of Chinese Universities,1999,20(9):1483(in Chinese). 郑强,杨碧波,吴刚,等.多组分高分子体系动态流变学研究[J].高等学校化学学报,1999,20(9):1483. 9 Hsuchiang Kuan, Chenchi M. Ma, Weiping Chang, et al. Synthesis, thermal, mechanical and rheological properties of multiwall carbon nanotube/waterborne polyurethane nanocomposites[J].Composites Science and Technology,2005,65(11):1703. 10 Lin P, Meng L H, Huang Y D, et al. Simultaneously functionalization and reduction of grapheme oxide containing isocyanate groups[J].Applied Surface Science,2015,324:784. 11 Zhao C G, Ji L J, Liu H J, et al. Functionalized carbon nanotubes containing isocyanate groups[J].Journal of Solid State Chemistry,2004,177:4394. 12 Kong H, Gao C, Yan D Y. Functionalization of multiwalled carbon nanotubes by atom transfer radical polymerization and defunctiona-lization of the products[J].Macromolecules,2004,37(11):4022. 13 Arunjunai Raja Shankar Santha Kumar, Francesco Piana, Matej Micusik, et al. Preparation of grapheme derivatives by selective reduction of graphite oxide and isocyanate functionalization[J].Materials Chemistry and Physics,2016,182:237. 14 Song H J, Zhang Z Z, Men X H. Surface-modified carbon nanotubes and the effect of their addition on the tribological behavior of a pol-yurethane coating[J].European Polymer Journal,2007,43:4092. 15 Satoshi Yamasaki, Daisuke Nishiguchi, Ken Kojio, et al. Effects of aggregation structure on rheological properties of thermoplastic pol-yurethane[J].Polymer,2007,48:4793. 16 Zhou Z B. Preparation and rheological properties research of PLA/PBAT composites system filled with modified nano-SiO2[D].Zhuzhou: Hunan University of Technology,2016(in Chinese). 周志斌.无机纳米SiO2填充PLA/PBAT复合材料体系的制备及流变性能研究[D].株洲:湖南工业大学,2016. 17 Arthur N Wilkinson, Ian A Kinloch, Raja N Othman. Low viscosity processing using hybrid CNT-coated silica particles to form electrically conductive epoxy resin composites[J].Polymer,2016,98:32. 18 Barick A K, Tripathy D K. Preparation and characterization of thermoplastic polyurethane/organoclay nanocomposites by melt intercalation technique: Effect of nanoclay on morphology, mechanical, thermal, and rheological properties[J].Journal of Applied Polymer Science,2010,117(2):639. 19 Xu E H, Guo Q C, Chen L, et al. Effect of the desperation of hectorite on the rheological behaviors of Nylon 6 nanocomposites[J].Polymer Materials Science & Engineering,2015,31(9):69(in Chinese). 许恩惠,郭前程,陈磊,等.锂皂石分散状态对尼龙6纳米复合材料流变行为的影响[J].高分子材料科学与工程,2015,31(9):69. 20 Pawan Verma, Meenakshi Verma, Anju Gupta, et al. Multi walled caobon nanotubes induced viscoelastic response of polypropylene copolymer nanocomposites effect of filler loading on rheological percolation[J].Polymer Testing,2016,55:1. 21 Wei W M, Zhang R, Liu Q T, et al. DC and AC electrical properties and rheological properties of ABS/graphite composites[J].Polymer Materials Science & Engineering,2017,33(3):95(in Chinese). 魏文闵,张荣,刘清亭,等.ABS/石墨复合材料的交直流导电特性及流变性能[J].高分子材料科学与工程,2017,33(3):95. 22 Claudia Roman, Moises Garcia-Morales, Jaipal Gupta, et al. On the phase affinity of multi-walled carbon nanotubes in PMMA: LDPE immiscible polymer blends[J].Polymer,2017,118:1. 23 Rojo E, Munoz M E, Santamaría A, et al. Correlation between conformational parameters and rheological properties of molten syndiotactic polypropylenes[J].Macromolecular Rapid Communication,2004,25:1314. 24 Hu X Y, Zheng Q, Liu D X, et al. Crystallization and rheological behavior of epoxy resin modified the low melting point of Nylon 6[J].Polymer Materials Science & Engineering,2016,32(8):69(in Chinese). 胡孝迎,郑强,刘典新,等.环氧树脂改性低熔点尼龙6复合材料的结晶行为与流变性能[J].高分子材料科学与工程,2016,32(8):69. 25 Barick A K, Tripathy D K. Effect of organically modified layered si-licate nanoclay on the dynamic viscoelastic properties of thermoplastic polyurethane nanocomposites[J].Applied Clay Science,2011,52:312. 26 Liu Q, Chen D J. Viscoelastic behaviors of poly(ε-caprolactone)/attapulgite nanocomposites[J].European Polymer Journal,2008,44:2046. 27 Meng B, Deng J J, Liu Q, et al. Transparent and ductile poly (lactic acid)/poly (butyl acrylate) (PBA) blends: Structure and properties[J].European Polymer Journal,2012,48:127.
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2018, Vol. 32 
