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- 2017
纳米SiO2功能化改性石墨烯/热塑性聚氨酯复合材料的制备与性能
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Abstract:
采用Hummers法制备了氧化石墨烯（Graphene Oxide，GO），再与经硅烷偶联剂（APTES）偶联改性纳米SiO2所得的产物（nano SiO2-NH2）混合，制备了石墨烯片（Graphene Sheets，GS）接枝纳米SiO2杂化材料（nano SiO2-g-GS）。以nano SiO2-g-GS为填料，热塑性聚氨酯（TPU）为基体，通过熔融共混法制备共混型nano SiO2-g-GS/TPU复合材料，并对填料和复合材料进行测试和表征。拉伸测试显示nano SiO2-g-GS的加入对基体TPU有一定的补强作用，使复合材料定伸应力（300%、500%和1 000%）增大。DSC测试显示，与纯TPU相比，nano SiO2-g-GS/TPU复合材料的结晶温度有大幅升高，填料含量为1wt%时，TPU的结晶温度升高了44℃。形状记忆测试结果显示，随nano SiO2-g-GS含量增加，nano SiO2-g-GS/TPU复合材料的形状回复率（Rr）逐渐降低，但形状固定率（Rf）逐渐升高。当nano SiO2-g-GS质量分数为1wt%时，nano SiO2-g-GS/TPU复合材料性能最佳。 The graphene oxide (GO) synthesized by Hummers' method was mixed into coupled product nano SiO2-NH2 obtained by silane coupling agent (APTES) modifying nano SiO2 to prepare nano SiO2 functionally modified graphene sheet composites (nano SiO2-g-GS) through the graphene sheets grafting with nano SiO2. The nano SiO2 functionally modified graphene/thermoplastic polyurethane composites (nano SiO2-g-GS/TPU) were fabricated by melt compounding method using the thermoplastic polyurethane (TPU) as the matrix and nano SiO2-g-GS as the filler, and then the fillers and composites were systematically characterized. The tensile tests show that the stress at definite elongation (300%, 500%, 1 000%) of nano SiO2-g-GS/TPU composites increases due to nano SiO2-g-GS has strengthening effects on the TPU. DSC tests show that the crystallinity temperature of the nano SiO2-g-GS/TPU composites increases significantly compared with pure TPU, and the crystallinity temperature of TPU with 1wt% mass fraction of nano SiO2-g-GS increases by 44℃. The shape memory testing results show that the shape recovery ratio (Rr) of nano SiO2-g-GS/TPU decreases and the shape fixing ratio (Rf) increases with the increase of the mass fraction of nano SiO2-g-GS. The nano SiO2-g-GS/TPU composites with 1 wt% nano SiO2-g-GS exhibit the best performance. 四川省教育厅青年基金（17ZB0422）；西华大学"青年学者培养计划"基金（01201404）；国家级大学生创新创业训练计划（201510623033）；四川省高校重点实验室开放研究基金（szjj2015-084；szjj2015-086）
| [1] | BARICK A K, TRIPATHY D K. Effect of nanofiber on material properties of vapor-grown carbon nanofiber rein-forced thermoplastic polyurethane (TPU/CNF) nanocom-posites prepared by melt compounding[J]. Composites Part A:Applied Science and Manufacturing, 2010, 41(10):1471-1482. |
| [2] | GEIM A K, NOVOSELOV K S. The rise of graphene[J]. Nature Materials, 2007, 6(3):183-191. |
| [3] | ZHANG C Z, LI T, YUAN Y, et al. An efficient and environment-friendly method of removing graphene oxide in wastewater and its degradation mechanisms[J]. Chemo-sphere, 2016, 153:531-540. |
| [4] | SHAMAILA S, SAJJAD A K L, LQBAL A. Modifications in development of graphene oxide synthetic routes[J]. Chemical Engineering Journal, 2016, 294:458-477. |
| [5] | KIM H, MIURA Y, MACOSKO C W. Graphene/Polyu-rethane nanocomposites for improved gas barrier and electri-cal conductivity[J]. Chemistry of Materials, 2010, 22(11):3441-3450. |
| [6] | 杨哲. 热致感应型形状记忆高分子材料的研究[J]. 高分子材料科学与工程, 1997, 13(4):19-23. YANG Z. Research of shape memory materials by heating[J]. Polymeric Materials Science and Engineering, 1997, 13(4):19-23(in Chinese). |
| [7] | BIAN J, LIN H L, HE F X, et al. Fabrication of microwave exfoliated graphite oxide reinforced thermoplastic polyu-rethane nanocomposites:Effects of filler on morphology, me-chanical, thermal and conductive properties[J]. Composites:Part A, 2013, 47(1):72-82. |
| [8] | 何飞雄, 卞军, 蔺海兰, 等. 母料-熔融共混法制备TPU/TRG纳米复合材料[J]. 西华大学学报:自然科学版, 2014, 33(6):57-61. HEI F X, BIAN J, LIN H L, et al. TPU/TRG nano-composites prepared by masterbatch-melting compounding process[J]. Journal of Xihua University:Natural Science Edition, 2014, 33(6):57-61(in Chinese). |
| [9] | 蔺海兰, 朱庆兰, 卞军, 等. 共混型石墨烯-nano SiO2/TPU复合材料的制备与性能[J]. 复合材料学报, 2016, 33(7):1382-1389. LIN H L, ZHU Q L, BIAN J, et al. Preparation and pro-perties of blended graphene oxide-nano SiO2/TPU composites[J]. Acta Materiae Compositae Sinica, 2016, 33(7):1382-1389(in Chinese). |
| [10] | HUMMERS Jr W S, OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of American Society, 1958, 80(6):1339-1339. |
| [11] | YADAV S K, CHO J W. Functionalized graphene nano-platelets for enhanced mechanical and thermal properties of polyurethane nanocomposites[J]. Applied Surface Science, 2013, 266(2):360-367. |
| [12] | CAI D Y, JIN J, YUSOH K, et al. High performance polyurethane/functionalized graphene nanocomposites with impro-ved mechanical and thermal properties[J]. Composites Science and Technology, 2012, 72(6):702-707. |
| [13] | 王诗任, 吕智, 赵伟岩等. 热致形状记忆高分子的研究进展[J]. 高分子材料科学与工程, 2000, 16(1):1-4. WANG S R, LV Z, ZHAO W Y, et al. The development of the thermally stimulated shaped memory polymer material[J]. Polymer Materials Science and Engineering, 2000, 16(1):1-4(in Chinese). |
| [14] | GU S Y, YAN B B, LIU L L, et al. Carbon nanotube-polyurethane shape memory nanocomposites with low trigger temperature[J]. European Polymer Journal, 2013, 49(12):3867-3877. |
| [15] | HUANG M, DONG X, GAO Y, et al. Probing the structure evolution/orientation induced by interaction between polyu-rethane segments and SiO2 surface in shape memory process[J]. Polymer, 2014, 55(16):4289-4298. |
| [16] | JIANG T, KUILA T, KIM N H, et al. Enhanced mechani-cal properties of silanized silica nanoparticle attached grap-hene oxide/epoxy composites[J]. Composites Science and Technology, 2013, 79(5):115-125. |
