原位聚合制备聚氨酯/氧化石墨烯纳米复合材料的力学性能和热稳定性能研究*

doi:10.11901/1005.3093.2013.393

材料研究学报

2014, Vol. 28

Issue (12): 901-908 DOI: 10.11901/1005.3093.2013.393

本期目录 | 过刊浏览

原位聚合制备聚氨酯/氧化石墨烯纳米复合材料的力学性能和热稳定性能研究*

李国兴¹,赵景珊¹,孙科¹,王强²,王明¹(

)

1. 西南大学化学化工学院重庆 400715
2. 西南大学材料与能源学部重庆 400715

Study on Mechanical Property and Thermal Stability of In-situ Nanocomposites of Polyurethane/ Oxidized Graphene

Guoxing LI¹,Jingshan ZHAO¹,Ke SUN¹,Qiang WANG²,Ming WANG^1,^**(

)

1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715
2. Faculty of Materials and Energy, South west University, Chongqing, 400715

引用本文:

李国兴,赵景珊,孙科,王强,王明. 原位聚合制备聚氨酯/氧化石墨烯纳米复合材料的力学性能和热稳定性能研究*[J]. 材料研究学报, 2014, 28(12): 901-908.
Guoxing LI, Jingshan ZHAO, Ke SUN, Qiang WANG, Ming WANG. Study on Mechanical Property and Thermal Stability of In-situ Nanocomposites of Polyurethane/ Oxidized Graphene[J]. Chinese Journal of Materials Research, 2014, 28(12): 901-908.

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摘要:

采用两步投料法, 将氧化石墨烯(GO)与4, 4′-二苯基甲烷二异氰酸酯(MDI)充分反应后、再加入聚醚多元醇和三羟甲基丙烷原位聚合制备聚氨酯(PU)/GO纳米复合材料。用广角x衍射、拉伸仪、热失重分析仪和扫描电子显微镜等研究了GO含量对PU/GO复合材料弹性模量、拉伸强度、断裂伸长率和热稳定性能的影响。研究发现当GO含量为0.2%时, GO在PU基体内分散均匀未出现团聚现象; 当GO含量增加时, 出现GO团聚体, 且随着GO含量增加而增加。GO团聚现象对PU/GO复合材料的力学性能和热稳定性提高具有不利的影响。未出现GO团聚体的PU/0.2%GO复合材料具有最佳力学性能和热稳定性。用连二亚硫酸钠、氢氧化钠水溶液就地还原制备还原PU/GO纳米复合材料(PU/rGO), 研究GO还原对复合材料力学性能和热稳定性的影响。结果发现, GO在PU基体内可以实现一定程度的就地还原, 还原后复合材料的力学性能有所下降, 但热稳定性能有所提高。

关键词 ：有机高分子材料, 氧化石墨烯, 原位聚合, 聚氨酯, 力学性能

Abstract：

The nanocomposites of polyurethane (PU)/oxidized grapheme (GO) were in-situ prepared by a two step process, i.e. firstly the oxidized graphene (GO) and 4, 4’-diphenylmethane diisocyanate (MDI) were fully reacted, and then polyether polyol and trimethylolpropane were further added to synthesize the nanocomposites. The mechanical property and thermal stability of the nanocomposites were investigated by wide-angle x-ray diffractormetry (WAXD), tensile test machine, TGA and SEM. The GOs evenly dispersed and no aggregation was found in PU matrix for the PU/GO nanocomposites with 0.2 % GO. However, the aggregation of GOs appeared and increased with the increasing GO content. The aggregation of GOs was harmful to the mechanical property and thermal stability of the PU/GO nanocomposites. The nanocomposites of PU/0.2% GO show the best mechanical property and thermal stability. The reduced nanocomposites of PU/GO (named as PU/rGO) were prepared by an in-situ reduction process in a solution of sodium hydrosulfite and sodium hydroxide. It follows that the GOs in the PU matrix could be partly reduced; however such partly reduction of GOs would decline the mechanical property, while enhance the thermal stability of the nanocomposites.

Key words： organic polymer materials graphene oxide in-situ polymerization polyurethane mechanical property

收稿日期: 2014-03-06

基金资助:* 国家自然科学基金51103119和重庆市科委自然科学基金CSTC2014TJYJA50024资助项目。

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https://www.cjmr.org/CN/10.11901/1005.3093.2013.393 或 https://www.cjmr.org/CN/Y2014/V28/I12/901

图1 两步投料法原位聚合PU/GO复合材料的制备过程示意图

图2 GO (a), MDI改性GO (b)和PU/GO原位聚合复合材料(0.2% GO) (c) 的傅立叶红外图谱

图3 氧化石墨烯还原前PU/GO与PU/rGO纳米复合材料颜色的变化情况

图4 氧化石墨烯还原前PU/GO (a)与PU/rGO (b)纳米复合材料的X射线衍射图

图5 PU/rGO纳米复合材料脆断面的SEM图: (a) PU/0.5%rGO, (b) PU/2.0%rGO, (c)和(d) PU/5.0%rGO

图6 还原前后不同GO含量的PU/GO纳米复合材料杨氏模量(a), 拉伸强度(b)和断裂伸长率(c)变化情况

表1 还原前后PU/GO纳米复合材料的TGA结果

图7 还原前后PU/GO纳米复合材料热重分析图

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