In-situ solution polymerization and properties of chitosan-graphene oxide/thermoplastic polyurethane composites
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摘要: 为了制备高力学性能、阻隔性能和导热性能的热塑性聚氨酯(TPU)复合材料，采用改进的原位溶液聚合法，将壳聚糖改性的氧化石墨烯(CS-GO)与TPU预聚体接枝，再经扩链反应得到CS-GO/TPU复合材料。利用FTIR、XRD、FESEM对CS-GO进行表征，并采用万能试验机、氧气透过仪和导热仪对CS-GO/TPU复合材料的性能进行测试分析。结果表明：CS与GO之间存在氢键作用，CS-GO在TPU基体中的分散性优于GO。CS-GO的均匀分散有效阻隔了O2的渗透，提高了CS-GO/TPU复合材料的阻隔性能。CS-GO与TPU基体之间的相互作用有利于应力载荷的传递和导热网络的形成，与纯TPU相比，当CS-GO含量为1wt%时，CS-GO/TPU复合材料的拉伸强度和断裂伸长率分别提高了106.8%和111.2%，导热系数提高了1.55倍。Abstract: An improved in-situ solution polymerization method was used in order to prepare the thermoplastic polyurethane (TPU) composite with high mechanical properties, barrier properties and thermal conductivity. Graphene oxide modified by chitosan (CS-GO) was grafted onto TPU prepolymer, then CS-GO/TPU composite was synthesized by chain extension reaction. The microstructure of CS-GO was characterized by FTIR, XRD and FESEM. The properties of CS-GO/TPU composites were tested by universal testing machine, oxygen transmission instrument and thermal conductivity meter. The results show that there is a hydrogen bond between CS and GO, and the dispersibility of CS-GO in the TPU matrix is better than GO. The enhancement of barrier property of CS-GO/TPU composites is due to the uniform dispersion of CS-GO which can effectively block the penetration of oxygen. The interaction between CS-GO and TPU matrix has positive effect on the transmission of stress load and the formation of a thermally conductive network. Compared with the pristine TPU, when mass fraction of the CS-GO is 1wt%, the tensile strength and elongation at break of CS-GO/TPU composites are increased by 106.8% and 111.2%, respectively; the thermal conductivity is 1.55 times higher than the pristine TPU.
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图 1 壳聚糖-氧化石墨烯(CS-GO)的结构示意图
Figure 1. Schematic illustration of chitosan-graphene oxide (CS-GO)
图 2 CS-GO/热塑性聚氨酯(TPU)和GO/TPU复合材料制备流程
Figure 2. Schematic illustration of CS-GO/thermoplastic polyurethane (TPU) and GO/TPU composites
PTMG—Polytetramethylene ether glycol; MDI—4,4’-methylene diisocyanate; BDO—1,4-butanediol; DTBL—Dibutyltin dilaurate
图 6 纯TPU(a)、CS-GO含量分别为0.25wt%(b)、0.5wt%(c)、0.75wt%(d)、1wt%(e)、1.25wt%(f)的CS-GO/TPU复合材料断面的FESEM图像
Figure 6. FESEM images of fracture surfaces of pristine TPU(a) and CS-GO/TPU composites with CS-GO mass fraction of 0.25wt%(b), 0.5wt%(c), 0.75wt%(d), 1wt%(e), 1.25wt%(f)
图 7 GO含量分别为0.25wt%(a)、0.5wt%(b)、0.75wt%(c)的GO/TPU复合材料断面的FESEM图像
Figure 7. FESEM images of fracture surfaces of GO/TPU composites with GO mass fraction of 0.25wt%(a), 0.5wt%(b), 0.75wt%(c)
图 8 GO/TPU和CS-GO/TPU复合材料的拉伸强度和断裂伸长率
Figure 8. Tensile strength and elongation at break of GO/TPU and CS-GO/TPU composites
图 9 GO/TPU和CS-GO/TPU复合材料的O2透过率
Figure 9. O2 transmission rate of GO/TPU and CS-GO/TPU composites
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