Preparation and properties of polydopamine modified nano-silica reinforced trans-1, 4-polyisoprene shape memory polymers
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摘要: 由于形状记忆聚合物(SMP)较低的力学强度，不足以满足现今大多数商用复合材料的使用标准，严重限制了其在许多高级应用中的使用。因此，为制备高性能SMP复合材料，利用聚多巴胺(PDA)对纳米SiO2进行表面改性，制备了一种新型纳米填料SiO2@PDA，并通过SEM、XPS和FTIR对其结构和性能进行了表征。将SiO2和SiO2@PDA作为纳米填料填充到反式-1, 4-聚异戊二烯(TPI)中，制备了TPI形状记忆复合材料，系统的研究了TPI/SiO2和TPI/SiO2@PDA复合材料的热稳定性、力学性能和形状记忆性能。结果表明：PDA修饰增强了SiO2在TPI基体中的分散性和界面相互作用，从而使TPI/SiO2@PDA复合材料的热稳定性、力学性能得到提升的同时仍能够保持良好的形状记忆性能。当SiO2@PDA含量为1.5% (以TPI的质量为基准，下同)时，TPI复合材料的冲击强度和拉伸强度达到最大值，分别比纯TPI提高了43.5%和25%。此外，复合材料固定率(Rf)和回复率(Rr)均超过97%。
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关键词:
- 反式-1, 4-聚异戊二烯 /
- 聚多巴胺 /
- 纳米二氧化硅 /
- 力学性能 /
- 形状记忆
Abstract: The low mechanical strength of shape memory polymers (SMP) are insufficient to meet the standards of most commercial composites today, severely limiting their use in many advanced applications. Therefore, in order to prepare high-performance SMP composite materials, a novel nano-filler SiO2@PDA was prepared by surface modification of nano-silica (SiO2) with polydopamine (PDA), its structure and properties were characterized by SEM, XPS and FTIR, respectively. Shape memory composites based on trans-1,4-polyisoprene (TPI) were prepared by filling SiO2 and SiO2@PDA into TPI as nano-fillers. The thermal stability, comprehensive mechanical properties and shape memory properties of TPI/SiO2 and TPI/SiO2@PDA composites were systematically studied. The results show that PDA modification enhances the dispersion and interfacial interaction of SiO2 in the TPI matrix, so that the thermal stability and mechanical properties of the TPI/SiO2@PDA composites can be improved, while maintaining good shape memory performance. The impact strength and tensile strength of the composite reach the maximum values when the SiO2@PDA content is 1.5% (based on the mass of TPI, the same below), which are 43.5% and 25% higher than that of the neat TPI, respectively. Moreover, shape fixation rate (Rf) and shape recovery rate (Rr) of the composites are over 97%.-
Key words:
- trans-1, 4-polyisoprene /
- polydopamine /
- nano-silica /
- mechanical properties /
- shape memory
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图 1 SiO2@聚多巴胺(PDA)制备工艺示意图
Figure 1. Schematic of preparation process for SiO2@polydopamine (PDA)
图 3 (a) SiO2和SiO2@PDA的XPS全谱；((b)~(d)) SiO2@PDA的N1s、O1s和Si2p的XPS图谱
Figure 3. (a) XPS survey specrta of SiO2 and SiO2@PDA; ((b)-(d)) N1s, O1s and Si2p XPS spectra of SiO2@PDA
图 5 反式-1, 4-聚异戊二烯(TPI)形状记忆复合材料的DSC曲线：(a)结晶过程；(b)熔融过程
Figure 5. DSC curves of trans-1, 4-polyisoprene (TPI) shape memory composites: (a) Crystallization; (b) Melting process
图 8 TPI形状记忆复合材料的力学性能：(a) 应力-应变曲线；(b) 拉伸强度及断裂伸长率
Figure 8. Mechanical properties of TPI shape memory composites: (a) Stress-strain curves; (b) Tensile strength and elongation at break
图 11 TPI形状记忆复合材料的形状记忆特性曲线
Figure 11. Shape memory characteristic curves of the TPI shape memory composites
表 1 反式-1, 4-聚异戊二烯(TPI)复合材料的命名
Table 1. Naming of trans-1, 4-polyisoprene (TPI) composites
Sample TPI/g SiO2/g SiO2@PDA/g Neat TPI 100 − − TPI/SiO2-0.5 g 100 0.5 − TPI/SiO2@PDA-0.5 g 100 − 0.5 TPI/SiO2@PDA-1.0 g 100 − 1.0 TPI/SiO2@PDA-1.5 g 100 − 1.5 TPI/SiO2@PDA-2.0 g 100 − 2.0 
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表 2 TPI复合材料的DSC测试数据
Table 2. DSC test data of TPI composites
Sample Xc/% Tm/℃ Tc/℃ ∆Hm/(J·g-1) Neat TPI 14.03 40.08 7.62 26.21 TPI/SiO2-0.5 g 13.77 40.33 1.06 25.72 TPI/SiO2@PDA-0.5 g 14.76 41.18 5.27 27.58 TPI/SiO2@PDA-1.0 g 15.28 41.68 7.32 28.55 TPI/SiO2@PDA-1.5 g 15.80 42.36 8.89 29.53 TPI/SiO2@PDA-2.0 g 15.20 41.46 5.53 28.40 Note: Xc, Tm, Tc and ∆Hm—Crystallinity, crystallization temperature, melting temperature and melting enthalpy of TPI shape memory composites, respectively.
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表 3 TPI形状记忆复合材料的TG测试数据
Table 3. TG test data for TPI shape memory composites
Sample T5%/℃ Tmax/℃ W600/wt% Neat TPI 277.13 371.21 2.39 TPI/SiO2-0.5 g 310.36 372.53 4.62 TPI/SiO2@PDA-0.5 g 318.93 373.68 5.52 TPI/SiO2@PDA-1.0 g 323.88 375.38 5.75 TPI/SiO2@PDA-1.5 g 326.46 379.06 9.12 TPI/SiO2@PDA-2.0 g 320.95 376.45 6.39 Notes: T5% and Tmax—Initial degradation temperature and maximum degradation temperature of TPI shape memory composites; W600—Mass fraction of residual carbon at 600℃.
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表 4 TPI形状记忆复合材料的形状记忆测试数据
Table 4. Shape memory test data for TPI shape memory composites
Sample Rf/% Rr/% Neat TPI 98.7 98.8 TPI/SiO2-0.5 g 98.3 98.1 TPI/SiO2@PDA-0.5 g 98.6 98.5 TPI/SiO2@PDA-2.0 g 98.5 97.9 Note: Rf and Rr—Shape fixation rate and shape recovery rate of TPI shape memory composites, respectively.
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