Synthesis of thermoreversible polyurethane based on D-A reaction and preparation and properties of its carbon fiber composites
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摘要: 以二异氰酸酯(MDI)、聚醚多元醇(PTMG)和2, 5-呋喃二甲醇合成了含有呋喃结构的线型聚氨酯，与双马来酰亚胺基二苯甲烷(BMI)通过Diels-Alder反应制备了热可逆聚氨酯固化物，并制备了碳纤维单向复合材料。通过高温红外和DSC分析了聚氨酯树脂的热可逆行为，研究了树脂的溶解性、熔融再加工性及力学性能，分析了碳纤维复合材料的力学性能和动态机械性能。结果表明：热可逆聚氨酯固化物在热循环中有反复断键-交联行为，160℃左右可完成逆反应；采用高温溶剂溶解法或热熔法均可以进行再加工，再加工3次后仍能保持原有力学性能；碳纤维单向复合材料的层间剪切呈二次失效特点，层间剪切强度为34.85 MPa，玻璃化转变温度为93.73℃。Abstract: The line type polyurethane containing furan rings was prepared by diisocyanate (MDI), polyether polyols (PTMG) and 2, 5-furandimethanol. The cured thermoreversible polyurethane was synthesized by Diels-Alder reaction between bismaleimide (BMI) and the line type polyurethane containing furan rings, and the unidirectional carbon fiber composite was prepared. The thermal reversible behavior of the cured thermoreversible polyurethane was analyzed through high-temperature FTIR and DSC. The solubility, melt reprocessing ability and mechanical properties of the cured thermoreversible polyurethane were studied, the mechanical properties and dynamic mechanical properties of carbon fiber composites were also analyzed. The results show that the cured thermoreversible polyurethane has a repeated behavior of bond breaking and cross-linking during thermal cycling, and the reversible reaction is completed about 160℃. Both high-temperature dissolution process and hot-melt process can be used for reprocessing. After being reprocessed three times, the original mechanical properties of the cured thermoreversible polyurethane can still be maintained. The interlaminar shear of unidirectional carbon fiber composites was characterized by secondary failure, and the interlaminar shear strength is 34.85 MPa. The glass transition temperature of thermoreversible polyurethane is 93.73℃.
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Key words:
- thermoreversible polyurethane /
- D-A reaction /
- composite /
- recycling /
- secondary failure
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图 2 含呋喃环线型聚氨酯及热可逆聚氨酯固化物红外图谱
Figure 2. Infrared spectra of line type polyurethane containing furan rings and cured thermoreversible polyurethane
图 3 热可逆聚氨酯固化物的升降温DSC曲线
Figure 3. Temperature heating and cooling DSC curves of cured thermoreversible polyurethane
图 4 热可逆聚氨酯高低温红外图谱
Figure 4. High and low temperature infrared spectra of thermoreversible polyurethane
图 5 单向碳纤维/热可逆聚氨酯复合材料层剪应力-应变曲线
Figure 5. Stress-strain curve of unidirectional carbon fiber/thermoreversible polyurethane under interlaminar shear
图 6 层剪测试前(a)、后((b), (c))单向碳纤维/热可逆聚氨酯复合材料的SEM图像
Figure 6. SEM images of unidirectional carbon fiber/thermoreversible polyurethane before (a) and after ((b), (c)) interlayer shear test
图 7 单向碳纤维/热可逆聚氨酯复合材料的DMA曲线
Figure 7. DMA curves of unidirectional carbon fiber/thermoreversible polyurethane
E'—Storage modulus; E''—Loss modulus; tanδ—Dissipation factor
表 1 热可逆聚氨酯再加工后力学性能
Table 1. Mechanical properties of thermoreversible polyurethane after reprocessing
High-temperature dissolution process Hot-melt process Tensile strength/MPa Break at elongation/% Tensile strength/MPa Break at elongation/% Original sample 25.2±3 76.7±15 25.2±3 76.7±15 1st reprocessed 27.3±3 72.3±15 23.4±3 75.5±15 2nd reprocessed 31.3±3 68.9±15 23.0±3 76.1±15 3rd reprocessed 30.0±3 69.2±15 23.0±3 74.2±15 
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