木质素增强可自修复聚脲弹性体的制备与性能

邹佳利; 于云鹏; 闫雨晴; 宋永明; 房轶群; 王清文

木质素增强可自修复聚脲弹性体的制备与性能

1.
东北林业大学　生物质材料科学与技术教育部重点实验室, 哈尔滨 150040
2.
华南农业大学　材料与能源学院, 广州 510642

基金项目: “十三五”国家重点研发计划项目(2019 YFD1101203); 黑龙江省自然科学基金项目(LH2022 C011)

详细信息

通讯作者:
房轶群，博士，副教授，博士生导师，研究方向为生物质复合材料　E-mail:yqfang@nefu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2022-10-27
- 修回日期: 2022-12-03
- 录用日期: 2022-12-20
- 网络出版日期: 2023-01-06

Fabrication and properties of lignin-reinforced self-healing polyurea elastomer

1.
Key Laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin 150040, China
2.
School of Materials and Energy, South China Agricultural University, Guangzhou 510642

Funds: National Key R&D Program of China in 13 th Five-Year Period(2019 YFD1101203)；Natural Science Foundation of Heilongjiang Province(LH2022 C011)

摘要

摘要: 目的自修复材料具有自发修复机械损伤并恢复材料原有功能的能力，这可以延长材料的使用时间、减少资源的浪费和环境的污染，但大多数自修复材料普遍存在力学性能较弱的问题，尤其是室温可自修复材料。因此，实现聚脲材料高效自修复性的同时，提升其力学性能方面还有待研究。本文利用天然可再生的生物质资源木质素作为增强相，通过与室温自修复聚脲材料复合，制备具有优异力学强度和室温下高效自修复性的木质素/聚脲弹性体，这实现了木质素的高效利用和室温自修复材料力学性能的增强。方法首先，将一定量的木质素溶于有机溶剂内，再将混合均匀的木质素溶液与异氰酸酯和二胺依次混合，采用一步法制备木质素/聚脲复合溶液；将对苯二甲醛加入到木质素/聚脲复合溶液内，通过席夫碱反应制备含有动态亚胺键的自修复聚脲溶液。将制备好的产物倒入聚四氟乙烯模具内，放入真空干燥箱内烘干后可得到木质素/自修复聚脲弹性体(T-L-PUA)。探究了木质素在不同添加量(10%、20%、30%、40%)下对自修复聚脲弹性体力学性能、UV阻隔性能，热稳定性能的影响并分析了T-L-PUA基于动态共价键的自修复特性以及可回收性。结果 SEM观察显示，T-L-PUA的表面以及断面均无木质素团聚情况发生，说明木质素在T-L-PUA中保持了良好的分散性。热重测试结果显示，T-L-PUA的热稳定性较未添加木质素的自修复弹性体(T-PUA)有明显提升。随木质素比例增加，T-L-PUA的Ch和R最多提升16.6%和23.1%，T和T最多升高25.7℃和9.6℃。紫外-可见光光谱显示，T-PUA和T-L-PUA在UVA/UVB区(280-400 nm)的平均透过率分别为41.6%和0.2%，T-L-PUA显示出对UV良好的阻隔效果。力学性能测试结果显示，木质素显著提高了聚脲弹性体的力学性能，添加量为20 wt%时，T-L-PUA的拉伸强度达到最大值12.44 MPa，对应弹性模量值为20.71 MPa，较T-PUA分别提升了937%和614%。继续添加过量木质素会导致拉伸强度有所降低。自修复性能测试结果显示，T-L-PUA具有良好的损伤后的自修复能力及可回收性。在超景深显微镜下观察到切断的T-L-PUA室温下修复5 h后，断口完全消失；修复48 h后，拉伸测试显示其拉伸强度、断裂伸长率以及弹性模量的恢复效率均在90%以上。可回收测试结果显示，破碎的T-L-PUA可通过三次以上热压回收或溶剂回收，且重塑后力学性能基本保持不变。结论通过物理共混的方式将木质素作为增强相引入到自修复聚脲弹性体内，利用木质素的天然芳香结构对自修复聚脲弹性体的力学性能、高温热稳定性、紫外屏蔽性等性能进行了改善，同时木质素的引入不会过多降低聚脲弹性体的自修复性能，这不仅实现了木质素的高值化利用，同时也为绿色功能化聚脲的开发创造了良好契机。
- 木质素 /
- 聚脲弹性体 /
- 自修复性 /
- 亚胺键 /
- 复合材料
Abstract: The preparation of polymeric materials with good mechanical properties and efficient self-healing properties at room temperature has been a difficult challenge. Herein, a lignin-reinforced self-healing polyurea elastomer was prepared by a two-step process (polyurea reaction and schiff base reaction) using natural aromatic-based lignin as the reinforcing phase. The effects of lignin content on the thermal, UV-blocking and mechanical properties of T-L-PUA were investigated and the self-healing property and recyclability based on dynamic reversible imine bonding (C=N) of T-L-PUA were analyzed. The results show that the thermal stability of T-L-PUA is significantly enhanced with the increase of lignin ratio, where the maximum increase of residual carbon is 16.6% compared with the sample without lignin. The low transmittance of T-L-PUA in the UV region(280~400 nm)helps to realize the UV-blocking function. Compared with the average transmittance of T-PUA (41.6%), the average transmittance of all T-L-PUAs is around 0.2%. The best mechanical property appears at 20wt% of lignin addition, and the corresponding tensile strength of T-L-PUA is 12.44 MPa, which is 937% higher than that of pure polyurea elastomer. T-L-PUA exhibits good self-healing properties. When T-L-PUA is repaired at room temperature for 48h, the recovery efficiencies of tensile strength and elongation at break is above 91% and 94%, respectively. In addition, the T-L-PUA can also be recovered by the hot-pressing and solvent dissolution processes, and the mechanical properties remain largely unchanged after remolding.
- lignin /
- polyurea elastomer /
- self-healing property /
- imine bond /
- composites

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图 1 自修复木质素/聚脲复合弹性体的制备示意图

Figure 1. Schematic diagram of the preparation of self-healing lignin/polyurea composite elastomer

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图 2 T-PUA及T-L-PUA涉及的化学合成

Figure 2. Chemical synthesis involved in T-PUA and T-L-PUA

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图 3 T-PUA的¹H NMR谱图(a)；T-PUA及其合成原料的FTIR谱图(b)和木质素及不同木质素添加量的T-L-PUA的FTIR谱图(c)

Figure 3. ¹H NMR spectrum of T-PUA (a); FTIR spectra of T-PUA and its synthetic raw materials (b) and FTIR spectra of lignin and T-L-PUA with different lignin additions (c)

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图 4 T-PUA及不同木质素含量T-L-PUA的TG、DTG曲线(a)以及DSC曲线(b)

Figure 4. TG and DTG curves (a) and DSC curves (b) of T-PUA and T-L-PUA with different lignin contents

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图 5 T-PUA及T-L-PUA的紫外-可见光透射光谱

Figure 5. Transmittance of the T-PUA and T-L-PUA in the UV and visible regions

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图 6 T-PUA及T-L-PUA溶液的照片(a)；T-L₂-PUA表面及截面的SEM图像(b)；T-PUA及不同木质素含量T-L-PUA的拉伸应力-应变曲线(c)和杨氏模量及断裂伸长率(d)

Figure 6. Pictures of the solutions of T-PUA and T-L-PUA (a); SEM image of T-L₂-PUA surface and section (b); Stress-strain curves (c), Young's modulus and elongation at break (d) of T-PUA and T-L-PUA with different lignin contents

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图 7 T-L-PUA自修复试验过程的照片(a)；修复0 h、1 h、5 h的T-L₂-PUA表面超景深光学图像(b)；T-L-PUA的自修复机制示意图(c)；修复12 h、24 h、48 h的T-L₂-PUA拉伸应力-应变曲线(d)以及恢复效率(e)；不同木质素含量T-L-PUA修复48 h后的恢复效率(f)

Figure 7. Pictures of the self-healing test process of T-L-PUA (a); Super depth-of-field optical images of surface of T-L₂-PUA repaired for 0 h, 1 h and 5 h; Schematic diagram of the self-healing mechanism of T-L-PUA (c); Tensile stress-strain curves (d) and recovery efficiencies (e) of T-L₂-PUA repaired for 12 h, 24 h and 48 h; Recovery efficiency of T-L-PUA with different lignin contents after 48 h healing (f)

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图 8 T-L₂-PUA热压回收前后的照片(a)；热压循环回收后的T-L₂-PUA的拉伸应力-应变曲线(b)；T-L₂-PUA溶剂回收工艺(c)；溶剂循环回收后的T-L₂-PUA的拉伸应力-应变曲线(d)

Figure 8. Photographs of T-L₂-PUA before and after hot-press recycling (a);Tensile stress-strain curve of T-L₂-PUA after hot-pressing cycle recovery (b); Solvent recovery process of T-L₂-PUA (c); Tensile stress-strain curves of T-L₂-PUA after solvent cycle recovery (d)

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表 1 T-PUA及不同木质素含量T-L-PUA的热性能结果

Table 1. Thermal properties of T-PUA and T-L-PUA with different lignin contents

Sample	T_5%/℃	T_50%/℃	T_max /℃	R_max/(%/min)	Ch/%
T-PUA	285.5	343.8	366.4	11.30	2.800
T-L₁-PUA	279.8	353.7	369.1	10.20	7.420
T-L₂-PUA	268.9	359.7	372.1	10.00	11.63
T-L₃-PUA	262.2	364.2	373.6	8.850	16.77
T-L₄-PUA	261.6	369.5	376.0	8.710	19.43
Notes：T_5% and T_50% are the temperature corresponding to mass loss of 5% and 50%, T_max is the temperature at the maximum rate of mass loss, R_max is the maximum mass loss rate, Ch is the residual mass fraction.

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