Diels-Alder型热修复木质素/三元乙丙橡胶的制备及性能

张润琦; 玄璐佳; 杨尚毅; 于萌萌; 王洪振

Diels-Alder型热修复木质素/三元乙丙橡胶的制备及性能

1.
青岛科技大学　高分子科学与工程学院, 青岛 266042
2.
中策橡胶(天津)有限公司, 天津 300452

基金项目: 国家重点研发计划项目(2022YFD2301204);山东省自然科学基金项目(ZR 2020MB 041)

详细信息

通讯作者:
王洪振，博士，副教授，硕士生导师，研究方向为环境友好型橡胶材料的制备及绿色加工　E-mail: qustwhz@163.com

中图分类号: TQ333.4; TB332
计量
- 文章访问数: 50
- HTML全文浏览量: 23
- 被引次数: 0
出版历程
- 收稿日期: 2024-06-25
- 修回日期: 2024-07-17
- 录用日期: 2024-07-26
- 网络出版日期: 2024-08-16

Preparation and properties of Diels-Alder reactive thermal-heating lignin/EPDM rubber

1.
School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2.
Zhongce Rubber (Tianjin) Co., Ltd, Tianjing 300452, China

Funds: National Key Research and Development Program of China (2022YFD2301204); Natural Science Foundation of Shangdong Province (ZR 2020MB 041)

摘要

摘要: 为改善橡胶材料废弃后的环境污染问题，以糠醛改性木质素(F-Lig)为填料，采用固相共混法制备了Diels-Alder型热修复三元乙丙橡胶(CEF-Lig)。通过可逆交联网络的断裂和重建赋予了CEF-Lig复合材料高温熔融加工、低温交联成型的特性，并探究了F-Lig含量对CEF-Lig材料的微观结构、力学性能和热修复性能的影响。结果表明：成功制备出具有热修复可回收特性的CEF-Lig复合材料；随F-Lig含量增加，拉伸强度呈现先增加后下降的趋势，CEF-Lig7的拉伸强度达到最大值4.6 MPa，为不含F-Lig对照组(CEPDM)的4.6倍；F-Lig的加入提高了CEF-Lig材料的热分解温度，CEF-Lig9最大分解速率对应的温度(T_max)相比CEPDM提升8.8 ℃；CEF-Lig材料具有良好的热修复能力，力学强度的一次修复效率均在70%以上，二次修复效率均在60%以上。此外，采用固相共混法工艺，有效避免了溶剂污染，提高了生产效率，为其他可逆交联聚合物的制备提供参考。
- 木质素 /
- 三元乙丙橡胶 /
- 复合材料 /
- Diels-Alder反应 /
- 力学强度
Abstract: In order to improve the environmental pollution of rubber materials after disposal, Diels-Alder reactive thermal-heating EPDM rubber (CEF-Lig) was prepared using furfural-modified lignin (F-Lig) as a filler in the solid phase blending method. The high-temperature melt processing and low-temperature cross-linking molding of CEF-Lig composites were endowed by the fracture and reconstruction of reversible cross-linking networks, and the effects of F-Lig content on the microstructure, mechanical properties, and thermal repair properties of CEF-Lig materials were explored. The results demonstrate that the CEF-Lig composites with thermally repairable recyclable properties are successfully prepared. With the increase of F-Lig content, the tensile strength shows the trend of increasing and then decreasing, and the tensile strength of CEF-Lig7 reaches the maximum value of 4.6 MPa, which is 4.6 times of that of the control group (CEPDM) without F-Lig. The F-Lig increases the thermal decomposition temperature of the CEF-Lig, and the temperature corresponding to the maximum decomposition rate (T_max) of CEF-Lig9 was increased by 8.8 ℃ compared to CEPDM. The CEF-Lig has a good thermal repair ability, the mechanical strength of the primary repair efficiency are more than 70%, and the secondary repair efficiency are more than 60%. In addition, the solid phase blending method is adopted to effectively avoid solvent contamination and improve the production efficiency, which provides a reference for the preparation of other reversible cross-linked polymers.
- Lignin /
- EPDM /
- Composite materia /
- Diels-Alder reaction /
- Mechanical strength

HTML全文

图 1 (a) F-Lig合成路线图；(b) F-Lig合成装置图；(c) CEF-Lig制备流程图

Figure 1. (a) Synthetic route of F-Lig; (b) Synthetic device of F-Lig; (c) Preparation process of CEF-Lig

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图 2 Lig与F-Lig的红外光谱图

Figure 2. FTIR spectra of Lig and F-Lig

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图 3 核磁共振氢谱图 (a)Lig；(b)F-Lig

Figure 3. ¹H NMR spectra (a)Lig; (b)F-Lig

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图 4 CEPDM和不同F-Lig用量CEF-Lig的红外光谱图

Figure 4. FTIR spectra of CEPDM and CEF-Lig with different F-Lig dosage

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图 5 CEPDM和不同F-Lig用量CEF-Lig的应力-应变曲线

Figure 5. Stress-strain curves of CEPDM and CEF-Lig with different F-Lig dosage

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图 6 CEPDM和不同F-Lig用量CEF-Lig的tanδ曲线

Figure 6. Tanδ curves of CEPDM and CEF-Lig with different F-Lig dosage

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图 7 (a) 室温下CEF-Lig在十氢萘溶剂中的溶胀示意图；(b) 高温下CEF-Lig在十氢萘溶剂中的溶解示意图

Figure 7. (a) Swelling diagram of CEF-Lig in decahydronaphthalene solvent at room temperature; (b) Schematic diagram of dissolution of CEF-Lig in decahydronaphthalene solvent at high temperature

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图 8 CEPDM和不同F-Lig用量CEF-Lig的(a) TG和(b) DTG曲线

Figure 8. (a) TG and (b) DTG curves of CEPDM and CEF-Lig with different F-Lig dosage

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图 9 脆性断裂面SEM图像 (a) CEPDM；(b) CEF-Lig3；(c) CEF-Lig5；(d) CEF-Lig7；(e)CEF-Lig9

Figure 9. SEM image of a brittle fracture surface (a) CEPDM; (b) CEF-Lig3; (c) CEF-Lig5; (d) CEF-Lig7; (e) CEF-Lig9

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图 10 (a) 修复后试样的宏观演示图；(b) CEF-Lig热修复机制示意图

Figure 10. (a) Macroscopic demonstration of repaired specimens; (b) Thermal repair schematic of CEF-Lig

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图 11 CEF-Lig3初始和修复后的红外光谱图

Figure 11. The initial and repaired FTIR spectra of CEF-Lig3

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图 12 初始材料和修复后材料的应力-应变曲线 (a)CEF-Lig1； (b) CEF-Lig3；(c) CEF-Lig5；(d) CEF-Lig7；(e) CEF-Lig9

Figure 12. Stress-strain curves of the initial and repaired specimens (a) CEF-Lig1; (b) CEF-Lig3; (c) CEF-Lig5; (d) CEF-Lig7; (e) CEF-Lig9

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图 13 CEF-Lig力学强度修复效率

Figure 13. Tensile strength repair efficiency of CEF-Lig

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图 14 CEF-Lig初始样品和修复后样品的硬度

Figure 14. Hardness of the initial and repaired samples of CEF-Lig

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图 15 CEF-Lig初始样品和修复后样品的交联密度

Figure 15. The crosslinking density of the initial and repaired samples of CEF-Lig

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表 1 CEPDM和不同F-Lig用量CEF-Lig的配方组成(质量份/phr)

Table 1. Formulation composition of CEPDM and CEF-Lig with different F-Lig dosages (mass parts/phr)

Samples	EPDM	SEF	F-Lig	BMI	DCP
CEPDM	100	6.5	0	10	0.2
CEF-Lig1	100	6.5	4	10	0.2
CEF-Lig3	100	6.5	12	10	0.2
CEF-Lig5	100	6.5	20	10	0.2
CEF-Lig7	100	6.5	28	10	0.2
CEF-Lig9	100	6.5	36	10	0.2
Notes: EPDM—Ethylene-propylene-diene monomer; SEF—Styrene-based furan monomer; F-Lig—Furan-modified lignin; BMI—1,1'-(Methylenedi-4,1-phenylene)bismaleimide; DCP—Dicumyl peroxide.

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表 2 CEPDM和不同F-Lig用量CEF-Lig的应力应变数据

Table 2. Stress-strain data of CEPDM and CEF-Lig with different F-Lig dosage

Samples	Tensile strength/MPa	Ultimate elongation/%
CEPDM	1.0±0.1	312.3±5.3
CEF-Lig1	2.5±0.3	349.4±6.1
CEF-Lig3	3.1±0.3	278.9±5.5
CEF-Lig5	3.8±0.2	238.8±7.4
CEF-Lig7	4.5±0.1	192.3±4.5
CEF-Lig9	4.4±0.1	147.2±3.2

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