Citation: Yue Han, Dong-Hao Tang, Guang-Xing Wang, Ya-Nan Sun, Ying Guo, Heng Zhou, Wen-Feng Qiu, Tong Zhao. Phthalonitrile Resins Derived from Vanillin: Synthesis, Curing Behavior, and Thermal Properties[J]. Chinese Journal of Polymer Science, ;2020, 38(1): 72-83. doi: 10.1007/s10118-019-2311-3 shu

Phthalonitrile Resins Derived from Vanillin: Synthesis, Curing Behavior, and Thermal Properties

Yue Han ^a ,
Dong-Hao Tang ^b ,
Guang-Xing Wang ^b,c,d ,
Ya-Nan Sun ^b,c ,
Ying Guo ^b ,
Heng Zhou ^b,, ,
Wen-Feng Qiu ^a,, ,
Tong Zhao ^a,b

a.
South China Advanced Institute for Soft Matter Science and Technology, South China University of Technology, Guangzhou 510640, China
b.
Laboratory of Advanced Polymeric Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China
d.
Sinosteel Anshan Research Institute of Thermo-Energy Co., LTD, Anshan 114044, China

Corresponding author: Heng Zhou, zhouheng@iccas.ac.cn Wen-Feng Qiu, wfqiu@scut.edu.cn
Received Date: 20 March 2019
Revised Date: 2 June 2019
Available Online: 3 September 2019

Vanillin was used as sustainable source for phthalonitrile monomer synthesis, and allyl/propargyl ether moieties were introduced to improve the processability at the minimal cost of thermal properties. The synthesis route was optimized to minimize side-reactions and simplify post-processing, and the monomers were obtained in high purity and good yields. The curing behavior, mechanism, and processability of the monomers were studied, and the thermal properties of cured polymers were evaluated. Of the two monomers, the allyl ether-containing one exhibited a wide processing window of 185 °C, and was mainly cured into phthalocyanine and linear aliphatic structures through self-catalytic curing process. Also, the glass transition temperature was higher than 500 °C. In contrast, the propargyl ether-containing monomer could only be partially cured, and heat resistance was found to be compromised. Compared with traditional petroleum-based phthalonitrile resins, the bio-based monomers could be cured without the addition of catalysts, and improvement in processability was achieved at no cost of thermal performances.
- Allyl ether,
- Curing mechanism,
- Phthalonitrile,
- Thermal properties,
- Vanillin
1. [1]
  Augustine, D.; Mathew, D.; Reghunadhan, N. C. P. Mechanistic and kinetic aspects of the curing of phthalonitrile monomers in the presence of propargyl groups. Polymer 2015, 60, 308−317. doi: 10.1016/j.polymer.2015.01.055
2. [2]
  Wang, M.; Ning, Y. Oligosilylarylnitrile: the thermoresistant thermosetting resin with high comprehensive properties. ACS Appl. Mater. Interfaces 2018, 10, 11933−11940. doi: 10.1021/acsami.8b00238
3. [3]
  Phua, E. J. R.; Liu, M.; Cho, B.; Liu, Q.; Amini, S.; Hu, X.; Gan, C. L. Novel high temperature polymeric encapsulation material for extreme environment electronics packaging. Mater. Design 2018, 141, 202−209. doi: 10.1016/j.matdes.2017.12.029
4. [4]
  Bulgakov, B. A.; Sulimov, A. V.; Babkin, A. V.; Timoshkin, I. A.; Solopchenko, A. V.; Kepman, A. V.; Avdeev, V. V. Phthalonitrile-carbon fiber composites produced by vacuum infusion process. J. Compos. Mater. 2017, 51, 4157−4164. doi: 10.1177/0021998317699452
5. [5]
  Zong, L.; Liu, C.; Zhang, S.; Wang, J.; Jian, X. Enhanced thermal properties of phthalonitrile networks by cooperating phenyl-s-triazine moieties in backbones. Polymer 2015, 77, 177−188. doi: 10.1016/j.polymer.2015.09.035
6. [6]
  Han, Y.; Wang, G.; Qiu, W.; Guo, Y.; Sun, Y.; Zhang, Y.; Zhou, H.; Zhao, T. Activated-carbon-supported calcium oxide: a selective and efficient catalyst for nitrile-containing diaryl ether synthesis. Asian J. Org. Chem. 2018, 7, 2511−2517. doi: 10.1002/ajoc.v7.12
7. [7]
  Xu, Y. L.; Dayo, A. Q.; Derradji, M.; Wang, J.; Liu, W. B.; Song, S.; Tang, T. Copolymerization of bisphthalonitrile/benzoxazine blends: curing behavior, thermomechanical and thermal properties. React. Funct. Polym. 2018, 123, 97−105. doi: 10.1016/j.reactfunctpolym.2017.12.013
8. [8]
  Sastri, S. B.; Armistead, J. P.; Keller, T. M. Phthalonitrile-carbon fiber composites. Polym. Compos. 1996, 17, 816−823. doi: 10.1002/(ISSN)1548-0569
9. [9]
  Song, Y.; Zong, L.; Bao, F.; Li, G.; Wu, Z.; Li, N.; Wang, J.; Jian, X. Reduced curing kinetic energy and enhanced thermal resistance of phthalonitrile resins modified with inorganic particles. Polym. Adv. Technol. 2018, 29, 1922−1929. doi: 10.1002/pat.v29.7
10. [10]
  Keller, T. M.; Dominguez, D. D. High temperature resorcinol-based phthalonitrile polymer. Polymer 2005, 46, 4614−4618. doi: 10.1016/j.polymer.2005.03.068
11. [11]
  Mohanty, A. K.; Vivekanandhan, S.; Pin, J. M.; Misra, M. Composites from renewable and sustainable resources: challenges and innovations. Science 2018, 362, 536−542. doi: 10.1126/science.aat9072
12. [12]
  Upton, B. M.; Kasko, A. M. Strategies for the conversion of lignin to high-value polymeric materials: review and perspective. Chem. Rev. 2016, 116, 2275−2306. doi: 10.1021/acs.chemrev.5b00345
13. [13]
  Auvergne, R.; Caillol, S.; David, G.; Boutevin, B.; Pascault, J. P. Biobased thermosetting epoxy: present and future. Chem. Rev. 2014, 114, 1082−1115. doi: 10.1021/cr3001274
14. [14]
  Qi, Y.; Weng, Z.; Wang, J.; Zhang, S.; Zong, L.; Liu, C.; Jian, X. A novel bio-based phthalonitrile resin derived from catechin: synthesis and comparison of curing behavior with petroleum-based counterpart. Polym. Int. 2018, 67, 322−329.
15. [15]
  Laskoski, M.; Clarke, J. S.; Neal, A.; Harvey, B. G.; Ricks-Laskoski, H. L.; Hervey, W. J.; Daftary, M. N.; Shepherd, A. R.; Keller, T. M. Sustainable high-temperature phthalonitrile resins derived from resveratrol and dihydroresveratrol. ChemistrySelect 2016, 1, 3423−3427. doi: 10.1002/slct.201600304
16. [16]
  Laskoski, M.; Shepherd, A. R.; Mahzabeen, W.; Clarke, J. S.; Keller, T. M.; Sorathia, U. Sustainable, fire-resistant phthalonitrile-based glass fiber composites. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1128−1132. doi: 10.1002/pola.v56.11
17. [17]
  Fache, M.; Boutevin, B.; Caillol, S. Vanillin, a key-intermediate of biobased polymers. Eur. Polym. J. 2015, 68, 488−502. doi: 10.1016/j.eurpolymj.2015.03.050
18. [18]
  Savonnet, E.; Grau, E.; Grelier, S.; Defoort, B.; Cramail, H. Divanillin-based epoxy precursors as DGEBA substitutes for biobased epoxy thermosets. ACS Sustain. Chem. Eng. 2018, 6, 11008−11017. doi: 10.1021/acssuschemeng.8b02419
19. [19]
  Wang, S.; Ma, S.; Xu, C.; Liu, Y.; Dai, J.; Wang, Z.; Liu, X.; Chen, J.; Shen, X.; Wei, J.; Zhu, J. Vanillin-derived high-performance flame retardant epoxy resins: facile synthesis and properties. Macromolecules 2017, 50, 1892−1901. doi: 10.1021/acs.macromol.7b00097
20. [20]
  Harvey, B. G.; Guenthner, A. J.; Meylemans, H. A.; Haines, S. R. L.; Lamison, K. R.; Groshens, T. J.; Cambrea, L. R.; Davis, M. C.; Lai, W. W. Renewable thermosetting resins and thermoplastics from vanillin. Green Chem. 2015, 17, 1249−1258. doi: 10.1039/C4GC01825G
21. [21]
  Xu, S.; Han, Y.; Guo, Y.; Luo, Z.; Ye, L.; Li, Z.; Zhou, H.; Zhao, Y.; Zhao, T. Allyl phenolic-phthalonitrile resins with tunable properties: curing, processability and thermal stability. Eur. Polym. J. 2017, 95, 394−405. doi: 10.1016/j.eurpolymj.2017.08.010
22. [22]
  Sheng, H.; Peng, X.; Guo, H.; Yu, X.; Naito, K.; Qu, X.; Zhang, Q. Synthesis of high performance bisphthalonitrile resins cured with self-catalyzed 4-aminophenoxy phthalonitrile. Thermochim. Acta 2014, 577, 17−24. doi: 10.1016/j.tca.2013.12.010
23. [23]
  Smith, M. B.; March, J. March's advanced organic chemistry: reactions, mechanisms, and structure. John Wiley & Sons, 2007.
24. [24]
  Ichikawa, H.; Maruoka, K. The Claisen rearrangement: methods and applications. Wiley-VCH Verlag GmbH & Co, 2007.
25. [25]
  Reghunadhan, N. C. P.; Krishnan, K.; Ninan, K. N. Differential scanning calorimetric study on the Claisen rearrangement and thermal polymerisation of diallyl ether of bisphenols. Thermochim. Acta 2000, 359, 61−67. doi: 10.1016/S0040-6031(00)00504-9
26. [26]
  Sumner, M. J.; Sankarapandian, M.; McGrath, J. E.; Riffle, J. S.; Sorathia, U. Flame retardant novolac-bisphthalonitrile structural thermosets. Polymer 2002, 43, 5069−5076. doi: 10.1016/S0032-3861(02)00354-3
27. [27]
  Zeng, K.; Zhou, K.; Zhou, S.; Hong, H.; Zhou, H.; Wang, Y.; Miao, P.; Yang, G. Studies on self-promoted cure behaviors of hydroxy-containing phthalonitrile model compounds. Eur. Polym. J. 2009, 45, 1328−1335. doi: 10.1016/j.eurpolymj.2008.12.036
28. [28]
  Ma, J. Z.; Cheng, K.; Lv, J. B.; Chen, C.; Hu, J. H.; Zeng, K.; Yang, G. Phthalonitrile-PPO blends: cure behavior and properties. Chinese J. Polym. Sci. 2018, 36, 497−504.
29. [29]
  Hu, J.; Liu, Y.; Jiao, Y.; Ji, S.; Sun, R.; Yuan, P.; Zeng, K.; Pu, X.; Yang, G. Self-promoted phthalimide-containing phthalonitrile resins with sluggish curing process and excellent thermal stability. RSC Adv. 2015, 5, 16199−16206. doi: 10.1039/C4RA17306F
30. [30]
  Guo, H.; Chen, Z.; Liu, X. Effect of processing conditions on physical properties of 3-aminophenoxyphthalonitrile/epoxy laminates. J. Appl. Polym. Sci. 2014, 131, 39746.
31. [31]
  Zhao, X.; Guo, H.; Lei, Y.; Zhao, R.; Zhong, J.; Liu, X. Effect of polyarylene ether nitriles on processing and mechanical behaviors of phthalonitrile-epoxy copolymers and glass fiber laminated composites. J. Appl. Polym. Sci. 2013, 127, 4873−4878. doi: 10.1002/app.38089
32. [32]
  Jiang, M.; Xu, M.; Jia, K.; Liu, X. Copolymerization of self-catalyzed phthalonitrile with bismaleimide toward high-temperature-resistant polymers with improved processability. High Perform. Polym. 2016, 28, 895−907. doi: 10.1177/0954008315606955
1. [1]
  Wenzhong Zhang , Zirui Yan , Lingcheng Chen , Yi Xiao . Sn-fused perylene diimides: Synthesis, mechanism, and properties. Chinese Chemical Letters, 2024, 35(10): 109582-. doi: 10.1016/j.cclet.2024.109582
2. [2]
  Xiao Zhu , Yanbing Mo , Jiawei Chen , Gaopan Liu , Yonggang Wang , Xiaoli Dong . A weakly-solvated ether-based electrolyte for fast-charging graphite anode. Chinese Chemical Letters, 2024, 35(8): 109146-. doi: 10.1016/j.cclet.2023.109146
3. [3]
  Kangrong Yan , Ziqiu Shen , Yanchun Huang , Benfang Niu , Hongzheng Chen , Chang-Zhi Li . Curing the vulnerable heterointerface via organic-inorganic hybrid hole transporting bilayers for efficient inverted perovskite solar cells. Chinese Chemical Letters, 2024, 35(6): 109516-. doi: 10.1016/j.cclet.2024.109516
4. [4]
  Yaping Zhang , Wei Zhou , Mingchun Gao , Tianqi Liu , Bingxin Liu , Chang-Hua Ding , Bin Xu . Oxidative cyclization of allyl compounds and isocyanide: A facile entry to polysubstituted 2-cyanopyrroles. Chinese Chemical Letters, 2024, 35(4): 108836-. doi: 10.1016/j.cclet.2023.108836
5. [5]
  Chong-Yang Shi , Jian-Xing Gong , Zhen Li , Chao Shu , Long-Wu Ye , Qing Sun , Bo Zhou , Xin-Qi Zhu . Gold-catalyzed intermolecular amination of allyl azides with ynamides: Efficient construction of 3-azabicyclo[3.1.0] scaffold. Chinese Chemical Letters, 2025, 36(2): 109895-. doi: 10.1016/j.cclet.2024.109895
6. [6]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
7. [7]
  Bharathi Natarajan , Palanisamy Kannan , Longhua Guo . Metallic nanoparticles for visual sensing: Design, mechanism, and application. Chinese Journal of Structural Chemistry, 2024, 43(9): 100349-100349. doi: 10.1016/j.cjsc.2024.100349
8. [8]
  Ruizhi Yang , Xia Li , Weiping Guo , Zixuan Chen , Hongwei Ming , Zhong-Zhen Luo , Zhigang Zou . New thermoelectric semiconductors Pb5Sb12+xBi6-xSe32 with ultralow thermal conductivity. Chinese Journal of Structural Chemistry, 2024, 43(3): 100268-100268. doi: 10.1016/j.cjsc.2024.100268
9. [9]
  Chaozheng He , Pei Shi , Donglin Pang , Zhanying Zhang , Long Lin , Yingchun Ding . First-principles study of the relationship between the formation of single atom catalysts and lattice thermal conductivity. Chinese Chemical Letters, 2024, 35(6): 109116-. doi: 10.1016/j.cclet.2023.109116
10. [10]
  Zhiqing Ge , Zuxiong Pan , Shuo Yan , Baoying Zhang , Xiangyu Shen , Mozhen Wang , Xuewu Ge . Novel high-temperature thermochromic polydiacetylene material and its application as thermal indicator. Chinese Chemical Letters, 2024, 35(11): 109850-. doi: 10.1016/j.cclet.2024.109850
11. [11]
  Guizhi Zhu , Junrui Tan , Longfei Tan , Qiong Wu , Xiangling Ren , Changhui Fu , Zhihui Chen , Xianwei Meng . Growth of CeCo-MOF in dendritic mesoporous organosilica as highly efficient antioxidant for enhanced thermal stability of silicone rubber. Chinese Chemical Letters, 2025, 36(1): 109669-. doi: 10.1016/j.cclet.2024.109669
12. [12]
  Shuai Liang , Wen-Jing Jiang , Ji-Xiang Hu . Achieving colossal anisotropic thermal expansion via synergism of spin crossover and rhombus deformation. Chinese Journal of Structural Chemistry, 2025, 44(2): 100430-100430. doi: 10.1016/j.cjsc.2024.100430
13. [13]
  Xiaoyu Chen , Jiahao Hu , Jingyi Lin , Haiyang Huang , Changqing Ye , Hongli Bao . Biisoindolylidene solvatochromic fluorophores: Synthesis and photophysical properties. Chinese Chemical Letters, 2025, 36(2): 109923-. doi: 10.1016/j.cclet.2024.109923
14. [14]
  Yuan Dong , Mutian Ma , Zhenyang Jiao , Sheng Han , Likun Xiong , Zhao Deng , Yang Peng . Effect of electrolyte cation-mediated mechanism on electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2024, 35(7): 109049-. doi: 10.1016/j.cclet.2023.109049
15. [15]
  Hongxia Li , Xiyang Wang , Du Qiao , Jiahao Li , Weiping Zhu , Honglin Li . Mechanism of nanoparticle aggregation in gas-liquid microfluidic mixing. Chinese Chemical Letters, 2024, 35(4): 108747-. doi: 10.1016/j.cclet.2023.108747
16. [16]
  Yixin Zhang , Ting Wang , Jixiang Zhang , Pengyu Lu , Neng Shi , Liqiang Zhang , Weiran Zhu , Nongyue He . Formation mechanism for stable system of nanoparticle/protein corona and phospholipid membrane. Chinese Chemical Letters, 2024, 35(4): 108619-. doi: 10.1016/j.cclet.2023.108619
17. [17]
  Jia Fu , Shilong Zhang , Lirong Liang , Chunyu Du , Zhenqiang Ye , Guangming Chen . PEDOT-based thermoelectric composites: Preparation, mechanism and applications. Chinese Chemical Letters, 2024, 35(9): 109804-. doi: 10.1016/j.cclet.2024.109804
18. [18]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
19. [19]
  Hai-Ling Wang , Zhong-Hong Zhu , Hua-Hong Zou . Structure and assembly mechanism of high-nuclear lanthanide-oxo clusters. Chinese Journal of Structural Chemistry, 2024, 43(9): 100372-100372. doi: 10.1016/j.cjsc.2024.100372
20. [20]
  Jia-hui Li , Jinkai Qiu , Cheng Lian . Lithium-ion rapid transport mechanism and channel design in solid electrolytes. Chinese Journal of Structural Chemistry, 2025, 44(1): 100381-100381. doi: 10.1016/j.cjsc.2024.100381

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(750)
HTML views(13)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142