Citation: Dong Wang, Li-ying Li, Hong-jun Ke, Kong-li Xu, Shan Lu, Wen-hua Gong, Huan Zhang, Guo-yong Wang, Ying-min Zhao, Ning Zhao. Preparation and Properties of Recyclable High-performance Epoxy Resins and Composites[J]. Acta Polymerica Sinica, ;2020, 51(3): 303-310. doi: 10.11777/j.issn1000-3304.2019.19167 shu

Preparation and Properties of Recyclable High-performance Epoxy Resins and Composites

Dong Wang ^1,, ,
Li-ying Li ¹ ,
Hong-jun Ke ¹ ,
Kong-li Xu ¹ ,
Shan Lu ¹ ,
Wen-hua Gong ¹ ,
Huan Zhang ² ,
Guo-yong Wang ^1,, ,
Ying-min Zhao ¹ ,
Ning Zhao ²

1.
Research Institute of Aerospace Special Materials and Processing Technology, Beijing 100074
2.
Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190

Corresponding author: Dong Wang, wangdong@iccas.ac.cn Guo-yong Wang, sock129@163.com
Received Date: 10 September 2019
Revised Date: 19 October 2019

Aiming at the demands for recyclable resins and composites in practical applications, high performance recyclable epoxy resins with excellent comprehensive properties are prepared using methyl teterahydrophthalic anhydride as the curing agent and zinc acetylacetonate hydrate as the catalyst. The effects of anhydride and catalyst concentrations on the structure, thermal and dynamic properties of epoxy vitrimers are systematically explored to achieve the resin formulation optimization. With the decrease of anhydride concentrations, the cross-linking densities decrease, and the epoxy vitrimers show decreased glass transition temperature (T_g) but enhanced dynamic properties, which is attributed to the sufficient hydroxyl groups in structure that could trigger the transesterification exchange reactions with ester bonds. The increase of catalyst concentrations can also lead to enhanced dynamic properties as a result of the accelerated transesterification rates. The epoxy vitrimer with epoxy/anhydride/catalyst ratios of 1:0.5:0.05 displays optimal comprehensive performance with intermediate thermal properties and excellent dynamic properties. Based on the dynamic transesterification reaction, the epoxy vitrimers can be well reprocessed by the physically hot pressing methods at 180 °C for 6 h under a pressure of 10 MPa, and the recycling efficiency can be up to 80%. Moreover, the epoxy vitrimer-based carbon fiber reinforced composites are prepared by the resin transfer molding (RTM) technique. The prepared carbon fabric composites show a tensile strength of 479 MPa and tensile modulus of 58 GPa, revealing comparable mechanical properties to those of traditional thermoset composites. After heating the composites in ethylene glycol solvent at 180 °C for 8 h, the clean carbon fiber fabric with the same dimension as fresh ones can be reclaimed due to the dissolution of epoxy vitrimer binder in alcohol solvent via transesterification. In addition, the collected dissolved polymers can form vitrimers again by evaporating the EG solvent in open air at 180 °C for 12 h. It is demonstrated that the carbon fibers and epoxy polymers can both be fully recycled from the composites by the alcohol solvent dissolution method.
- Epoxy resins,
- Composites,
- Recyclable,
- Transesterification reaction
1. [1]
  Jambeck J R, Geyer R, Wilcox C, Siegler T R, Perryman M, Andrady A, Narayan R, Law K L. Science, 2015, 347: 768 − 771 doi: 10.1126/science.1260352
2. [2]
  Denissen W, Winne J M, Du Prez F E. Chem Sci, 2016, 7: 30 − 38 doi: 10.1039/C5SC02223A
3. [3]
  Imbernon L, Norvez S. Eur Polym J, 2016, 82: 347 − 376 doi: 10.1016/j.eurpolymj.2016.03.016
4. [4]
  Röttger M, Domenech T, van der Weegen R, Breuillac A, Nicolaÿ R, Leibler L. Science, 2017, 356: 62 − 65 doi: 10.1126/science.aah5281
5. [5]
  Fortman D J, Brutman J P, De Hoe G X, Snyder R L, Dichtel W R, Hillmyer M A. ACS Sustain Chem Eng, 2018, 6: 11145 − 11159 doi: 10.1021/acssuschemeng.8b02355
6. [6]
  Zhang Zeping(张泽平), Rong Minzhi(容敏智), Zhang Mingqiu(章明秋). Acta Polymerica Sinica(高分子学报), 2018, (7): 829 − 852 doi: 10.11777/j.issn1000-3304.2018.18060
7. [7]
  Huang Xin(黄鑫), Liu Hanchao(刘汉超), Fan Zheng(樊正), Wang Hao(王豪), Huang Guangsu(黄光速), Wu Jinrong (吴锦荣). Acta Polymerica Sinica(高分子学报), 2019, 50(5): 535 − 542
8. [8]
  Montarnal D, Capelot M, Tournilhac F, Leibler L. Science, 2011, 334: 965 − 968 doi: 10.1126/science.1212648
9. [9]
  Lan Xiaoyu(兰晓雨), Ma Xiaofeng(马晓峰), Dai Peng(戴鹏), Li Bengang(李本刚), Luo Zhenyang(罗振扬). Polymer Bulletin(高分子通报), 2018, (3): 31 − 39
10. [10]
  Chen Xingxing(陈兴幸), Zhong Qianyun(钟倩云), Wang Shujuan(王淑娟), Wu Youshen(吴宥伸), Tan Jidong(谭继东), Lei Hengxin(雷恒鑫), Huang Shaoyong(黄绍永), Zhang Yanfeng(张彦峰). Acta Polymerica Sinica(高分子学报), 2019, 50(5): 469 − 484
11. [11]
  Long R, Qi H J, Dunn M L. Soft Matter, 2013, 9: 4083 − 4096 doi: 10.1039/c3sm27945f
12. [12]
  Capelot M, Montarnal D, Tournilhac F, Leibler L. J Am Chem Soc, 2012, 134: 7664 − 7667 doi: 10.1021/ja302894k
13. [13]
  Capelot M, Unterlass M M, Tournilhac F, Leibler L. ACS Macro Lett, 2012, 1: 789 − 792 doi: 10.1021/mz300239f
14. [14]
  Brutman J P, Delgado P A, Hillmyer M A. ACS Macro Lett, 2014, 3: 607 − 610 doi: 10.1021/mz500269w
15. [15]
  Pei Z, Yang Y, Chen Q, Terentjev E M, Wei Y, Ji Y. Nat Mater, 2014, 13: 36 − 41 doi: 10.1038/nmat3812
16. [16]
  Yang Z, Wang Q, Wang T. ACS Appl Mater Interfaces, 2016, 8: 21691 − 21699 doi: 10.1021/acsami.6b07403
17. [17]
  Imbernon L, Norvez S, Leibler L. Macromolecules, 2016, 49: 2172 − 2178 doi: 10.1021/acs.macromol.5b02751
18. [18]
  Shi Q, Yu K, Kuang X, Mu X, Dunn C K, Dunn M L, Wang T, Qi H J. Mater Horiz, 2017, 4: 598 − 607 doi: 10.1039/C7MH00043J
19. [19]
  Liu W, Schmidt D F, Reynaud E. Ind Eng Chem Res, 2017, 56: 2667 − 2672 doi: 10.1021/acs.iecr.6b03829
20. [20]
  Zhang H, Cai C, Liu W, Li D, Zhang J, Zhao N, Xu J. Sci Rep, 2017, 7: 11833 doi: 10.1038/s41598-017-11485-6
21. [21]
  Yang Yang(杨洋), Zhang Xiqi(张锡奇), Wei Yen(危岩), Ji Yan(吉岩). Acta Polymerica Sinica(高分子学报), 2017, (10): 1662 − 1667 doi: 10.11777/j.issn1000-3304.2017.17134
22. [22]
  Yu K, Taynton P, Zhang W, Dunn M L, Qi H J. RSC Adv, 2014, 4: 10108 − 10117 doi: 10.1039/C3RA47438K
23. [23]
  Demongeot A, Mougnier S J, Okada S, Soulié-Ziakovic C, Tournilhac F. Polym Chem, 2016, 7: 4486 − 4493 doi: 10.1039/C6PY00752J
24. [24]
  Yu K, Shi Q, Dunn M L, Wang T, Qi H J. Adv Funct Mater, 2016, 26: 6098 − 6106 doi: 10.1002/adfm.201602056
25. [25]
  Altuna F I, Pettarin V, Williams R J J. Green Chem, 2013, 15: 3360 − 3366 doi: 10.1039/c3gc41384e
26. [26]
  Yang Y, Pei Z, Zhang X, Tao L, Wei Y, Ji Y. Chem Sci, 2014, 5: 3486 − 3492 doi: 10.1039/C4SC00543K
27. [27]
  Yang Y, Pei Z, Li Z, Wei Y, Ji Y. J Am Chem Soc, 2016, 138: 2118 − 2121 doi: 10.1021/jacs.5b12531
28. [28]
  Pei Z, Yang Y, Chen Q, Wei Y, Ji Y. Adv Mater, 2016, 28: 156 − 160 doi: 10.1002/adma.201503789
29. [29]
  Liu T, Hao C, Wang L, Li Y, Liu W, Xin J, Zhang J. Macromolecules, 2017, 50: 8588 − 8597 doi: 10.1021/acs.macromol.7b01889
30. [30]
  Chabert E, Vial J, Cauchois J P, Mihaluta M, Tournilhac F. Soft Matter, 2016, 12: 4838 − 4845 doi: 10.1039/C6SM00257A
31. [31]
  Lu L, Pan J, Li G. J Mater Chem A, 2017, 5: 21505 − 21513 doi: 10.1039/C7TA06397K
32. [32]
  Liu T, Hao C, Zhang S, Yang X, Wang L, Han J, Li Y, Xin J, Zhang J. Macromolecules, 2018, 51: 5577 − 5585 doi: 10.1021/acs.macromol.8b01010
33. [33]
  Kuang X, Shi Q, Zhou Y, Zhao Z, Wang T, Qi H J. RSC Adv, 2018, 8: 1493 − 1502 doi: 10.1039/C7RA12787A
34. [34]
  Kuang X, Guo E, Chen K, Qi H J. ACS Sustain Chem Eng, 2019, 7: 6880 − 6888 doi: 10.1021/acssuschemeng.8b06409
35. [35]
  Kuang X, Zhou Y, Shi Q, Wang T, Qi H J. ACS Sustain Chem Eng, 2018, 6: 9189 − 9197 doi: 10.1021/acssuschemeng.8b01538
36. [36]
  Li Liying(李丽英), Meng Songhe(孟松鹤), Xu Chenghai(许承海), Zhang Tao(张涛), Wang Guoyong(王国勇), Liu Jianjun(刘建军). Materials Science and Technology(材料科学与工艺), 2015, 23: 6 − 12 doi: 10.11951/j.issn.1005-0299.20150502
1. [1]
  Yihan Xue , Xue Han , Jie Zhang , Xiaoru Wen . NCQDs修饰FeOOH基复合材料的制备及其电容脱盐性能. Acta Physico-Chimica Sinica, 2025, 41(7): 100072-. doi: 10.1016/j.actphy.2025.100072
2. [2]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
3. [3]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
4. [4]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
5. [5]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
6. [6]
  Jiatong Hu , Qiyi Wang , Ruiwen Tang , Jiajing Feng . Photocatalytic Journey of Perylene Diimides in a Competitive Arena. University Chemistry, 2025, 40(5): 328-333. doi: 10.12461/PKU.DXHX202407015
7. [7]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
8. [8]
  Bowen Yang , Rui Wang , Benjian Xin , Lili Liu , Zhiqiang Niu . C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100015-. doi: 10.3866/PKU.WHXB202310024
9. [9]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
10. [10]
  Guanghui SUI , Yanyan CHENG . Application of rice husk-based activated carbon-loaded MgO composite for symmetric supercapacitors. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 521-530. doi: 10.11862/CJIC.20240221
11. [11]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
12. [12]
  Min LI , Xianfeng MENG . Preparation and microwave absorption properties of ZIF-67 derived Co@C/MoS₂ nanocomposites. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1932-1942. doi: 10.11862/CJIC.20240065
13. [13]
  Xin Zhou , Zhi Zhang , Yun Yang , Shuijin Yang . A Study on the Enhancement of Photocatalytic Performance in C/Bi/Bi₂MoO₆ Composites by Ferroelectric Polarization: A Recommended Comprehensive Chemical Experiment. University Chemistry, 2024, 39(4): 296-304. doi: 10.3866/PKU.DXHX202310008
14. [14]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
15. [15]
  Meng Lin , Hanrui Chen , Congcong Xu . Preparation and Study of Photo-Enhanced Electrocatalytic Oxygen Evolution Performance of ZIF-67/Copper(I) Oxide Composite: A Recommended Comprehensive Physical Chemistry Experiment. University Chemistry, 2024, 39(4): 163-168. doi: 10.3866/PKU.DXHX202308117
16. [16]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
17. [17]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
18. [18]
  Limei CHEN , Mengfei ZHAO , Lin CHEN , Ding LI , Wei LI , Weiye HAN , Hongbin WANG . Preparation and performance of paraffin/alkali modified diatomite/expanded graphite composite phase change thermal storage material. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 533-543. doi: 10.11862/CJIC.20230312
19. [19]
  Lijuan Liu , Xionglei Wang . Preparation of Hydrogels from Waste Thermosetting Unsaturated Polyester Resin by Controllable Catalytic Degradation: A Comprehensive Chemical Experiment. University Chemistry, 2024, 39(11): 313-318. doi: 10.12461/PKU.DXHX202403060
20. [20]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(302)
HTML views(23)

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