生物基氢化香豆素增韧环氧树脂的制备及性能

doi:10.7503/cjcu20190007

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 1043.doi: 10.7503/cjcu20190007

生物基氢化香豆素增韧环氧树脂的制备及性能

韩涛¹, 蔡小霞¹(), 李聪², 乔从德¹, 赵辉^1,³

1. 齐鲁工业大学(山东省科学院)材料科学与工程学院
2. 生物基材料与绿色造纸国家重点实验室, 济南 250353
3. 电子科技大学基础与前沿研究院, 成都 610054

收稿日期:2019-01-04 出版日期:2019-04-17 发布日期:2019-04-17
作者简介:
联系人简介: 蔡小霞, 女, 博士, 副教授, 主要从事功能高分子材料及复合材料方面的研究. E-mail: cxx@qlu.edu.cn
基金资助:
齐鲁工业大学(山东省科学院)青年博士合作基金项目(批准号: 2018BSHZ0028, 2018BSHZ0020)和四川省科技创新人才项目(批准号: 2018RZ0113)资助.

Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin^†

HAN Tao¹, CAI Xiaoxia^1,^*(), LI Cong², QIAO Congde¹, ZHAO Hui^1,³

1. School of Material Science and Engineering
2. State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology(Shandong Academy of Sciences), Jinan 250353, China
3. Institute of Fundamental Sciences and Frontiers, University of Electronic Sciences and Technology of China, Chengdu 610054, China

Received:2019-01-04 Online:2019-04-17 Published:2019-04-17
Contact: CAI Xiaoxia E-mail:cxx@qlu.edu.cn
Supported by:
† Supported by the Young Doctoral Cooperation Funds of Qilu University of Technology(Shandong Academy of Sciences), China(Nos.2018BSHZ0028, 2018BSHZ0020) and the Sichuan Provincial Science and Technology Innovation Talents, China(No.2018RZ0113)

摘要/Abstract

摘要：

通过生物基原料氢化香豆素(DHC), 在铬(Ⅲ)络合物和氯化铵复合物协同催化作用下, 与环氧醚类物质交替共聚, 获得一类三维网状聚合物, 进而与环氧树脂(EP)单体在固化过程中构建双网络结构, 实现有效的应力传递和外部能量吸收, 达到对环氧树脂增韧增强的效果. 凝胶渗透色谱结果表明, DHC基网络(DHC-net)分子量随反应时间延长而增加. ¹H NMR证实了合成的DHC-net分子结构. 同时, 考察了环氧树脂的热力学及力学性能, 发现DHC-net与环氧树脂基体具有良好的相容性; 改性后的环氧树脂断裂伸长率比纯环氧树脂有大幅提高; 拉伸与冲击测试显示, DHC-net含量小于30%时, 改性后环氧树脂的拉伸强度和抗冲击强度均比纯环氧树脂有大幅提高.

关键词: 环氧树脂, 生物基氢化香豆素, 双网络分子结构, 增韧

Abstract:

A kind of 3D polymeric network, obtained through alternating copolymerization of dihydrocoumarin(DHC) and epoxides with the aid of chromium(Ⅲ) complexes and bis(triphenylphosp-hosphoranylidene) ammonium chloride(PPNCl) catalysts, was introduced into the diglycidyl ether of bisphenol A(DGEBA) matrix to build a double network structure. This structure can achieve an effective stress transfer and energy absorption for the DGEBA toughness. The gel permeation chromatography(GPC) results showed that the molecular weight of DHC-net increased with the react time. DHC-based network(DHC-net) structure was confirmed via the ¹H NMR spectrum. Moreover, the chemical structures of epoxy resin(EP), DHC-net and EP/DHC-net double networks were confirmed via the FTIR spectra. DMA, DSC and TGA tests indicated that a good compability between the DHC-based network and the DGEBA matrix. Mechanical test showed that an obvious increase in the elongation at break was achieved after the DHC-based network was introduced into the DGEBA matrix. Furthermore, compared to the neat DGEGA resin, remarkable improvements in tensile and impact strength were found after the introduction of DHC-based network with content no higher than 30%(mass fraction) into the DGEBA matrix.

Key words: Epoxy resin, Biobased dihydrocoumarin, Double network structure, Toughen

中图分类号:

O633

TrendMD:

韩涛, 蔡小霞, 李聪, 乔从德, 赵辉. 生物基氢化香豆素增韧环氧树脂的制备及性能. 高等学校化学学报, 2019, 40(5): 1043.

HAN Tao,CAI Xiaoxia,LI Cong,QIAO Congde,ZHAO Hui. Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin^†. Chem. J. Chinese Universities, 2019, 40(5): 1043.

图/表 13

Scheme 1 Ring-opening reaction of PEGDE with DHC and formation of DHC-net

Table 1 Molecular weights and distributions of DHC-net with different polymerization reaction time

Polymerization reaction time/h	10^-3M_n	10^-3M_w	10^-3M_p	10^-3M_z	Polydispersity
1	1.521	2.264	1.055	7.705	1.488
3	3.114	3.659	3.031	4.905	1.175
6	—	—	—	—	—

Fig.1 1H NMR spectrum of DHC-net

Scheme 2 Formation of epoxy resin cured cross-linking reaction and EP/DHC-net dual network

Fig.2 FTIR spectra of pure EP(a), DHC-net(b) and EP/DHC-net(c)

Fig.3 DSC thermograms of EP and EP/DHC-net(A) and conversion against temperature of the curing of EP and EP/DHC-net(B) a. EP; b. EP/10%DHC-net; c. EP/40%DHC-net.

Table 2 DSC results of the neat epoxy and DHC-net modified epoxy resins

Sample	m(EP)∶m(DHC-net)	T_i/℃	T_p/℃
EP	1∶0	149.71	157.69
EP/10%DHC-net	9∶1	145.98	162.49
EP/40%DHC-net	6∶4	129.01	158.29

Fig.4 DSC curves of the EP, DHC-net and EP/DHC-neta. EP; b. EP/10%DHC-net; c. EP/20%DHC-net; d. EP/30%DHC-net; e. EP/40%DHC-net; f. DHC-net.

Fig.5 Fig.5 tanδ versus temperature for the cured EP and the DHC-net modified epoxy resins(A) and Tg-composition behavior of the blends(B)(A) a. EP; b. EP/10%DHC-net; c. EP/20%DHC-net; d. EP/30%DHC-net; e. EP/40%DHC-net.(B) ○ Tg measured from DMA; · Tg calculated based on Fox equation.Inset of (B) shows the k value of each component calculated by the Gorden-Taylor equation.

Fig.6 Impact(A) and tensile(B) properties of EP and EP/DHC-net

Fig.7 Impact(A) and tensile(B) properties of EP and EP/PEGDE Inset of (B) shows elongation of EP and EP/PEGDE.

Fig.8 TGA curves of pure EP, DHC-net and EP/DHC-net

Fig.9 SEM images of impact fracture surface of pure EP(A) and EP/DHC-net(B)

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生物基氢化香豆素增韧环氧树脂的制备及性能

Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin^†

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生物基氢化香豆素增韧环氧树脂的制备及性能

Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin†

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Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin^†