Preparation and Properties Characterization of Biobased Dihydrocoumarin Toughened Epoxy Resin†

doi:10.7503/cjcu20190007

Abstract

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

CLC Number:

O633

TrendMD:

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

Figures/Tables 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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