Curing kinetics and properties of gallic acid epoxy resin/ricinoleic acid⁃based polyamine thermosetting system

doi:10.19491/j.issn.1001-9278.2022.02.012

Abstract

Abstract:

Ricinoleic acid?based polyamine （COAPA） was synthesized as a curing agent using castor oil and three ethyle?ne four amine as raw materials and then was mixed with gallic acid epoxy resin （GAER） to form a whole biological cu?ring system. The curing process of GAER/COAPA composite system was investigated using a nonisothermal DSC method. The optimum mass ratio of GAER to COAPA was determined to be 7：3 for the curing system， and the optimum curing temperatures were obtained. The activation energy and kinetic parameters of curing reaction were obtained by fitting and calculation using the Kissinger equation together with the ?esták?Berggren autocatalytic model. The pro?perties of the cured GAER system were compared with that of the bisphenol?A epoxy cured system. The results indica?ted that the average activation energy of the GAER/COAPA system was 62.28 kJ/mol. When the conversion rate of cu?ring reaction was less than 60 %， the curing kinetics conformed to the ?esták?Berggren autocatalytic model. Compared to the bisphenol?A epoxy thermoset， the gallic acid epoxy thermoset exhibited a lower thermal decomposition temperature and a higher carbon residue rate at 800 ℃， and its tensile strength and flexural modulus were lower， the flexural strength and glass transition temperature were also slightly higher.

Key words: gallic acid epoxy resin, castor oil polyamine, curing kinetics, nonisothermal differential scanning calorimetry, property

CLC Number:

TQ323.5

LIU Zhen, YU Yun, ZHANG Menghang, YIN Liuye, DUAN Yufei, HOU Guixiang. Curing kinetics and properties of gallic acid epoxy resin/ricinoleic acid⁃based polyamine thermosetting system[J]. China Plastics, 2022, 36(2): 75-81.

Figures/Tables 13

Fig.1. GAER synthesis reaction equation

Fig.2. FTIR spectrum of COAPA

Fig.3. FTIR spectrum of GAER

Fig.4. 1H?NMR spectrum of GAER

Fig.5. DSC curves of GAER/COAPA curing system with different GAER and CORPA mass ratio

GAER/COAPA质量比	固化峰值温度/℃	固化放热焓/J·g^-1
8∶2	79.8	144.46
7∶3	79.3	183.53
6∶4	76.6	130.78

Tab.1. Curing and exothermic conditions of different systems

Fig.6. DSC curves of GAER/COAPA cured systems at different heating rates

Fig.7. α?T curves of GAER/COAPA cured systems

Fig.8. Ea?α curves of GAER/COAPA cured systems

β/^oC·min^-1	E_a/kJ·mol^-1	p	lnA	lnA平均数	n	n平均数	m	m平均数
5	62.28	0.100 1	25.498 0	25.423 4	2.035 3	2.011 9	0.203 7	0.209 5
10		0.101 9	25.391 0		1.975 0		0.201 2
15		0.119 8	25.408 9		1.987 7		0.238 1
20		0.095 1	25.395 7		2.049 6		0.194 9

Table 2. Curing kinetic parameters of GAER/COAPA curing systems

Fig.9. Comparison of experimental and calculated DSC curves for GAER/COAPA systems

Fig.10. Thermal weight loss of the sample

样品

拉伸强度/

MPa

弯曲强度/

MPa

弯曲模量/

GPa

玻璃化转变

温度/℃

92.3

90.3

Tab.3. Mechanical properties of the samples

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