咪唑改性氧化石墨烯对阻燃环氧固化动力学的促进作用

doi:10.7503/cjcu20170059

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (10): 1906.doi: 10.7503/cjcu20170059

• 高分子化学 • 上一篇

咪唑改性氧化石墨烯对阻燃环氧固化动力学的促进作用

胡建华^1,²(), 单继业², 童真²()

1. 中国广州分析测试中心, 广东省化学危害应急检测技术重点实验室, 广州 510070
2. 华南理工大学材料科学研究所, 广州 510640

收稿日期:2017-01-23 出版日期:2017-10-10 发布日期:2017-09-05
作者简介:联系人简介: 胡建华, 男, 博士, 助理研究员, 主要从事材料结构与性能研究. E-mail:fox7709@126.com;童真, 男, 博士, 教授, 博士生导师, 主要从事高分子物理研究. E-mail:mcztong@scut.edu.cn
基金资助:
国家自然科学基金-广东省联合基金(批准号: U1201243)和广东省科学院人才资助专项(批准号: 2017GDASCX-0826)资助

Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide^†

HU Jianhua^1,^2,^*(), SHAN Jiye², TONG Zhen^2,^*()

1. Guangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals,China National Analytical Center(Guangzhou), Guangzhou 510070, China
2. Research Institute of Materials Science, South China University of Technology, Guangzhou 510640, China

Received:2017-01-23 Online:2017-10-10 Published:2017-09-05
Contact: HU Jianhua,TONG Zhen E-mail:fox7709@126.com;mcztong@scut.edu.cn
Supported by:
† Supported by the Joint Fund of the National Natural Science Foundation of China and the Natural Science Foundation of Guangdong Province, China(No.U1201243) and the Foundation for the Talents of the Guangdong Academy of Sciences, China(No.2017GDASCX-0826)

摘要/Abstract

摘要：

讨论了添加量为1%(Per hundreds of resin)的咪唑改性的氧化石墨烯(GO-IPDI-MZ)对磷质量分数为1.5%的环氧树脂体系(1.5P-D-U-EMI)固化的影响. 差示扫描量热法(DSC)研究结果表明, 当GO-IPDI-MZ添加量为1%时不会改变1.5P-D-U-EMI的非等温自催化固化反应特征. 添加1% GO-IPDI-MZ的磷质量分数为1.5%的环氧树脂(1.5P-D-GOM-1)的固化起始温度(T_onset)和峰顶温度(T_p)均比1.5P-D-U-EMI体系低, 而总的固化热(ΔH)比1.5P-D-U-EMI体系高. 说明GO-IPDI-MZ添加量为1%时, 对环氧体系起到一定的促进固化和共固化作用. 等温DSC分析表明, 在固化反应后期, 体系出现了玻璃化转变现象, 在此阶段, 含扩散控制因子的Kamal模型预测结果与实验结果吻合较好. GO-IPDI-MZ的加入使固化反应相对均匀地进行, 对固化反应会产生促进和共固化作用.

关键词: 咪唑改性氧化石墨烯, 阻燃环氧, 固化动力学, 共固化, 差示扫描量热法

Abstract:

The curing kinetics of a flame-retardant epoxy resin(1.5P-D-U-EMI) containing 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide(DOPO) with imidazole grafting graphene oxide(GO-IPDI-MZ) was investigated by differential scanning calorimetry. The non-isothermal autocatalysis curing mechanism of 1.5P-D-U-EMI was not changed by adding 1% of GO-IPDI-MZ. T_onset and T_p of the flame-retardant epoxy resin with 1 Phr of GO-IPDI-MZ(1.5P-D-GOM-1) were decreased compared with those of 1.5P-D-U-EMI, and the total curing heat ΔH of 1.5P-D-GOM-1 was higher than that of 1.5P-D-U-EMI. 1% of GO-IPDI-MZ plays a catalytic and co-curing action on the epoxy system. The phenomenon of diffusion control was observed at the later stage of isothermal curing, especially at low temperatures. The Kamal-Sourour model modified with diffusion expressed the observed reaction rate curves fairly well. The curing reaction became steady and uniform by introducing GO-IPDI-MZ.

Key words: Imidazole grafting graphene oxide, Flame retardant epoxy, Curing kinetics, Catalytic and co-curing action, Differential scanning calorimetry

中图分类号:

O631
O643.1

TrendMD:

胡建华, 单继业, 童真. 咪唑改性氧化石墨烯对阻燃环氧固化动力学的促进作用. 高等学校化学学报, 2017, 38(10): 1906.

HU Jianhua, SHAN Jiye, TONG Zhen. Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide^†. Chem. J. Chinese Universities, 2017, 38(10): 1906.

图/表 12

Scheme 1 Structures of DGEBA, 11DB07, DICY, U-52 and EMI-2,4

Fig.1 TG and DTG thermograms of 1.5P-D-GOM-x with indicated x(A) and non-isothermal DSC thermograms of curing reaction for 1.5P-D-GOM-x systems(B)

Table 1 Parameters from the non-isothermal curing reaction thermograms of 1.5P-D-U-GOM-x(10 ℃/min)

Sample	T_onset/℃	T_p/℃	T_end/℃	ΔH/(J·g^-1)	ΔH/(kJ·mol^-1 epoxide)
1.5P-D-U-EMI	133.3	148.9	179.7	327.9	87.7
1.5P-D-GOM-0.25	130.3	146.0	176.8	331.2	88.8
1.5P-D-GOM-0.5	128.9	143.8	174.5	364.1	97.9
1.5P-D-GOM-0.75	126.9	142.6	173.4	374.0	100.7
1.5P-D-GOM-1	120.2	140.7	167.0	397.7	107.4
1.5P-D-GOM-1.25	124.7	141.5	167.5	390.2	105.5

Fig.2 Non-isothermal DSC thermograms at indicated heating rates for the curing reaction of 1.5P-D-GOM-1(a) compared with that of 1.5P-D-U-EMI(b) Heating rate/(℃·min-1): (A) 2.5; (B) 5; (C) 10; (D) 15.

Fig.3 Conversion α of 1.5P-D-GOM-1(a—d) and 1.5P-D-U-EMI(e—h) systems plotted as a function of temperature during the non-isothermal curing at indicated heating ratesHeating rate/(℃·min-1): a,e. 2.5; b,f. 5; c,g. 10; d,h. 15.

Fig.4 Kissinger plot of -ln(β/Tp2) vs. l/Tpa. 1.5P-D-U-EMI; b. 1.5P-D-GOM-1.

Table 2 Parameters for the non-isothermal curing reaction thermograms of 1.5P-D-GOM-1 and 1.5P-D-U-EMI systems*

System	β/(℃·min^-1)	T_onset/℃	T_p/℃	ΔH/(J·g^-1)
1.5P-D-U-EMI	2.5	119.5	130.9	327.2
	5	125.7	140.2	327.7
	10	133.3	148.9	327.9
	15	142.1	158.6	328.3
1.5P-D-GOM-1	2.5	114.1	128.8	397.5
	5	120.2	135.7	392.2
	10	132.0	147.9	397.7
	15	140.7	157.2	398.4

Fig.5 Conversion α for 1.5P-D-GOM-1 as a function of curing time at different isothermal temperaturesTemperature/℃: a. 110; b. 120; c. 130; d. 140; e. 150.

Table 3 Maximum conversion αT of the isothermal curing for the 1.5P-D-GOM-1 and 1.5P-D-U-EMI systems

System	α_T
System	110 ℃	120 ℃	130 ℃	140 ℃	150 ℃
1.5P-D-U-EMI	0.727	0.845	0.906	0.958	0.981
1.5P-D-GOM-1	0.790	0.846	0.907	0.980	0.998

Fig.6 Comparison of Kamal model(a), the diffusion factor modified Kamal model(b) and experimental data(c) for the isothermal curing of 1.5P-D-GOM-1 Temperature of curing/℃: (A)110; (B) 120; (C) 130; (D) 140; (E) 150.

Table 4 Kinetic parameters of the autocatalytic model for isothermal curing

T/℃	10⁴k₁/s^-1	10³k₂/s^-1	m	n	α_c	C
110	0.84	2.79	0.918	2.18	0.66	68.2
120	1.65	4.72	0.766	2.04	0.74	76.4
130	2.78	6.65	0.733	1.81	0.82	84.6
140	4.29	11.00	0.658	1.68	0.90	92.3
150	8.10	17.40	0.625	1.49	0.98	104.8

Fig.7 Arrhenius plots of lnk1(a) and lnk2(b) vs. 1/T

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咪唑改性氧化石墨烯对阻燃环氧固化动力学的促进作用

Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide^†

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咪唑改性氧化石墨烯对阻燃环氧固化动力学的促进作用

Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide†

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Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide^†