基于主客体包合作用的自修复绝缘材料制备及性能

doi:10.7503/cjcu20180236

摘要/Abstract

摘要：

制备了一种能自我修复的电缆绝缘护套材料. 该材料基于主-客体分子间的相互作用, 以β-环糊精(CD)-Al₂O₃纳米粒子(NPs)为主体, 2-羟基乙基-甲基丙烯酸酯和金刚烷(HEMA-Ad)为客体, 通过主客体相互识别进行组装, 然后将组装体与HEMA、丙烯酸丁酯(BA)和聚乙烯吡咯烷硐(PVP)进行自由基共聚, 得到一种新型的PVP/p(HEMA-co-BA)自修复材料. 通过红外光谱、二维红外光谱、核磁氢谱和碳谱、动态热机械分析仪、万能拉伸试验机及超景深三维显微镜等对材料进行表征. 结果表明, 该材料中存在主-客体相互作用和氢键2种超分子作用力; PVP/p(HEMA-co-BA) 材料具有良好的热稳定性(耐热温度可达200 ℃); 20 ℃时材料的储能模量随着交联剂含量的增大而增大(最高可达432 MPa); 材料具有自修复效果(修复效率可达85.2%)且能多次自修复, 自修复效率随着交联剂含量的增加而降低.

关键词: 绝缘材料, 自修复, 主-客体包合作用, 金刚烷, β-环糊精-三氧化二铝纳米粒子

Abstract:

In order to solve the damage and crack of the insulating material during the installation and operation of the power cable, we prepared a self-healing cable insulating material PVP/p(HEMA-co-BA). This self-healing material was synthesized by the radical polymerization using HEMA, BA, PVP and a host-guest assembly, which is assembled through the interaction between the host(CD-Al₂O₃ NPs) and guest molecule(HEMA-Ad). The material was characterized by infrared spectroscopy, 2D infrared spectroscopy, ¹H NMR spectroscopy, ¹³C NMR spectroscopy, dynamic thermomechanical analyzer, universal tensile tester, and 3D ultra-depth of focus microscopy. The results show that there are two kinds of supramolecular interactions(the host-guest interaction and the hydrogen bond) in the material. The self-healing material PVP/p(HEMA-co-BA) has good thermal stability(the heat-resisting temperature can reach 200 ℃) and good insulation property. It also has property of self-healing and can self-heal for many times. The storage modulus of the material increases(up to 432 MPa) with the increase of the cross-linking agent at 20 ℃. The self-healing efficiency decreases with the cross-linking agent increases.

Key words: Insulation material, Self-healing, Host-guest cooperation, Adamantane, β-Cyclodextrin-Al₂O₃ nanoparticles

中图分类号:

O633

TrendMD:

林木松, 彭磊, 付强, 钱艺华, 陈天生, 张晟, 马晓茜. 基于主客体包合作用的自修复绝缘材料制备及性能. 高等学校化学学报, 2018, 39(11): 2572.

LIN Musong, PENG Lei, FU Qiang, QIAN Yihua, CHEN Tiansheng, ZHANG Sheng, MA Xiaoqian. Research on Self-healing Insulating Material Based on Host-guest Cooperation^†. Chem. J. Chinese Universities, 2018, 39(11): 2572.

图/表 18

Scheme 1 Preparation processes for the host-guest self-healing material

Table 1 Composition of samples for synthesis of PVP/p(CHEMA-co-BA)

Sample	V(HEMA)/mL	V(BA)/mL	m(PVP)/g	m(HEMA-Ad)/g	m(CD-Al₂O₃ NPs)/g	V(EGDMA)/μL
1	0.5	2.37	0.66	0.6	0.3	0
2	0.5	2.37	0.66	0.6	0.3	0.5
3	0.5	2.37	0.66	0.6	0.3	1
4	0.5	2.37	0.66	0.6	0.3	2
Ref.[1]	0.5	2.37	0.66	0.6	0	1
Ref.[2]	0.5	2.37	0	0.6	0.3	1

Scheme 2 Self-healing of PVP/p(HEMA-co-BA)(Ⅰ) and self-healing after adding competitive molecules(Ⅱ)

Fig.1 1H NMR(A) and 13C NMR(B) spectra of HEMA-Ad

Fig.2 1H NMR(A) and 13C NMR(B) spectra of TOS-CD

Fig.3 Infrared spectra of Al2O3 NPs(a), CD-Al2O3 NPs(b) and TOS-CD(c)

Fig.4 TG analysis of Al2O3 NPs(a), NH2-Al2O3 NPs(b) and CD-Al2O3(c)

Fig.5 TEM image of CD-Al2O3 NPs

Fig.6 Infrared spectra of PVP(a) and samples 1(b) and 3(c)

Fig.7 Two-dimensional infrared spectra of material(A) Synchronous infrared signal; (B) asynchronous infrared signal.

Fig.8 TEM image of CD-Al2O3 NPs in material

Table 2 Dynamic thermo-mechanical analysis of PVP/p(HEMA-co-BA)

Sample	Storage modulus/MPa			$r E' 1$		T_g/℃
Sample	20 ℃	50 ℃	90 ℃	E'_{20 ℃}/E'_{50 ℃}	E'_{50 ℃}/E'_{90 ℃}	T_g/℃
2	300.8	48.83	1.127	6.16	43.32	78.1
3	399.0	79.13	2.313	5.04	34.21	81.3
4	432.3	64.78	1.030	6.67	62.08	95.8

Table 2 Dynamic thermo-mechanical analysis of PVP/p(HEMA-co-BA)

Sample	Storage modulus/MPa			$r E' 1$		T_g/℃
Sample	20 ℃	50 ℃	90 ℃	E'_{20 ℃}/E'_{50 ℃}	E'_{50 ℃}/E'_{90 ℃}	T_g/℃
2	300.8	48.83	1.127	6.16	43.32	78.1
3	399.0	79.13	2.313	5.04	34.21	81.3
4	432.3	64.78	1.030	6.67	62.08	95.8

Fig.9 tanδ-temperature curve of PVP/p(HEMA-co-BA) materials

Fig.10 TG curve of sample 3

Table 3 Insulating properties of PVP/p(HEMA-co-BA)

Condition	Volume resistivity/ (Ω·m)	Surface resistivity/Ω	Relative permittivity	AC electrical strength (inoil)/(MV·m^-1)	DC electrical strength (in oil)/(MV·m^-1)
Normal	3.2×10⁷	7.2×10^10[30]	21.7	12.5^[31]	14.7^[31]
Drying for 2h at 50 ℃, vacuum	4.1×10⁸	3.5×10^10[30]	18.7

Scheme 3 Self-healing process of the material(Ⅰ) and 3D ultra-depth of focus figures of material before and after self-healing(Ⅱ)

Table 4 Mechanical properties and self-healing efficiency of PVP/p(HEMA-co-BA)

Sample	E_Y/MPa	ε/(%)		σ/MPa		Self-healing efficiency, η(%)
Sample	E_Y/MPa	Before self-healing	After self-healing	Before self-healing	After self-healing	Self-healing efficiency, η(%)
1	0.36	337.65	225.33	0.612	0.519	85.2
2	7.64	173.33	24.76	0.812	0.586	72.2
3	9.42	161.39	70.66	1.452	0.987	67.98
4	15.00	98.41	29.11	2.036	1.341	65.89
Ref.[1]	9.14	158.35	0	1.431	0	0
Ref.[2]	8.53	150.23	40.37	1.128	0.413	36.61

Fig.11 Samples without CD-Al2O3 NPs(A), without PVP(B) and self-healing test of PVP/p(HEMA-co-BA) after smearing cyclodextrin solution at cutting surface(C)

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