基于多重可逆作用的自修复聚氨酯弹性体的制备及性能

doi:10.7503/cjcu20190454

摘要/Abstract

摘要：

在聚氨酯主链上引入可逆二硫键, 同时使用硼酸构建的硼酸酯键作为可逆交联点, 使聚氨酯内部形成交联网络结构, 制备了一种兼具高强度、高韧性及高修复效率的自修复聚氨酯弹性体. 红外光谱、动态力学分析、力学测试、电子显微镜及修复测试结果表明, 制备的自修复聚氨酯具有硬而韧的特性, 原样强度高达23.3 MPa, 断裂伸长率可达1177%, 并且修复条件温和, 剪断拼接的试样经60 ℃, 24 h修复后可恢复99%的原样强度, 且该修复过程可重复多次进行. 此外, 该材料还具有多通道修复特性, 通过热修复或水辅助热修复的方式均可实现材料的修复, 并且水辅助热修复速率更快.

关键词: 多通道自修复, 聚氨酯, 多重可逆作用, 二硫键, 硼酸酯

Abstract:

Self-healing materials received widely concerns because of its ability for prolonging the service life of materials and fulfilling the need for sustainable development in recent years. To solve the problem that self-healing materials can’t do both well in self-healing property and mechanical property, we prepared a self-healing polyurethane elastomer with high strength, high toughness and high repair efficiency in this paper, on the basis of the designability of polyurethanes, we introduced disulfide bond to the polyurethane main chainis and used boric acid ester bond constructed using boric acid as a reversible cross-linking point to form the cross-linked network structure. The materials was characterized by infrared spectroscopy, dynamic mechanical analysis, mechanical test, electron microscope and self-healing test. The results show that the self-healing polyurethane has the characteristics of hard and tough, which the strength of the original sample has 23.3 MPa, the elongation at break can reach 11.77%, and can self-heal at a mild conditions. After repairing at 60 ℃ for 24 h, the original strength of the sample can be restored to 99%, and the self-healing process can be repeated many times. In addition, the material has the characteristics of multi-channel self-healing, which can be repaired by means of thermal self-healing or water-assisted thermal self-healing, and the latter is faster.

Key words: Multi-channel self-healing, Polyurethane, Multiple reversible action, Disulfide bond, Boronic ester

中图分类号:

O633

TrendMD:

盛叶明,程波,卢珣. 基于多重可逆作用的自修复聚氨酯弹性体的制备及性能. 高等学校化学学报, 2020, 41(3): 572.

SHENG Yeming,CHENG Bo,LU Xun. Research on Self-healing Polypolyurethane Elastomer Based on Multiple Reversible Action ^†. Chem. J. Chinese Universities, 2020, 41(3): 572.

图/表 16

Scheme 1 Synthesis of IP-PBA

Scheme 2 Synthesis of IP-DTDA-BA

Table 1 Composition of raw materials for synthesis of polyurethane elastomers

Sample	n(IPDI)/mol	n(PBA-2000)/mol	n(DTDA)/mol	n(MDA)/mol	n(BA)/mol	n(TMP)/mol
IP-DTDA-BA	0.02	0.01	0.0048	0	0.0048	0
IP-DTDA-TMP	0.02	0.01	0.0048	0	0	0.0048
IP-MDA-BA	0.02	0.01	0	0.0048	0.0048	0
IP-MDA-TMP	0.02	0.01	0	0.0048	0	0.0048

Fig.1 FTIR spectra of prepolymerization reaction(A) and cross-linking reaction and extension reaction(B) (A) a. PBA-2000; b. IPDI; c. IP-PBA. (B) a. BA; b. IP-PBA; c. IP-DTDA-BA.

Fig.2 Stress-strain curves of IP-DTDA-BA sampleat different healing times Healing time/h: a. 0.5; b. 1; c. 2; d. 4; e. 6; f. 12; g. 24; h. pristine.

Fig.3 Optical microscopes of different crack healing states of IP-DTDA-BA at 60 ℃ (A) Original. Healing time/h: (B) 0.5; (C) 1; (D) 2; (E) 4; (F) 6; (G) 12; (H) 24.

Table 2 Composition of raw materials for synthesis of IP-DTDA-BA with different chain expansion ratio of DTDA/BA

n(DTDA/BA)/n(IP-DTDA-BA)	n(IPDI)/mol	n(PBA-2000)/mol	n(DTDA)/mol	n(BA)/mol
0/1	0.02	0.01	0	0.008
0.2/0.8	0.02	0.01	0.0024	0.0064
0.4/0.6	0.02	0.01	0.0048	0.0048
0.5/0.5	0.02	0.01	0.006	0.004
0.6/0.4	0.02	0.01	0.0072	0.0032
0.8/0.2	0.02	0.01	0.0096	0.0016
1/0	0.02	0.01	0.012	0

Fig.4 Self-healing properties of IP-DTDA-BA with different chain expansion ratio of DTDA/BA a. Stress; b. strain.

Table 3 Summary of IP-DTDA-BA with different chain expansion ratios of DTDA/BA

n(DTDA)/n(BA)	Original		Healed
n(DTDA)/n(BA)	Stress/MPa	Strain(%)	Stress/MPa	Strain(%)
0/1	15.8±0.6	1208±62	10.9±0.4	929±40
0.2/0.8	25.6±0.8	1354±64	21.3±0.6	1103±46
0.4/0.6	23.3±0.6	1177±56	23.2±0.6	950±42
0.5/0.5	17.9±0.5	774±36	17.2±0.5	684±36
0.6/0.4	11.4±0.3	819±36	11.3±0.3	766±32
0.8/0.2	10.9±0.3	548±22	10.9±0.3	502±20
1/0	12.6±0.3	786±37	12.5±0.3	782±36

Table 4 Healing efficiency of IP-DTDA-BA in different healing conditions

Healing condition	Stress/MPa	Healing efficiency(%)	Strain(%)	Strain healing efficiency(%)	Healing time/h
60 ℃	23.2±0.6	99	950±42	81	24
60 ℃, wetting	23.2±0.5	99	1206±48	100	12

Fig.5 Self-healing performance of IP-DTDA-BA under different repair conditions a. Pristine; b. 60 ℃, 24 h; c. 60 ℃, wetting, 12 h.

Scheme 3 Self-healing mechanism diagram of IP-DTDA-BA

Fig.6 FTIR spectra of different polyurethane elastomer a. IP-MDA-TMP; b. IP-DTDA-TMP; c. IP-MDA-BA; d. IP-DTDA-BA.

Fig.7 Line chart of self-healing properties, stress of original and stress of healed of IP-DTDA-BA(a), IP-DTDA-TMP(b), IP-MDA-BA(c) and IP-MDA-TMP(d)

Fig.8 Activation energy characterization of polyurethane elastomer with different kinds of chain extender (A) DMA spectrogram; (B) E' and E″ values for IP-DTDA-BA at 60 ℃; (C) lnf-103 T-1 curve; (D) histogram ofmain transition activation energy(Ea).

Fig.9 Cyclic tensile(A, B) and lag analysis(C, D)of IP-DTDA-BA(A, C) and IP-MDA-TMP(B, D)

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