Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds

doi:10.19894/j.issn.1000-0518.220226

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (2): 277-287.DOI: 10.19894/j.issn.1000-0518.220226

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Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds

Bi-Ru SHI¹^,², Hao-Hao WU¹^,²^,³, Hao-Pu XIE¹^,²^,³, Xin-Xin TIAN¹^,², Ying-Lu SUN¹^,², Xiang-Dong LIU¹(), Yu-Ming YANG¹^,²()

^1.Key Laboratory of High-Performance Synthetic Rubber and Its Composite Materials，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.University of Science and Technology of China，Hefei 230026，China
^3.Xi'an Northern Hui-An Chemical Industry Co. Ltd. ，Xi'an 710302，China

Received:2022-06-27 Accepted:2022-11-24 Published:2023-02-01 Online:2023-02-27
Contact: Xiang-Dong LIU,Yu-Ming YANG
About author:ymyang@ciac.ac.cn； liuxiangdong@ciac.ac.cn
Supported by:
the National Natural Science Foundation of China(22175171)

Abstract

Abstract:

DA diol containing Diels-Alder （DA） bond is firstly prepared by one-step method. HDI is then used to terminate Poly-tetrahydrofuran （PTMG-2000） and DA diol. Finally， 1，1，1-tris （hydroxymethyl） propane （TMP） reacts with the NCO-end products to form a crosslinked polyurethane material （DPU）. The reversibility and the excellent thermal properties of DA structure in DPU is successfully detected. The DA reverse reaction （r-DA） temperature is proven to be 135 ℃. DPU-Ⅳ with the highest content of DA bond has the highest self-healing efficiency of 89.0% along DPU. DPU-Ⅳ and DPU-Ⅳ both show excellent adhesive properties， DPU-Ⅲ possesses great matrix tolerance and DPU-Ⅳ has the ability of repeated bonding which could be used as repeated PU adhesive.

Key words: Diels-alder bonds, Cross-linked polyurethane, Self-healing adhesive, High shear strength

CLC Number:

O631

Bi-Ru SHI, Hao-Hao WU, Hao-Pu XIE, Xin-Xin TIAN, Ying-Lu SUN, Xiang-Dong LIU, Yu-Ming YANG. Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds[J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 277-287.

Figures/Tables 15

Fig.1 Synthesis route of m-A， m-B and DPU

Table 1 Ingredients for DPU synthesis

Sample	m-A		m-B		n（TMP）/mmol	w（DA diol）/ %
Sample	n（HDI）/mmol	n（DA diol）/mmol	n（HDI）/mmol	n（PTMG-2000）/mmol	n（TMP）/mmol	w（DA diol）/ %
DPU-?Ⅰ	4	2	16	8	6.67	5.42
DPU-?Ⅱ	8	4	12	6		12.62
DPU-?Ⅲ	12	6	8	4		22.65
DPU-Ⅳ	16	8	4	2		28.08

Fig.2 FT-IR spectra of （A） DA diol， BMI and FA during the synthetic process of DA diol，（B） m-A、m-B and DPU-Ⅲ during the synthetic process of DPU-Ⅲ， and （C） DPU with different composition

Fig.3 （A） TG，（B） DTG and （C） DSC curves of DPU

Fig.4 （A） 1H NMR and FT-IR spectra of （B） —C—H connected to CC around 694 cm-1 and （C） specified peak of DA abduct around 827 cm-1

Fig.5 Proofs for cross-linked structure and dynamic reversibility of DPU-ⅢNote： A. Original samples； B. Samples immersed in DMF at room temperature； C. Samples heated at 75 ℃ for 12 h； D. Samples heated at 135 ℃ for 30 min； E. Samples heated at 75 ℃ for 12 h； F. Samples heated at 135 ℃ for 30 min； G. Samples heated at 75 ℃ for 12 h

Fig.6 Self-healing behavior of scratches on DPU-Ⅲ filmsNote： A. Origin state； B. 80 ℃， 30 min； C. 100 ℃， 30 min； D. 120 ℃， 30 min； Scratches 2： E. Origin state； F. 135 ℃， 5 min

Fig.7 Strain-stress curves of DPU

Table 2 Mechanical properties of original DPU

Sample	Tensile strength/MPa	Strain/%	Young's modulus/MPa	Toughness/（MJ·m^-3）
DPU-Ⅰ	28.45±1.64	948±174	4.06±0.51	81.30±4.92
DPU-Ⅱ	30.61±2.15	855±141	6.97±1.06	96.92±5.49
DPU-Ⅲ	39.43±3.06	566±119	26.7±4.28	108.73±7.61
DPU-Ⅳ	27.15±2.91	203±85	391±34.1	45.06±3.19

Table 3 Mechanical properties of DPU after self-healing process

Sample	Tensile strength/MPa	Strain/%	Toughness/（MJ·m^-3）	SE/%
DPU-Ⅰ	1.04±0.29	117±27	0.781±0.14	3.66
DPU-Ⅱ	2.71±0.67	162±31	2.48±0.58	8.85
DPU-Ⅲ	20.99±1.95	587±96	43.6±3.77	53.2
DPU-Ⅳ	24.17±2.44	88±18	13.0±1.25	89.0

Fig.8 Adhesive properties of DPU on steel

Fig.9 Adhesive properties of DPU-Ⅲ on steel and aluminum

Fig.10 Adhesive properties of DPU-Ⅳ

Fig.11 The lap shear test progress

Fig.12 Adhesive failure caused by thermal spray gun heating. （A） 2 kg mass on one piece of steel ribbon，（B） the heat gun heats the overlap for 40 s and （C） two steel ribbons are separated

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Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds

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