Preparation and properties of self⁃healing waterborne polyurethane based on disulfide bonds

doi:10.19491/j.issn.1001-9278.2022.06.008

Abstract

Abstract:

A series of self?healing waterborne polyurethane materials （WPUs） was prepared using a aromatic disulfide compound， 2，2'?diaminodiphenyldisulfide （AD）， as a raw material. The resulting WPUs were characterized using FTIR spectrometer， Raman spectrometer， thermogravimetric analyzer， particle size analyzer， hot?stage polarized light microscope， and contact angle meter. Their thermal stability， surface hydrophobicity and self?healing properties were investigated together with its tensile properties and self?healing efficiency evaluated quantitatively though a tensile experiment. The results showed that AD was successfully introduced into the molecular chain of WPUs. The thermal stability of WPUs decreased gradually with an increase in AD content， and its surface hydrophobicity increased as well. The sample WPU?3 presented a static contact angle of 81.2 ° and tensile strength of 5.6 MPa. However， WPU?0 only has tensile strength of 1.1 MPa. On the other hand， WPU?1 has a tensile strain healing efficiency of 81 % after heating for 3 h under a moderate healing temperature of 80 ℃.

Key words: self?healing, waterborne polyurethane, dynamic disulfide bond, healing efficiency

CLC Number:

TQ323.8

CHEN Liang, ZHANG Pingbo, JIANG Pingping, BAO Yanmin, GAO Xuewen, XIA Jialiang. Preparation and properties of self⁃healing waterborne polyurethane based on disulfide bonds[J]. China Plastics, 2022, 36(6): 46-53.

Figures/Tables 12

样品编号	IPDI/g	PTMG/g	DMPA/g	AD/g	TEA/g	EDA/g	H₂O/g
WPU⁃0	2.22	5.90	0.43	0.00	0.32	0.05	35.72
WPU⁃1	2.22	5.14	0.40	0.24	0.30	0.05	33.44
WPU⁃2	2.22	4.47	0.37	0.45	0.28	0.05	31.44
WPU⁃3	2.22	3.69	0.35	0.69	0.26	0.05	29.10

Tab. 1. Formulation of waterborne polyurethane

Fig.1. Synthesis process of waterborne polyurethane

Fig 2. FTIR spectra of modified waterborne polyurethane coating

Fig.3. Raman spectra of WPU?1

Fig.4. Particle size distribution of modified polyurethane emulsion

Fig.5. TG curves of AD modified WPU films

样品	T_{5 %}/℃	T_{50 %}/℃	250 ℃残碳率/%	500 ℃残碳率/%
WPU⁃0	267.33	404.66	96.57	2.13
WPU⁃1	238.33	403.66	93.99	2.02
WPU⁃2	231.66	396.67	92.68	1.88
WPU⁃3	140.00	341.00	74.91	2.12

Tab.2. Thermal properties of AD modified polyurethane films

Fig.6. Stress?strain curves of modified WPU films

Fig.7. Water contact angle of modified WPU films

Fig.8. Micrographs of modified WPU magnified 50 times at 70℃ for different times

Fig.9. Photographs of WPU?1 being cut and healed at 70 ℃ for 24 h， and then magnified 50 and 100 times under the microscope and the self?healing mechanism

Fig.10. Stress?strain curves of WPU?1 at different temperature and time and its corresponding healing efficiency

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