Synthesis and Properties of Polyurethane Containing Polypeptide from Silk Fibroin

doi:10.19894/j.issn.1000-0518.240123

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (10): 1425-1435.DOI: 10.19894/j.issn.1000-0518.240123

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Synthesis and Properties of Polyurethane Containing Polypeptide from Silk Fibroin

Yun HONG¹^,², Xiao-Ye MA¹, Jing-Wei HOU¹^,², Ding-Xiao JIANG¹^,², Chuan-Qing KANG¹^,²()

^1.CAS 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 230022，China

Received:2024-04-15 Accepted:2024-08-23 Published:2024-10-01 Online:2024-10-29
Contact: Chuan-Qing KANG
About author:kangcq@ciac.ac.cn
Supported by:
the Natural Science Foundation of Jilin Province-Major Program for the State Key Laboratory(SKL202302036)

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Abstract

Abstract:

Silk fibroins have excellent mechanical properties due to their special structure. A variety of diamino chain extenders containing Gly-Ala-Gly-Ala （GAGA） sequence peptides and a series of modified polyurethanes were prepared. The addition of the tetrapeptide-like structure to the backbone improved the ratio of hydrogen bonds of the modified polyurethane， which resulted in a significant increase in mechanical properties with the strain at break increasing from 29.3 to 50.9 MPa. Besides， the shape memory performance of modified polyurethane was also improved with the deformation retention increasing from 74.3% to 100%. Notably， tetrapeptide content positively correlated with the mechanical property and shape memory performance improvements. Additionally， modified polyurethane containing tetrapeptide-like chain extender also had excellent recyclability， thermal stability and hydrolysis stability under physiological conditions， which can be used in various fields and recycled multiple times.

Key words: Silk fibroin, Polyurethane, Mechanical property, Shape memory performance, Recyclability

CLC Number:

O633.4

Yun HONG, Xiao-Ye MA, Jing-Wei HOU, Ding-Xiao JIANG, Chuan-Qing KANG. Synthesis and Properties of Polyurethane Containing Polypeptide from Silk Fibroin[J]. Chinese Journal of Applied Chemistry, 2024, 41(10): 1425-1435.

Figures/Tables 12

Fig.1 Synthetic route of tetrapeptide-derived chain extenders

Fig.2 Synthetic route of polyurethane containing tetrapeptide-derived chain extenders

Fig.3 FT-IR spectra of the polyurethanes

Fig.4 Deconvolution FT-IR spectra and results of absorption peaks at 1600 ~1800 cm-1 （RHB： ratio of hydrogen bonds）

Table 1 Relative molecular mass of the polyurethanes

	10^-3M_p	10^-3M_n	10^-3M_w	10^-3M_z	10^-3M_z+1	10^-3M_v	PDI
C6/1	116	93	426	1 736	3 344	329	4.57
C6/2	183	68	358	1 052	1 936	294	5.28
SC2	107	45	179	515	1 113	150	4.02
DC2	92	46	226	1 007	2 418	177	4.86
DC6	130	57	369	1 689	3 873	282	6.45

Fig.5 Stress-strain curves of the polyurethanes

Fig.6 The process of ‘Shape coding-Shape memory-Shape recovery’ （A） and plots of deformation recovery ratio versus time for polyurethanes （B） and the deformation retention （Rkeep） of modified polyurethanes at 0 ℃ for 10 min （C）

Fig.7 Recycle of the polyurethanes （A） and stress-strain curves of the polyurethanes before and after recycling （B）

Fig.8 TGA （A） and DSC （B） curves of the polyurethanes

Table 2 Characteristic degradation temperatures and glass transition temperature （Tg） of the polyurethanes

	T_5% /℃	T_10%/℃	T_max/℃	Residual/%	T_g/℃
C6/1	226.9	239.0	274.1	5.7	-47.77
C6/2	237.1	250.4	295.8	2.7	-47.97
SC2	258.4	276.5	325.2	5.1	-46.61
DC2	257.2	269.2	336.0	2.8	-44.85
DC6	283.2	302.4	357.6	3.1	-46.02

Fig.9 Degradation curves of polyurethanes in PBS solution

Fig.10 Degradation curves of the polyurethanes in lipase solution

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Synthesis and Properties of Polyurethane Containing Polypeptide from Silk Fibroin

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