Supporting information
支持信息

Synergistic cross-linking strategy with oxime-carbamate and hydrogen bonding arrays for excellent damage self-healing and reprocess ability of thermoset polyurethanes
与肟-氨基甲酸酯和氢键阵列的协同交联策略，可实现热固性聚氨酯出色的损伤、自修复和再加工能力

Pengwu Xu ^a*, Ning Ding ^a, Hong Wang ^a, Jieyu Guan ^a, Yirui Shen ^b, Deyu Niu ^a, Weijun Yang ^a, Piming Ma ^a*
徐鹏武 ^a*， 丁宁 ^a， 王宏 ^a， 关洁玉 ^a， 沈逸瑞 ^b， 牛德玉 ^a， 杨伟军 ^a， 马碧明 ^a*

^a The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, China
^a 中国无 214122 锡市蠡湖路 1800 号江南大学化学与材料工程学院， 合成与生物胶体教育部重点实验室

^b School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, Zhejiang, China
^b 宁波工业大学材料与化学工程学院，中国 315211

Corresponding email: pengwuxu@jiangnan.edu.cn; p.ma@jiangnan.edu.cn
对应邮箱：pengwuxu@jiangnan.edu.cn; p.ma@jiangnan.edu.cn

General characterization
一般特征

The chemical structure of time-gradient PCL-DOU during the synthesis was characterized using a Fourier Transform Infrared Spectrometer (Nicolet 6700, Thermo Fisher Scientific, USA). The measurements were conducted in the attenuated total reflectance (ATR) mode, with a scanning range of 400-4000 cm⁻¹. Each sample for each time interval was scanned 64 times at a resolution of 2 cm⁻¹.
使用傅里叶变换红外光谱仪 （Nicolet 6700，Thermo Fisher Scientific，美国） 表征合成过程中时间梯度 PCL-DOU 的化学结构。测量在衰减全反射 （ATR） 模式下进行，扫描范围为 400-4000 cm⁻¹。每个时间间隔的每个样品以 2 cm⁻¹ 的分辨率扫描 64 次。

The thermal stability of PCL-DOU_0.3, PCL-DOU_0.5, and PCL-DOU_0.9 was analyzed using a thermogravimetric analyzer (TGA2 SF/1100, METTLER TOLEDO, Switzerland). Samples were heated from 40 °C to 600 °C at a rate of 20 °C/min under a nitrogen atmosphere.
使用热重分析仪（TGA2 SF/1100，瑞士梅特勒托利多）分析 PCL-DOU_0.3、PCL-DOU_0.5 和 PCL-DOU_0.9 的热稳定性 。在氮气气氛下，以 20 °C/min 的速率将样品从 40 °C 加热至 600 °C。

Dynamic mechanical analysis of the samples was conducted using a dynamic mechanical analyzer (TA, DMA850) in a film tensile mode. The samples were heated from -80 °C to 60 °C at a rate of 3 °C/min, with a frequency of 1 Hz and tested under a preload of 0.1%. The storage modulus (E') and the peak temperature of the loss factor (tan δ) were recorded, with the peak corresponding to the glass transition temperature (T_g). For the stress relaxation test, a pre-tension of 0.01 N and a constant strain of 1% were applied. Once the furnace reached the set temperature, the sample was relaxed for 10 minutes, and the relaxation modulus was recorded.
在薄膜拉伸模式下使用动态机械分析仪 （TA， DMA850） 对样品进行动态力学分析。将样品以 3 °C/min 的速率从 -80 °C 加热到 60 °C，频率为 1 Hz，并在 0.1% 的预载荷下进行测试。记录储能模量 （E'） 和损失因子的峰值温度 （tan δ），峰值对应于玻璃化转变温度 （T_g）。对于应力松弛测试，施加了 0.01 N 的预张力和 1% 的恒定应变 。一旦炉子达到设定温度，将样品松弛 10 分钟，并记录松弛模量。

Temperature sweep tests were conducted using a rotational rheometer (MCR302e) with an 8 mm diameter plate, at a strain of 0.5% and a frequency of 1 Hz, over a temperature range of 30 °C to 130 °C.
使用带有 8 mm 直径板的旋转流变仪 （MCR302e） 在 30 °C 至 130 °C 的温度范围内以 0.5% 的应变和 1 Hz 的频率进行温度扫描测试。

The mechanical properties and cyclic stretching performance of the samples were tested using a universal testing machine (Instron 5967X). The tensile tests were conducted at room temperature, with samples prepared in a dumbbell shape measuring 35 mm in length, 2 mm in width, and 0.2-0.25 mm in thickness. All tensile tests were performed at a strain rate of 20 mm/min. For reprocessing performance testing, samples of PCL-DOU_0.5 were preheated in a 120 °C flat vulcanizing machine for 5 minutes, followed by hot pressing for 5 minutes before tensile testing. For self-healing performance testing, the PCL-DOU_0.5 strips were cut in half and then adhered together. After being placed at 80 °C for 4, 8, 12, and 16 hours, tensile tests were conducted.
使用万能试验机 （Instron 5967X） 测试样品的机械性能和循环拉伸性能。拉伸试验在室温下进行，制备长 35 毫米、宽 2 毫米、厚 0.2-0.25 毫米的哑铃形样品。所有拉伸试验均以 20 mm/min 的应变速率进行。为了进行再处理性能测试，PCL-DOU_0.5 在 120 °C 平面硫化机中预热 5 分钟，然后在拉伸试验前热压 5 分钟。对于自愈性能测试，PCL-DOU_0. 将 ₅ 条切成两半，然后粘在一起。 在 80 °C 下放置 4、8、12 和 16 小时后，进行拉伸试验。

Scratch self-healing tests on the sample surface were conducted using an ultra-depth-of-field 3D microscope (KEYENCE, VHX-100C). A surgical blade was used to create scratches of 0.2 μm on the sample surface. The PCL-DOU_0.5 samples were then placed at 80 °C for 4, 8, 12, and 16 hours to observe the self-healing of the scratches.
使用超景深 3D 显微镜（KEYENCE、VHX-100C）对样品表面进行划痕自修复试验。使用手术刀片在样品表面产生 0.2 μm 的划痕 。PCL-DOU_0. 然后将 ₅ 个样品在 80 °C 下放置 4、8、12 和 16 小时，以观察划痕的自愈情况。

The resistance changes of the samples under different actions (tension, bending, and compression) were tested using a digital multimeter (Keithley, DMM7510).
使用数字万用表 （Keithley， DMM7510） 测试样品在不同动作 （拉伸、弯曲和压缩） 下的电阻变化。

Table S1 Formula for PCL-DOU_x sample .
表 S1 PCL-DOU_x 样品的公式 .

Figure S1 (a) Storage modulus of PCL-DOU_0.3, PCL-DOU_0.5, PCL-DOU_0.9 versus temperature recorded by DMA.
图 S1 （a） DMA 记录的 PCL-DOU_0.3、PCL-DOU_0.5、PCL-DOU_0.9 的储能模量与温度的关系。

Table S2 Summary of the assignment of the deconvoluted subpeaks in the FTIR C=O absorption bands for the PCL-DOU_0.3, PCL-DOU_0.5 and PCL-DOU_0.9.
表 S2 PCL-DOU_0.3、PCL-DOU_0.5 和 PCL-DOU_0.9 的 FTIR C=O 吸收带中去卷积子峰的分配总结 。

Figure S2 Temperature-dependent FTIR spectra of the PCL-DOU_0.5 from 30 ^oC to 150 ^oC in the wavenumber range of (a) 1800-1640 cm^-1 and (b) 1640-1600 cm^-1.
图 S2：PCL-DOU_0.5 在 （a） 1800-1640 cm-1 和 （b） 1640-1600 ^cm-1 波数范围内的温度相关 FTIR 光谱，从 30 °C 到 150 ^°C。

Figure S3 Temperature-dependent curves of storage modulus of PCL-DOU_0.5.
图 S3 PCL-DOU 储能模量的温度相关曲线 _0.5.

Figure S4 FTIR spectra of (a) original PCL-DOU_0.5, (b) Stretched PCL-DOU_0.5 and (c) Recycled PCL-DOU_0.5 in the C=O stretching vibration region.
图 S4 FTIR 光谱，（a） 原始 PCL-DOU_0.5，（b） 拉伸 PCL-DOU_0.5 和 （c） C=O 拉伸振动区域中的回收 PCL-DOU_0.5。

Table S2 Summary of the assignment of the deconvoluted subpeaks in the FTIR C=O absorption bands for the original PCL-DOU_0.5, stretched PCL-DOU_0.5 and recycled PCL-DOU_0.5.
表 S2 原始 PCL-DOU_0.5、拉伸 PCL-DOU_0.5 和回收 PCL-DOU_0.5 的 FTIR C=O 吸收带中去卷积子峰的分配总结 。

Figure S5 Healing efficiencies of PCL-DOU_0.5 under different temperatures
图 S5 不同温度下 PCL-DOU_0.5 的愈合效率

Figure S6 Ashby plot of “toughness” and “tensile strength of PCL-DOU_0.5 and other oxime-carbamate-based self-healing materials reported in literatures.
图 S6 文献中报道的 PCL-DOU _0.5 和其他基于氨基甲酸酯的自修复材料的 “韧性”和“拉伸强度”的 Ashby 图 。

Table S3 Swelling ratio of PCL-DOU in DMF and THF.
表 S3 DMF 和 THF 中 PCL-DOU 的溶胀比。

Figure S7 Resistance changes before and after self-healing.
图 S7 自愈前后的阻力变化。

Figure S8 Changes in (R-R₀)/R₀ after 1200 cycles of cyclic bending.
图 S8 循环弯曲 1200 次循环后 （R-R₀）/R₀ 的变化。

Figure S9 The 3D surface shapes of PCL-DOU_0.5 with (a) scratches and (b) after 16 hours of self-healing.
图 S9 PCL-DOU_0.5 的 3D 表面形状 ，有 （a） 划痕和 （b） 自我修复 16 小时后。

Figure S10 Thermo-oxidative aging tests for PCL-DOU_0.5 at 80 °C.
图 S10 PCL-DOU_0.5 在 80 °C 下的热氧化老化试验。

Figure S11 The acid and alkali resistance tests for PCL-DOU_0.5.
图 S11 PCL-DOU_0.5 的耐酸碱性测试。

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引用：

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