深圳大学学报理工版

以环氧树脂作为囊芯材料,以三乙烯四胺为固化剂,采用界面聚合法制备一种在环氧树脂液滴表面形成交联结构环氧树脂囊壁包覆环氧树脂液芯的自修复微胶囊. 设计L9(34)正交试验,研究乳化剂用量、固化剂用量、固化温度及固化剂滴加速率对环氧树脂微胶囊囊芯含量和储存期的影响. 采用扫描电镜和广角静态动态同步激光散射仪分别对微胶囊表面形貌、粒径大小及分布情况进行表征,采用傅里叶变换红外光谱和热失重分析仪分别研究环氧树脂微胶囊囊壁的反应机理及环氧树脂微胶囊热稳定性. 实验表明,乳化剂和固化剂的质量分数均为1.2%,固化剂滴加速率为1.2 g/h,固化温度为50 ℃时,制得的微胶囊呈规则球形,表面致密性及分散性好、热稳定性佳; 囊芯的质量分数为82.3%,平均粒径为275.3 μm,这种环氧树脂微胶囊的化学稳定性较差,在室温放置12 d后囊芯的质量分数下降2.0%. 通过万能电子拉力机对质量分数为2.0% 的200～300 μm微胶囊的环氧树脂复合材料进行损伤,经修复后测得修复率为67.04%.

Self-healing epoxy resin microcapsules are prepared by interfacial polymerization, in which the core materials are epoxy resin, the wall materials are constructed with triethylenetetramine(TETA)and the epoxy resin. The orthogonal experiments L9(34)are designed to investigate the influence of emulsifier dosage, hardener dosage, curing temperature and hardener adding rate on the core content and storage life of epoxy resin microcapsule. Scanning electron microscope and static dynamic wide angle laser light scattering instrument synchronization are used to characterize surface topography, particle size and distribution. Fourier transform infrared spectroscopy and thermo-gravimetric analyzer are used to study reaction mechanism of the microcapsule wall materials and thermal stability of the microcapsules, respectively. The results indicate that when the dosage of emulsifier is 1.2%, the dosage of hardener is 1.2%, the hardener droplets adding rate is 1.2 g/h and the curing temperature is 50 °C, the microcapsules prepared are spherical in shape with good surface compactness, dispersibility and thermal stability and the capsule core content is 82.3% and the average particle size is 275.3 μm. However, this type of epoxy resin microcapsule has relatively poor chemical stability. The core content decreases by 2.0% after 12 d storedat room temperature. After epoxy resin composite doped with 2.0% mass fraction of 200～300 μm microcapsules is damaged by the tensile testing machine, their repair rate is 67.04%.

引言
1 实验
2 结果与讨论
3 结论

图1 环氧树脂与三乙烯四胺反应前后的红外光谱<br/>Fig.1 FTIR spectra of epoxy resin

图1 环氧树脂与三乙烯四胺反应前后的红外光谱
Fig.1 FTIR spectra of epoxy resin

图2 反应过程中环氧树脂相对光密度的变化<br/>Fig.2 Changes in relative absorbance of epoxy resin during the reaction

图2 反应过程中环氧树脂相对光密度的变化
Fig.2 Changes in relative absorbance of epoxy resin during the reaction

图3 反应过程中官能团反应程度的变化<br/>Fig.3 Changes in extent of reaction of epoxy resin during the reaction

图3 反应过程中官能团反应程度的变化
Fig.3 Changes in extent of reaction of epoxy resin during the reaction

表1 伯胺、仲胺和环氧官能团相对光密度的变化<br/>Table 1 Comparison of FTIR bands of primary amine and epoxy

表1 伯胺、仲胺和环氧官能团相对光密度的变化
Table 1 Comparison of FTIR bands of primary amine and epoxy

表2 正交实验因素与水平<br/>Table 2 Factors and levels of L9(34)for epoxy microcapsules

表2 正交实验因素与水平
Table 2 Factors and levels of L9(34)for epoxy microcapsules

表3 环氧树脂微胶囊制备工艺正交设计及实验结果<br/>Table 3 The condition and results of orthodoxy experiment L9(34)for epoxy microcapsules

表3 环氧树脂微胶囊制备工艺正交设计及实验结果
Table 3 The condition and results of orthodoxy experiment L9(34)for epoxy microcapsules

图4 环氧树脂微胶囊囊芯含量及囊芯环氧基反应程度随储存时间的变化<br/>Fig.4 Changes of the core content and the reaction degree of epoxy groups in various experimentals

图4 环氧树脂微胶囊囊芯含量及囊芯环氧基反应程度随储存时间的变化
Fig.4 Changes of the core content and the reaction degree of epoxy groups in various experimentals

图5 微胶囊粒径分布<br/>Fig.5 Particle size distributions of microcapsules

图5 微胶囊粒径分布
Fig.5 Particle size distributions of microcapsules

图6 通过SEM观察环氧树脂微胶囊表面形貌<br/>Fig.6 SEM micrographs of microcapsules

图6 通过SEM观察环氧树脂微胶囊表面形貌
Fig.6 SEM micrographs of microcapsules

图7 环氧树脂与环氧树脂微胶囊热失重曲线<br/>Fig.7 TGA curve of epoxy resin and epoxy microcapsules

图7 环氧树脂与环氧树脂微胶囊热失重曲线
Fig.7 TGA curve of epoxy resin and epoxy microcapsules

图8 环氧树脂微胶囊囊壁表面的红外光谱<br/>Fig.8 FTIR spectra of E-51 microcapsules surface

图8 环氧树脂微胶囊囊壁表面的红外光谱
Fig.8 FTIR spectra of E-51 microcapsules surface

$图9 通过SEM观察环氧树脂微胶囊与环氧树脂基体结合情况<br/>Fig.9 The fractured surface for the epoxy microcapsules embedded into epoxy matrix$

图9 通过SEM观察环氧树脂微胶囊与环氧树脂基体结合情况
Fig.9 The fractured surface for the epoxy microcapsules embedded into epoxy matrix

图10 环氧树脂微胶囊用量10%的拉伸修复性能<br/>Fig.10 healing performance of tension in epoxy resin microcapsules content 10%

图10 环氧树脂微胶囊用量10%的拉伸修复性能
Fig.10 healing performance of tension in epoxy resin microcapsules content 10%

图11 通过SEM观察微胶囊修复机理<br/>Fig.11 Observation of microcapsule repair mechanism

图11 通过SEM观察微胶囊修复机理
Fig.11 Observation of microcapsule repair mechanism

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