Preparation of nano-SiO2-IPBC microcapsule and its application in mildew resistance of Hevea brasiliensis
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摘要:目的 制备一种新型纳米SiO2-IPBC微胶囊防霉剂并探究其性能，旨在提高3-碘-2-丙炔基氨基甲酸丁酯（IPBC）在木材中的固着性能和耐老化性能，使其具有长效缓释性能，拓宽其在木材防霉领域的应用范围。方法 通过溶胶–凝胶法合成的纳米SiO2粉末为囊壁，以IPBC为囊芯，采用真空共混法制备纳米SiO2-IPBC微胶囊木材防霉剂。采用傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）、热重分析（TGA）、耐光老化和缓释性能分析等方法对微胶囊进行表征；以橡胶木为研究对象，可可球二孢、黑曲霉、绿色木霉、桔青霉为被试菌种，对不同质量分数纳米SiO2-IPBC微胶囊防霉剂处理的橡胶木抑菌效力进行综合评价，获得微胶囊防霉剂的综合性能指标。结果 纳米SiO2-IPBC微胶囊呈规则球状，粒径分布在20 ~ 100 nm之间，包覆率达46.33%。微胶囊发生热失重温度为120 ~ 280 ℃；经紫外灯照射60 min仅产生轻微黄变。微胶囊在质量分数20%的乙醇水溶液中，前60 min释放速率较快，后180 min释放缓慢，240 min时释放率达50%。FTIR分析表明微胶囊有Si−OH键生成。SEM表明微胶囊除了分布于木材导管中，还大量沉积在木材纹孔内。橡胶木防霉实验结果表明：随着微胶囊防霉剂质量分数的增加，其对4种霉菌的防治效力逐渐提高，当微胶囊防霉剂的质量分数为1.25%时，其对可可球二孢、桔青霉、绿色木霉、黑曲霉的防治效力均达到最高值，分别为78.125%、75.000%、68.750%和62.750%，防治效力由强到弱的顺序为可可球二孢 > 桔青霉 > 绿色木霉 > 黑曲霉。结论 本研究制备的纳米SiO2-IPBC微胶囊新型防霉剂，改善了IPBC的耐光老化性能，并具有缓释效果。微胶囊防霉剂对于4种橡胶木常见的霉菌均有较好的抑制作用，其中对蓝变菌可可球二孢的防治效果最佳。Abstract:Objective This paper aims to prepare a new nano SiO2-IPBC microcapsule fungicide and study its characteristics, as well as improve the fixation and aging resistance of 3-iodo-2-propynyl-butyl-carbamate (IPBC) in wood, and expand its application in the field of wood mildew proof.Method Nano SiO2-IPBC microcapsules were prepared by blending IPBC and nano SiO2 particles in a vacuum, nano SiO2 prepared by sol-gel method was the capsule wall, and IPBC was the capsule core. The microcapsules were characterized by Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), UV-aging resistance, and slow-release performance. Taking Hevea brasiliensis as the research object, Botryodiplodia theobromae, Aspergillus niger, Trichoderma viride, and Penicillium citrinum as the tested strains. The comprehensive indicators were obtained from different mass fraction microcapsule-ethanol impregnated rubber wood treatments.Result Nano SiO2-IPBC microcapsules were regular spherical, with particle size distribution between 20–100 nm and coating rate of 46.33%. The temperature of the weight loss of microcapsules was 120–280 ℃. Only slight yellowing occurred after 60-min UV aging; in 20% ethanol aqueous solution, the release rate of microcapsules was fast in the first 60 min, gradually slowed down in the next 180 min, and its release rate reached 50% in 240 min. FTIR analysis showed that there were Si−OH bonds in the microcapsules. SEM showed that microcapsules were not only distributed in wood vessels, but also deposited in wood pits. The results of mildew proof experiment showed that with the increase of the mass fraction of the microcapsule fungicide, the control effect against 4 fungi had gradually improved. When the mass fraction of microcapsule fungicide increased to 1.25%, the control effect against Botryodiplodia theobromae, Aspergillus niger, Trichoderma viride and Penicillium citrinum reached the highest level, which were 78.125%, 75.000%, 68.750% and 62.750%, respectively. The order of control effect (from strong to weak) was as follows: Botryodiplodia theobromae > Penicillium citrinum > Trichoderma viride > Aspergillus niger.Conclusion The nano SiO2-IPBC microcapsules prepared in this study improve the UV aging resistance of IPBC, as well as has a slow-release effect. The microcapsule fungicide has an excellent inhibitory effect on the 4 common mildews of rubber wood and has the best control effect on Botryodiplodia theobromae.
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Keywords:
- 3-iodo-2-propynyl-butyl-carbamate (IPBC) /
- nano SiO2 /
- microcapsule /
- rubber wood /
- anti-photoaging /
- anti-mildew
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图 1 纳米SiO2（a）、纳米SiO2-IPBC微胶囊防霉剂（b）、IPBC（c）的TG-DTG曲线
Figure 1. TG-DTG curves of nano SiO2 (a), nano SiO2-IPBC microcapsule anti-mould agent (b) and IPBC (c)
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图 2 不同紫外老化时间对纳米SiO2-IPBC微胶囊和IPBC的外观影响
Figure 2. Appearance effect of UV aging on IPBC and nano SiO2-IPBC microcapsule at different time
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图 3 IPBC释放标准曲线 （a）和纳米SiO2-IPBC微胶囊防霉剂释放曲线 （b）
Figure 3. IPBC release standard curve (a) and nano SiO2-IPBC microcapsule anti-mould agent release curve (b)
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图 4 纳米SiO2-IPBC微胶囊SEM表征 （a）、微胶囊分布 （b） 和相对频率 （c）
Figure 4. SEM characterization of nano SiO2-IPBC microcapsules (a), microcapsules distribution (b) and relative frequency (c)
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图 5 纳米SiO2和纳米SiO2-IPBC微胶囊防霉剂的FTIR
Figure 5. FTIR of nano SiO2 and SiO2-IPBC microcapsule anti-mould agent
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图 6 不同质量分数防霉剂浸渍材SEM表征
Figure 6. SEM characterization of impregnated wood with different mass fraction anti-mould agents
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图 7 不同质量分数防霉剂浸渍材和未浸渍处理材红外光谱图
Figure 7. FTIR of impregnated samples of different mass fractions and unimpregnated sample
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图 8 不同质量分数防霉剂浸渍材和未浸渍处理材受霉菌感染的感染值变化
Figure 8. Changes of mildew infection value of different impregnated wood with different mass fractions of anti-mould agent and unimpregnated wood
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图 9 不同质量分数微胶囊防霉剂浸渍处理材的霉变防治效力
Figure 9. Effects of different mass fractions of microcapsule anti-mould agent on mildew control of impregnated wood
表 1 试件受霉菌表面感染值分级
Table 1 Grade of surface infection of specimen affected by mold
感染值
Infection value试件表面感染面积比例
Proportion of infection area of specimen surface0 无菌丝、无霉点 No mycelium growth and mould 1 ≤ 1/4 2 （1/4 ~ 1/2] 3 （1/2 ~ 3/4] 4 > 3/4 
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表 2 不同质量分数微胶囊防霉剂的霉菌抑菌圈平均直径
Table 2 Average diameter of inhibition zone of microcapsule anti-mould agent against different mass fractions
mm 供试菌 Tested mold 对照组
Control0.25%样品
0.25% sample0.50%样品
0.50% sample0.75%样品
0.75% sample1.00%样品
1.00% sample1.25%样品
1.25% sample可可球二孢
Botryodiplodia theobromae7.22 ± 0.13 10.97 ± 0.56 12.56 ± 0.18 29.06 ± 0.59 38.06 ± 1.26 55.38 ± 1.22 黑曲霉
Aspergillus niger7.51 ± 0.26 9.64 ± 0.48 12.22 ± 0.09 25.71 ± 1.12 28.06 ± 0.83 48.85 ± 1.17 绿色木霉
Trichoderma viride7.43 ± 0.12 10.42 ± 0.39 13.28 ± 0.73 23.42 ± 0.98 34.12 ± 1.24 50.42 ± 0.96 桔青霉
Penicillium citrinum7.94 ± 0.22 9.85 ± 0.42 15.72 ± 0.13 27.09 ± 0.67 36.81 ± 0.95 52.86 ± 1.67
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