【作者】 徐国祺；

【导师】 刘君良；

【作者基本信息】 中国林业科学研究院 ， 木材科学与技术， 2011， 博士

【摘要】 与传统的化学防腐剂相比植物源防腐剂作为一种环境友好的新型防腐剂将会成为今后研究的重要方向。开发出适用于毛竹（Phyllostachys edulis（Carr.）H.de Lehaie）防腐的植物源防腐剂可以扩大毛竹应用范围,这一研究具有重要理论意义和应用价值。本文通过对几种植物提取物抑菌性能的筛选确定樟树叶提取物为本研究的主要物质。通过对提取工艺的优化,以及与固着剂（三聚氰胺改性脲醛树脂预聚物（MFU））进行复配,将其制备成耐腐性、热稳定性好的试剂。并对其抑菌性能、耐腐性能,以及固着、腐朽机理进行研究,为植物源防腐剂的研发、应用提供科学依据。主要结果如下:（1）对樟树叶、巨尾桉叶、杉木叶、红松松针4种植物叶的水提物、苯-醇提取物的性状观察,由于溶剂的差异导致提取的活性成分差异,使同一种植物提取物随溶剂的不同,性状有明显差异。樟树叶水提取物的抑菌性能最好,确定为本文用以研究植物源防腐剂的原材料。（2）分析超临界CO₂提取和微波提取两种方法提取的樟树叶活性物质,以及两种提取方法对樟树叶中木质素、纤维素等成分影响的X射线光电子能谱（XPS）表征,确定最优提取方法为微波提取法。提取物中含有D-樟脑、石竹素、桉树醇、芳樟醇、α-松油醇、4-萜烯醇等物质。确定提取工艺为:提取温度70℃,提取时间15min,液料比12:1,提取功率500w。樟树叶提取物的提取率平均为2.514%。（3）樟树叶提取物与固着剂复配（含10%樟树叶提取物、10%MFU）。添加固着剂对于试剂的抑菌能力无显著影响,随着培养时间的延长,复配试剂的抑菌效力更持久,固着剂对樟树叶提取物的活性成分起到包覆作用,延长防治效力。复配制剂和固着剂的红外谱图整体趋势一致,没有新的特征峰出现。樟树叶提取物与固着剂复配是物理混合,没有生成新的物质。热稳定性的顺序依次为:固着剂>复配试剂>樟树叶提取物。复配后的试剂的热稳定性远远优于樟树叶提取物。采用Doyle Ozawa法计算了各试剂在各热解阶段的热解活化能,建立热解动力学模型,樟树叶提取物为197 KJ·mol^-1,复配试剂分别为210 KJ·mol^-1,468 KJ·mol^-1,固着剂分别为241 KJ·mol^-1,494 KJ·mol^-1。（4）用“满细胞法”处理竹材,前真空-0.08MPa,时间30min,加压压力为0.8MPa,保压时间2小时。复配试剂处理后的竹材内部维管束周围的薄壁细胞中有球状颗粒物质。未处理的竹材内部未发现物质存在。竹材内部的颗粒状物质是试剂经低温固化后,固着剂MFU受热缩聚形成微囊结构,将活性成分包覆于内部,有利于活性成分的缓慢释放。复配试剂处理竹材的防霉、耐腐、野外耐腐性能最好,质量损失率平均为6.07%;樟树叶提取物处理的竹材抑菌性能次之,质量损失率平均为16.39%,但是远远优于对照试材;对照试材的质量损失率平均为37.28%。复配试剂处理的竹材达到强耐腐等级,樟树叶提取物处理的竹材达到耐腐标准,对照试材为稍耐腐等级。复配试剂完全可以作为植物源防腐剂加以开发和使用。（5）维管束中后生木质部的导管是腐朽菌侵袭的主要通道,靠近维管束的薄壁细胞最容易受到侵袭,靠近竹黄的部分受腐朽菌侵袭较靠近竹青部分更严重。通过傅里叶变换红外光谱（FTIR）、XPS分析推断褐腐菌对半纤维素的分解能力强于白腐菌,白腐菌对木质素的分解能力强于对半纤维素的分解能力。复配试剂处理的竹材抵御腐朽能力更强。气相色谱/质谱联用（GC/MS）分析处理材中含有4种樟树叶提取物所具有的化合物,包括:芳樟醇、D-樟脑、α-松油醇、石竹素。推断处理材的抑菌能力可能为这几种化合物共同作用的结果。更多还原

【Abstract】 As a even more environmental friendly new protection than the chemical protection, plant-based protection will be an important research tendency in the future. Development of a plant-based protection for bamboo protection can widen their applications.The extractive of camphor leaves was determined to be the main substance studied in this research through the screening of the function of bacteriostat in ten plant extractives. The process for extraction was optimized, the extractive was mixed with MFU, and the mixed reagent was prepared with decay resistance, heat resistance effect. Aiming at founding the foundation for the plant-based bamboo protection, the function and mechanism of bacteriostat were researched. The main research findings were summarized as follows:The traits of water and benzyl-alcohol extractives stemming from camphor leaves, europhylla leaves, Chinese Fir leaves, and Korean pine leaves were observed. As the compounds of extractive were different with different solvent, and the traits of extractive were also different. The decay resistance function of camphor leaves was the best, so the extractive of camphor leaves was used as the main material for developing plant-based protection.The extractive of camphor leaves by SFE CO₂ and MAE was analyzed respectively. And the surface chemical composition and structure of treated residue was analyzed by XPS, which can forecast the effects of extract method to lignin and cellulose of camphor leaves, and the method of extract was determined. The extractives contain D-camphor, caryophyllin, encalyptole, linalool,α-terpineol, and 4-terpineol, which have an antibacterial, desinsectization, antiviral, decay resistance effect. The process for extraction was set down as: in 70℃extract 15min, and liquid-to-solid ratio was 12:1, the power of extract was 500w. The extraction efficiency of camphor leaves was 2.514%.The extractive of camphor leaves was mixed with MFU （10% extractive and 10% MFU）, the decay resistance of mixed reagent wasn’t clearly different by comparing with the extractive. But the mixed reagent had more lasting decay resistance than the extractive of camphor leaves, because the active composition of extractive was coated by MFU. The general trend of FTIR spectra for MFU was accord with the mixed reagent, and there was no new characteristic peak appeared. So the mixed was physical mixed, and the mixed reagent didn’t exist new substance. The order of heat resistance was: MFU>mixed reagent>extractive of camphor leaves. According to the pyrogenation rate equation, the dynamies parameters of samples were calculated to obtain activation energy E and the equation of samples.The optimal vacuum-pressure preservative impregnation parameters for bamboo treatment are: pre-vacuum keeping time 30min, pre-vacuum pressure -0.08Mpa, treated pressure 0.8Mpa, keeping time 2h. After treated by mixed reagent, the parenchyma cells around the vascular budles of bamboo existed ball granule. The ball granule didn’t exist in untreated bamboo. When the treated bamboo was heated, MFU polymerized. So the ball granule in bamboo was micro-capsule of mixed reagent that the active composition of extractive was coated by MFU. The structure of micro-capsule was beneficial to control release of active composition.The antimold, antistain, decay resistance effect of bamboo treated by mixed reagent was the best with the average weight lost of 6.07%; the bamboo treated by extractive was the secondary with the average weight lost of 16.39%. And the antimold, antistain, decay resistance effect of bamboo treated by extractive was far better than untreated bamboo. The average weight lost of untreated bamboo was 37.28%. The decay resistant grade of bamboo treated by mixed reagent reached to strong decay resistant, treated by extractive reached to decay resistant, the untreated reached only to slightly decay resistant. So the mixed reagent may serve as a plant-based protection to develop.The vessels were the primary path that the mycelium spread in bamboo, the parenchyma cells were destroyed badly, and the place near tabasheer was attacked hardest. Cellulose was easier decomposed by brown-rot than write-rot according to FTIR, XPS analysis, and lignin was easier decomposed by write-rot than cellulose. The decay resistant of bamboo treated by mixed reagent was strongest. The extractive of camphor leaves contained linalool, D-camphor,α-terpineol, caryophyllin by GC/MS analysis. It was concluded that the decay resistant of treated bamboo might be caused by both 4 composition.更多还原