化学学报 ›› 2008, Vol. 66 ›› Issue (1): 121-128. 上一篇    下一篇

研究论文

昆虫激素十二醇微胶囊的制备与释放行为研究

朱晓丽,顾相伶,廉洁,张志国,孔祥正*   

  1. (济南大学化学化工学院 济南 250022)
  • 投稿日期:2007-05-09 修回日期:2007-06-12 发布日期:2008-01-14
  • 通讯作者: 孔祥正

Preparation of Insect Sex Pheromone Dodecanol Containing Microcapsules and Their Controlled Release

ZHU Xiao-Li GU Xiang-Ling LIAN Jie ZHANG Zhi-Guo KONG Xiang-Zheng*   

  1. (College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022)
  • Received:2007-05-09 Revised:2007-06-12 Published:2008-01-14
  • Contact: Kong Xiang Zheng

利用昆虫雌性激素对昆虫进行干扰交配是近年来使用的一种新技术,可替代农药杀虫剂达到高选择性无毒无药灭害的目的。迄今为止的相关研究及应用技术都是使用载有昆虫激素的棉条、纸片、塑胶管等装置,以一定密度置于果园或农田。十二醇是较为简单的一个存在于多种昆虫的雌性激素中化合物。本文首次探索使用聚合物微球水分散体系将昆虫激素十二醇(C12OH)包覆在聚合物微球中,通过改变水分散体系的制备方法、复合微球壁的交联度等探讨了此类体系对C12OH的可控释放。本工作首先通过测定阿拉伯胶明胶复凝聚过程的透光率、ζ电位,确定了阿拉伯胶-明胶的重量配比为1时可达最大复凝聚。在此基础上,制备了一系列不同交联剂戊二醛含量的复合微胶囊。结果表明微胶囊壁材的交联度随交联剂量明显上升,其对C12OH的包覆率经1%戊二醛交联后即提高至未交联体系的约三倍。但进一步提高戊二醛的含量,虽然胶囊的交联度仍明显上升,但对C12OH的包覆率基本保持恒定。使用同样量的甲醛可达同样交联效果,但对C12OH的包覆率有明显提高。在恒温恒湿条件下对各胶囊的C12OH释放行为进行了表征,结果显示交联胶囊可明显提高C12OH的恒速释放时间,交联度越高,恒速释放越稳定。本工作表明通过本方法确实可以达到将昆虫激素包覆在聚合物颗粒中并达到可控释放。

关键词: 复凝聚法, 微胶囊, 交联, 昆虫激素, 可控缓释

Acacia gum (GA) and gelatin (GE) were coacervated with presence of dodecanol (C12OH) in order to prepare microcapsules with C12OH encapsulated. C12OH was chosen for the encapsulated core material in consideration of its structural similarity to authentic insect sex pheromones, which are mainly consisting of unsaturated alcohol, acetate ester and aldehyde of hydrocarbons with carbon numbers between 10 and 24. In a first step, Zeta potential and transmittance of the solution mixture of GA and GE during the coacervation were followed in order to determine the optimum ratio of GA and GE. It was observed that maximum coacervation was achieved at GA/GE weight ratio at unity. In the presence of formaldehyde or glutaraldehyde as the crosslinker of the wall materials, microcapsules were prepared at different crosslinking level. With increase of glutaraldehyde from 1% to 4% relative to total polymer mass, the crosslinking significantly increased from 27.8% to 78.5%, similar performance was seen when formaldehyde was used instead of glutaraldehyde. Particle size and size distribution data showed that particle size decreased with a narrower size distribution when crosslinking agent was increased. C12OH encapsulation by this complex coacervation was examined for capsules prepared with C/W (core/wall) ratio of 1/2. It was revealed that crosslinking could remarkably enhance C12OH encapsulation. For the microcapsules without crosslinking agent, only 16% of the added C12OH was detected encapsulated, which led to a C12OH loading of 7%. Compared with the capsules without crosslinking agent, those prepared with 1% glutaraldehyde gave capsules with increased C12OH loading up to 20%. And C12OH loading was relatively constant while the crosslinking agent varied from 1% to 4%. It was found that capsules prepared using formaldehyde produced similar crosslinking, however, a much higher C12OH loading was observed when compared with those prepared using same levels of glutaraldehyde. To investigate C12OH release from the capsules, samples were placed into an incubator with constant temperature (30℃) and relative humidity (50% RH), and taken out for C12OH examination by gas chromatography and weighing the samples. It was found that all samples manifested a three-step-release profile, i.e. a quick start followed by a constant plateau region, representing a very low release rate or stopped release, and terminated by a release increase. C12OH expressed by percentage of capsules showed that all glutaraldehyde crosslinked capsules had a higher release rates than the sample without crosslinking; and the higher the crosslinking, the lower the release rate for all crosslinked samples. This gave a longest time and the most constant release rate in the capsules done with 4% glutaraldehyde. This work indicates that release of C12OH can be well controlled through capsule structure design, this is of great importance for our on-going study on controlled release of authentic insect semiochemicasls.

Key words: Complex Coacervation, Microcapsules, Crosslinking, Insect pheromone, Controlled release