本文關(guān)鍵詞： 纖維素 功能化改性 緩控釋農(nóng)藥 抗紫外 熒光　出處：《中國農(nóng)業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：纖維素是自然界含量最為豐富的天然高分子材料,它具有良好的生物相容性和降解性,是一種非常具有潛力的石油化工產(chǎn)品的替代物。通過對纖維素進(jìn)行改性,并根據(jù)實(shí)際需求,為農(nóng)藥量身打造功能性纖維素膜材料,可以進(jìn)一步拓寬纖維素的應(yīng)用范圍。本論文制備出兩種功能性纖維素材料(抗紫外纖維素膜材料和熒光性纖維素膜材料),并研究了兩種膜材料在緩控釋農(nóng)藥上的應(yīng)用性能。(1)我們以LiCl/DMAc溶劑體系溶解微晶纖維素,以4,4'-二羥基苯甲酮(DHBP)為紫外線吸收劑,2,4-甲苯二異氰酸酯(TDI)為交聯(lián)劑,制備出具有抗紫外性能的纖維素膜材料。通過紅外和熒光譜圖對該材料的化學(xué)結(jié)構(gòu)進(jìn)行確定,并對該膜材料的力學(xué)性能、熱力學(xué)性能、抗紫外性能、親疏水性進(jìn)行探討。結(jié)果表明,DHBP的引入,為纖維素添加了抗紫外的能力。通過增加交聯(lián)劑的用量,可以提高纖維素材料的交聯(lián)度,從而對膜的力學(xué)性能、熱力學(xué)性能、抗紫外性能、親疏水性能進(jìn)行調(diào)節(jié)。(2)以上述具有抗紫外功能的改性纖維素膜為研究對象,通過紫外照射實(shí)驗(yàn),對纖維素膜的紫外吸收能力進(jìn)行表征。并在滲透擴(kuò)散池中,對改性纖維素膜的控釋性能進(jìn)行表征。結(jié)果表明,改性后的纖維素膜材料表現(xiàn)出良好的紫外線保護(hù)能力,四種生物農(nóng)藥降解很少。根據(jù)太陽光照射下的四種生物農(nóng)藥的對比實(shí)驗(yàn),可以大體估計(jì)改性纖維素膜材料可以對農(nóng)藥實(shí)現(xiàn)長效防護(hù)。通過滲透實(shí)驗(yàn),改性纖維素膜的滲透速率可以根據(jù)交聯(lián)度進(jìn)行調(diào)控,交聯(lián)度越大滲透越慢。(3)我們以熒光素和萘乙酸首先合成出熒光素二萘乙酸酯(FNE),并將其通過異佛爾酮二異氰酸酯(IPDI)接到乙基纖維素上,制備出具有熒光效應(yīng)的纖維素膜材料。根據(jù)FNE的水解實(shí)驗(yàn),發(fā)現(xiàn)其在中性條件下水解受萘乙酸濃度影響。通過對其力學(xué)性能、熱力學(xué)性能進(jìn)行測試,發(fā)現(xiàn)交聯(lián)后的纖維素膜材料力學(xué)性能和耐熱性比未交聯(lián)的更好,FNE的加入對這些性質(zhì)沒有太大影響。(4)以上述熒光性纖維素膜材料為研究對象,通過對其化學(xué)控釋、物理控釋、低濃度指示作用進(jìn)行了研究。結(jié)果表明,改性后的纖維素膜具有一定的化學(xué)釋放萘乙酸的能力;萘乙酸的滲透速率與膜兩側(cè)的濃度差相關(guān);當(dāng)萘乙酸濃度過低時(shí),改性纖維素膜的熒光開始恢復(fù),并能通過肉眼進(jìn)行觀察。本論文的研究結(jié)果表明,纖維素膜材料通過改性后可以為農(nóng)藥量身打造合適的緩控釋包膜。同時(shí),改性纖維素膜材料在光引發(fā)、發(fā)光材料等方面,也具有良好的發(fā)展前景。由于缺乏相應(yīng)的包膜技術(shù),將纖維素膜材料進(jìn)行進(jìn)一步的實(shí)際應(yīng)用,仍有待更多的研究。
[Abstract]:Cellulose is the most abundant natural polymer materials in nature, it has good biocompatibility and biological degradation, as a substitute for a potential oil chemical products. The cellulose was modified according to the actual demand for pesticides, tailored functional cellulose membrane materials, can further broaden the application the range of cellulose. This paper prepared two kinds of functional cellulose materials (UV resistant cellulose membrane materials and fluorescence of the cellulose membrane material), and study the two kinds of membrane materials in controlled release pesticide application performance. (1) we use LiCl/DMAc solvent system to dissolve cellulose, 4,4'- two hydroxy benzene ketone (DHBP) as a UV absorber, 2,4- toluene diisocyanate (TDI) as crosslinking agent, preparation of cellulose membrane material with anti UV properties. Through infrared and fluorescence spectra of chemical structure diagram of the material To determine the mechanical properties, the thermodynamic properties of membrane materials, anti UV properties, hydrophobicity were discussed. The results show that the introduction of DHBP, adding anti UV ability for cellulose. By increasing the amount of crosslinking agent, can improve the cellulose crosslinking degree, and mechanical properties of film the thermodynamic properties, anti UV properties, hydrophobic properties were adjusted. (2) the above has the function of anti ultraviolet modified cellulose membrane as the research object, through the ultraviolet irradiation experiments were characterized on cellulose membrane UV absorption capacity. And in the diffusion pool, the modified cellulose membrane controlled release properties were characterized. The results show that the modified cellulose membrane material after showing good UV protection capability, four kinds of biological pesticide degradation is few. Based on the contrast experiments of four kinds of biological pesticide under sunlight irradiation, can be modified to roughly estimate Cellulose membrane material can achieve long-term protection. Through the pesticide penetration test, penetration rate of modified cellulose membrane can be adjusted according to the degree of crosslinking crosslinking, the greater the degree of penetration is slower. (3) we first synthesized fluorescein fluorescein and NAA two naphthalene acetate (FNE), and then by isophorone diisocyanate (IPDI) from ethyl cellulose, preparation of cellulose membrane materials with fluorescent effect. According to the hydrolysis experiments FNE, found in the neutral condition by the NAA concentration. The effect of hydrolysis on the mechanical properties, thermodynamic performance test, found that the crosslinked cellulose membrane material mechanical properties and heat resistance than uncrosslinked better, the addition of FNE has little effect on these properties. (4) on the fluorescence of the cellulose membrane material as the research object, based on its chemical physical release, controlled release, indicating the effect in low concentration The study results showed that grafted cellulose membrane has certain ability of chemical release of NAA; concentration and membrane permeation rate on both sides of the difference of NAA; when NAA concentration is too low, the fluorescence modified cellulose membrane began to recover, and can be observed by the naked eye. The research results show that cellulose the membrane material of modified can be tailored for the pesticide controlled-release capsule suitable. At the same time, modified cellulose membrane material in photopolymerization, luminescent materials etc, also has good prospects for development. Due to the lack of appropriate coating technology, cellulose membrane materials for practical application further, still needs more research.

【學(xué)位授予單位】：中國農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ352.7;TQ450.4

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