本文選題：丁烯氟蟲腈　切入點：微膠囊　出處：《山東農(nóng)業(yè)大學》2017年博士論文　論文類型：學位論文

【摘要】：微膠囊制劑具有緩釋控釋提高藥效持效期的作用,對農(nóng)藥的減量增效具有重要的意義。但是作為不太成熟的小劑型品種,其制備方法較為單一,且對其性能檢測和釋放機理的研究較少。本文選取丁烯氟蟲腈原藥為研究對象,使用層層自組裝技術制備了多種類型微膠囊,同時對其制備工藝路線進行了描述評價,并對各種類型微膠囊的性能進行了對比分析。首先確定了層層自組裝技術制備微膠囊的最佳條件,然后研究了不同組裝層數(shù)、不同囊壁材料、不同緩釋條件、不同囊芯物狀態(tài)對微膠囊釋放的影響。最后通過模擬釋放動力學方程研究了層層自組裝技術制備微膠囊的釋放機理。本文主要研究結(jié)果可概括如下:1.微膠囊的制備(1)采用層層自組裝技術以殼聚糖和海藻酸鈉為壁材制備微膠囊,研究了制備過程中不同條件的變化對微膠囊包封率和緩釋性能的影響,從而確定最佳制備條件:每層囊壁的組裝時間為20 min;組裝溫度為室溫;聚電解質(zhì)溶液中鹽離子濃度為0.5 mol/L;pH值在5.1左右。(2)分別使用CS/ALG、CS/SL、PAH/PSS為壁材制備不同組裝層數(shù)的微膠囊,制備過程中測定了不同組裝層數(shù)微膠囊的Zeta電勢、平均粒徑和表觀形貌。研究結(jié)果表明三類壁材制備微膠囊過程中變化規(guī)律基本相同:Zeta電勢隨著組裝正負聚電解質(zhì)的加入發(fā)生周期性變化;微膠囊的平均粒徑隨著組裝層數(shù)的增加逐漸增加;微膠囊顆粒表面的粗糙度也隨著組裝層數(shù)的增加而增加;通過紅外光譜分析也可證明帶有相反電荷的聚電解質(zhì)已經(jīng)成功地將丁烯氟蟲腈固體原藥包裹在囊芯內(nèi)。(3)以殼聚糖和SDS為壁材制備了包覆液體溶液、油懸浮劑和固體顆粒的微膠囊,其中,溶液為丁烯氟蟲腈二氯甲烷溶液,油懸浮劑使用的介質(zhì)油為玉米油,分散劑為3478B。通過測定制備過程中的Zeta電勢的變化、光學顯微鏡觀察微膠囊的表觀形貌來確定成功制備了包覆不同囊芯物狀態(tài)的微膠囊。2.微膠囊的表征(1)以殼聚糖和海藻酸鈉為壁材制備了不同組裝層數(shù)的微膠囊,測定了不同組裝層數(shù)微膠囊的表觀形貌、包封率和載藥量、抗光解性能。研究結(jié)果表明:隨著組裝層數(shù)的增加,微膠囊表面的粗糙度明顯增加;載藥量和包封率均是先升高再降低,當組裝層數(shù)為4層時載藥量達到最大值55%,而組裝層數(shù)為6層時包封率達到最大值83%;隨著組裝層數(shù)的增加微膠囊中原藥的光解率先快速降低,當組裝層數(shù)為6層時光解率降到了21.7%,隨后趨于平穩(wěn);(2)使用上述三類壁材制備了組裝4層的微膠囊,比較了不同壁材微膠囊的包封率、載藥量、抗光解性能的差異。研究結(jié)果表明:載藥量和包封率的差異相同,pah/pss為壁材制備的微膠囊載藥量和包封率均最好,cs/sl為壁材制備的微膠囊次之,cs/alg為壁材制備的微膠囊的載藥量和包封率最小;三類壁材制備微膠囊抗光解能力由強到弱依次是cs/alg、pah/pss、cs/sl。3.微膠囊釋放規(guī)律的研究(1)組裝層數(shù)對微膠囊釋放性能的影響不同組裝層數(shù)微膠囊的釋放規(guī)律基本相同,釋放速率先快速升高,然后放緩。隨著組裝層數(shù)的增加微膠囊的緩釋能力逐漸增強。且瞬時釋放的峰值向后推遲。(2)囊壁材料對微膠囊釋放性能的影響pah/pss為壁材制備的微膠囊緩釋性能最好,而以cs/sl和cs/alg為壁材制備的微膠囊的緩釋性能相差不大。(3)緩釋條件對微膠囊釋放性能的影響以殼聚糖和海藻酸鈉為壁材制備組裝6層的微膠囊為研究對象,研究了緩釋介質(zhì)中乙醇含量、鹽離子濃度、ph、溫度對微膠囊緩釋性能的影響。研究結(jié)果表明:隨著緩釋介質(zhì)中乙醇含量的增加,其釋放速率逐漸增加;而隨著緩釋介質(zhì)中外加鹽離子濃度的增加,微膠囊的釋放速率降低;緩釋介質(zhì)的ph為中性或者偏堿性微膠囊的釋放速率基本相同,ph值為5時釋放速率明顯升高;升高緩釋介質(zhì)的溫度能夠顯著提高微膠囊的緩釋速率。(4)囊芯物狀態(tài)對微膠囊釋放性能的影響測定了不同囊芯物狀態(tài)微膠囊的緩釋情況,使用動力學方程模擬了不同微膠囊的釋放曲線,研究結(jié)果表明:三類微膠囊的釋放規(guī)律大體相同,一開始都具有“突釋現(xiàn)象”,接著釋放就會逐漸放緩,當囊芯物是溶液時,微膠囊的釋放速率最快,而當囊芯物是油懸浮劑時,釋放的速率最慢。4.釋放動力學研究(1)不同組裝層數(shù)微膠囊釋放動力學研究將組裝4層、6層和8層的微膠囊累積釋放質(zhì)量百分數(shù)低于60%的釋放數(shù)據(jù)代入ritger-pappas模型,得到相應的的n值非常相近,說明它們的釋放機理相同,為fick擴散和溶出機理的偶合,也就是說藥物從微膠囊中釋放是溶出和擴散共同控制的過程。(2)不同囊心物狀態(tài)微膠囊釋放動力學研究使用動力學方程模擬釋放曲線可以知道在突釋階段,囊芯物為固體或者油懸浮劑時用Higuchi模型擬合的效果最好,釋放符合Fick定律,當囊芯物為溶液時,藥物以零級釋放,對應于溶出控制機理。進入緩釋階段后,囊芯物是固體或者溶液的微膠囊在緩釋階段使用一級釋放動力學方程擬合的效果較好,而當囊芯物是油懸浮時,其釋放動力學曲線仍符合Higuchi模型。
[Abstract]:The micro capsule has the effect of sustained release efficacy duration, is of great significance to the reduction efficiency. But as pesticide immature small dosage varieties, the preparation method is single, and to test its performance and release mechanism research is less. This paper selects butylenes fipronil for technical research the object, using the self-assembly technology to prepare various types of micro capsule, and its preparation process are described, and performance of various types of micro capsules were studied. Firstly, optimum conditions of self-assembly technique for preparing microcapsules were determined, and then study the different assembly layers, different capsule wall materials, different release conditions, effects of different capsule core material of the microcapsule release state. Finally, through the simulation of release kinetics of release mechanism of self-assembly technique for preparing microcapsules. The main Research results can be summarized as follows: 1. preparation of microcapsule (1) by self-assembly technique using chitosan and sodium alginate as wall material of microencapsulation, study the influence of different conditions in the process of preparation of encapsulation efficiency and release property of microcapsules, so as to determine the optimal preparation conditions: assembly time of each layer of the cyst wall was 20 min; the assembly room temperature; poly salt ion concentration in the electrolyte is 0.5 mol/L; the pH value is about 5.1. (2) using CS/ALG, CS/SL, microcapsule wall material of PAH/PSS were prepared with different number of layers, in the preparation process of measuring the Zeta potential of different assembly the number of microcapsules, the average particle size and surface morphology. The results show that variation of the three types of wall material of microencapsulation process is basically the same: Zeta potential with the periodic change of positive and negative assembly of polyelectrolytes; the average particle size of microcapsules with assembly layers The increased; microcapsule particle surface roughness also increased with the increase of the number of the layers increases; the infrared spectral analysis also proved that the oppositely charged polyelectrolyte has successfully butenefipronil solid TC wrapped in the capsule core. (3) the wall materials were prepared by liquid solution with chitosan and SDS, microcapsule, oil suspension and solid particles in solution for butene fipronil dichloromethane solution, medium oil suspending agent used for corn oil, dispersing agent 3478B. through the changes of Zeta potential in the preparation process of measurement, optical microscopy micro capsule to determine the apparent morphology characterization.2. microcapsules with different capsule core material state of the microcapsules were prepared (1) microcapsules prepared by different layers of assembled wall material prepared using chitosan and sodium alginate, different assembly layers of microcapsules to measure the apparent morphology, The encapsulation efficiency and drug loading, anti photolysis performance. The results show that: with the increase of the number of the layers, microcapsule surface roughness increased significantly; the drug loading and encapsulation efficiency were increased first and then decreased, when the assembly layer is 4 when the loading rate reaches the maximum value of 55%, and the assembly of 6 layer at the encapsulation efficiency reached the maximum 83%; with the increase of the number of micro capsule assembly photolysis central medicine quickly took the lead to reduce, when the assembly layer is 6 time solution rate dropped to 21.7%, then remained stable; (2) using the above three kinds of wall material was prepared by assembling micro capsule 4 layer, different wall microcapsule encapsulation efficiency, drug loading, different anti photolysis performance. The results show that: the difference of loading and entrapment efficiency of the same pah/pss as the wall material of microcapsule by drug loading and encapsulation efficiency were the best, cs/sl the wall material of microcapsules prepared by microencapsulated cs/alg as the wall material preparation The entrapment efficiency and drug loading capacity of three kinds of minimum; anti photolysis wall material of microcapsule is prepared from strong to weak cs/alg, pah/pss, cs/sl.3. microcapsules release (1) release of assembly layers to influence the release property of microcapsules in different layers of assembled microcapsules are basically the same, the release rate of the first fast increased, then slow. With the ability to increase the number of the layers sustained-release microcapsules gradually. And the peak instantaneous release postponed. (2) the capsule wall material effect on release property of microcapsule wall material of pah/pss microcapsules prepared by the good sustained-release properties, cs/sl and cs/alg as the release property of the microcapsule wall material preparation are similar. (3) sustained release conditions on the release properties of microcapsules using chitosan and sodium alginate as wall material to prepare microcapsule assembling 6 layer as the research object, the research content of ethanol release medium, salt ion concentration, PH, the effect of temperature on the release characteristics of the microcapsule. The results show that with the increase of ethanol release medium, its release rate gradually increased; with the increase of salt concentration and release medium, the release rate of microcapsules decreased; release medium pH for release rate or alkaline microcapsule basic the same, pH value is 5 when the release rate increased significantly; increased release medium temperature can significantly increase the release rate of microcapsules. (4) capsule core material state determination of different slow-release capsule core material of microcapsules of state influence the release property of microcapsules, the simulation curves of different release microcapsules using kinetic equation the research results show that, three kinds of microcapsules release roughly the same, beginning with "burst release phenomenon", and then release will gradually slow down, when the capsule core material is the solution, the release speed of microcapsule The fastest rate, and when the capsule core material is oil suspension agent, release kinetics of the release rate of the slowest.4. (1) of different layers assembled microcapsules release kinetics of the assembly of the 4 layer, 6 layer and 8 layer of microcapsules and the cumulative release percentage is lower than the quality of release data into the ritger-pappas model 60%, corresponding the n values are very similar, that they have the same release mechanism, Fick diffusion and dissolution mechanism of coupling, that is to say the drug release from the microcapsule is dissolution and diffusion of the common control. (2) different capsule heart state micro capsule release kinetics using dynamic equation simulation release curve can know in the stage of burst release, capsule core material is solid or oil suspension fitted with Higuchi model had the best effect, release consistent with Fick's law, when the capsule core material for solution, drug release to zero level, corresponding to the dissolution into the release control mechanism. After the stage, the solid core of the capsule is solid or solution microcapsule. In the slow release stage, the first order release kinetics equation is better. When the core is oil suspension, the release kinetics curve is still consistent with the Higuchi model.

【學位授予單位】：山東農(nóng)業(yè)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TQ450.6

【參考文獻】

相關期刊論文 前10條

1 李海燕;崔業(yè)翔;王晴;李爽;李帥;;溶劑揮發(fā)法制備聚砜包覆桐油自修復微膠囊[J];中國塑料;2016年05期

2 馬濤;袁會珠;閆曉靜;楊代斌;;10%噻唑磷微囊的研制及其對番茄根結(jié)線蟲的防治效果[J];農(nóng)藥;2016年04期

3 董瑜;田華;馮超;袁會珠;張成省;孔凡玉;;15%甲霜靈微膠囊緩釋劑制備及對煙草黑脛病的防治效果[J];植物保護學報;2015年03期

4 Hongwei Shi;Fuchun Liu;En-Hou Han;;Surface-engineered Microcapsules by Layer-by-layer Assembling for Entrapment of Corrosion Inhibitor[J];Journal of Materials Science & Technology;2015年05期

5 李佳;余丹;林煌丁;李輝;王寧;徐澤禧;馮勝利;;緩釋型農(nóng)藥的制備與性能研究[J];化學與黏合;2015年01期

6 肖俊俊;盧向陽;巨修練;李川東;;層層組裝那他霉素微膠囊釋放速率對抗光解的影響[J];農(nóng)藥;2014年12期

7 王子希;宋思思;李曉剛;;溶劑揮發(fā)法制備噻唑磷微膠囊[J];廣東化工;2014年22期

8 廖科超;路福綏;劉村平;夏慧;;丁烯氟蟲腈緩釋微膠囊的制備及其性能[J];應用化學;2014年09期

9 張壯麗;王陸巡;趙寧;趙志鴻;王桂芳;張小俊;;噴霧干燥法制備鹽酸千金藤堿微囊[J];中成藥;2014年08期

10 章彬;林鈺婷;任璐;李曉剛;;改性β-環(huán)糊精為載體的七氟菊酯微膠囊的制備及性能測試[J];農(nóng)藥;2014年05期

相關博士學位論文 前5條

1 向育君;改性木質(zhì)素磺酸鈉水凝膠的制備和應用研究[D];湖南大學;2013年

2 陳劍秋;幾種新型緩控釋肥工藝及養(yǎng)分釋放特征研究[D];山東農(nóng)業(yè)大學;2012年

3 段路路;緩控釋肥料養(yǎng)分釋放機理及評價方法研究[D];山東農(nóng)業(yè)大學;2009年

4 陳幼芳;疏水性藥物微膠囊的自組裝構(gòu)筑及其緩釋性能研究[D];浙江大學;2006年

5 張繼穩(wěn);緩釋、控釋制劑藥動學理論研究及其在大環(huán)內(nèi)酯類藥物生物利用度研究中的應用[D];沈陽藥科大學;2001年

相關碩士學位論文 前10條

1 肖俊俊;層層組裝制備那他霉素微膠囊及性能測試[D];武漢工程大學;2015年

2 史曉磊;丁烯氟蟲腈的殘留及其對水稻生理特性和稻米品質(zhì)的影響[D];哈爾濱師范大學;2014年

3 章彬;溶劑揮發(fā)法制備的七氟菊酯生物可降解農(nóng)藥微膠囊研究[D];湖南農(nóng)業(yè)大學;2014年

4 陸靜;高效氯氟氰菊酯微膠囊懸浮劑的研制及釋放機理研究[D];浙江工業(yè)大學;2013年

5 付志英;殼聚糖包覆水溶性藥物微膠囊的制備與表征[D];華南理工大學;2013年

6 王曉靜;層層自組裝殼聚糖/木質(zhì)素磺酸鈉微膠囊的制備及性能研究[D];北京化工大學;2013年

7 杜超;PUA/PSS層層自組裝藥物載體的制備及智能響應性藥物釋放[D];鄭州大學;2013年

8 張琳;載藥CS/β-TCP復合微球制備及藥物緩釋機理研究[D];廣西大學;2012年

9 田可;苯甲酰脲類農(nóng)藥微膠囊的制備及其性能研究[D];東北林業(yè)大學;2010年

10 邢樹禮;噴霧干燥法制備藥物微囊和微球的研究[D];青島科技大學;2009年

，

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