含無毒抗生物劑4，5-二氯-N-辛基-4-異噻唑啉-3-酮 (DCOIT)防污微膠囊之製備

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陳柔樺(Rou-Hua Chen) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

含無毒抗生物劑4，5-二氯-N-辛基-4-異噻唑啉-3-酮 (DCOIT)防污微膠囊之製備

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摘要(中)

本研究探討以內部相分離法和無乳化劑乳化聚合法製備應用於船體塗層中之防污
微膠囊的可行性，所包覆之核心物質為具有廣泛抗生物特性之4，5-二氯-N-辛基-4-異噻唑啉-3-酮(DCOIT)防污劑。微膠囊必須具備高包覆量、耐溶劑性以及5μm 以下之粒徑。利用熱重損失分析儀(TGA)、可見光紫外光分光光譜儀(UV-vis)、傅立葉轉換紅外線光譜儀(FTIR)、光學顯微鏡(OM)、掃描式電子顯微鏡(SEM)和動態光散射儀(DLS)來進行微膠囊特性分析。內部相分離法以醋酸纖維素(CA)為包覆基材，探討不同均質時間、有機相濃度、有機相對水相比例對微膠囊之表面形貌與粒徑大小影響。結果顯示微膠囊具有分布廣泛的微米級粒徑且表面形貌為不規則球型。使用無乳化劑乳化聚合法製備微膠囊是以甲基丙烯酸甲酯(MMA)與苯乙烯(St)為單體，二乙烯苯(DVB)為交聯劑，將DCOIT 溶於單體中進行聚合反應，以一階段與二階段添加單體的方式製備微膠囊。一階段製備的部分探討DCOIT 和單體添加量對微膠囊的包覆性與耐溶劑性之影響。二階段添加單體的方法可製備出核殼結構的微膠囊，深入探討單體比例、一階段轉化率、停止加熱時間與交聯密度對外觀、包覆量及釋放速率的影響。實驗結果顯示微膠囊皆為均一球型，粒徑範圍為179nm-417nm。第二階段添加防污劑，核心為St 時可達最高包覆量29.1%且具有耐溶劑性，微膠囊皆以零級釋放之模式穩定釋出包覆之防污劑。

摘要(英)

In this study, the feasibility of antifouling microcapsules preparation via internal phase separation and soap-free emulsion polymerization was investigated. The biocide, 4,5-dichloro-2n-octyl-3-isothiazolone (DCOIT), with multiple anti-organism characteristic was chosen to be the encapsulation biocide. The microcapsules must have high biocide content, solvent resistance and a particle size less than 5 μ m in order to apply in ship hull coating. Thermogravimetric analysis (TGA), scanning electron microscope (SEM), Fourier-transform
infrared spectrometer (FTIR), optical microscope (OM) and dynamic light scattering (DLS)were used to determine the characterization of microcapsules. Cellulose acetate was used as encapsulation matrix in internal phase separation method.
The effects of homogeneous time, organic phase concentration and organic phase ratio to morphology and particle size were discussed. The results showed microcapsules with irregular
spherical shape and wide distribution particle size in micrometer scale. In soap-free emulsion polymerization method, MMA and St used as monomer and DVB as cross-linking agent. DCOIT was dissolved in monomer and encapsulated by polymerization. One-stage and two stage monomer adding methods were used to prepare microcapsule. In onestage method, the effects of monomer and DCOIT amount were discussed. In two stage method, the effect of monomer ratio, first stage conversion, stop heat time and crosslink density to microcapsule morphology, solvent resistance, biocide content, and release profile were discussed. The microcapsule had uniform spherical shape and particle size 170-417nm. The
microcapsule with highest biocide content 29.1% and solvent resistance was prepared by using PS as the core material. The microcapsules release profile showed a steady biocide release in a zero order tendency.

關鍵字(中)

★ 防污劑包覆
★ 微膠囊
★ 內部相分離法
★ 無乳化劑乳化聚合
★ 4，5-二氯-N-辛基- 4-異噻唑啉-3-酮

關鍵字(英)

★ biocide encapsulation
★ microcapsule
★ internal phase separation
★ soap-free emulsion polymerization
★ 4,5-dichloro-2n-octyl-3-isothiazolone

論文目次

目錄
摘要…………………………………………………………………………………… i
目錄…………………………………………………………………………………... v
圖目錄………………………………………………………………………………. vii
表目錄……………………………………………………………………………….. ix
第一章緒論 ................................................. 1
1-1 生物污染與防污劑 ......................................... 1
1-2 微膠囊化技術和方法........................................ 5
1-3 研究動機與目的 ........................................... 9
第二章實驗 ................................................. 12
2-1 實驗藥品 ................................................ 12
2-2 實驗儀器 ................................................ 13
2-3 實驗方法 ................................................ 15
2-3-1 以相分離法製備防污微膠囊 ............................... 15
2-3-2 以一階段無乳化劑乳化聚合法製備防污微膠囊 ................ 17
2-3-3 以二階段無乳化劑乳化聚合法製備防污微膠囊 ................ 19
2-4 防污微膠囊物性分析 ...................................... 21
2-4-1 傅立葉轉換紅外線光譜儀 (FTIR) ......................... 21
2-4-2 氣相層析質譜分析儀 (GC-MS) ............................ 21
2-4-3 熱重損失分析儀 (TGA) ................................. 21
2-4-4 光學顯微鏡 (OM) ...................................... 21
2-4-5 掃描式電子顯微鏡 (SEM) ............................... 22
2-4-6 穿透式電子顯微鏡 (TEM) ............................... 22
2-4-7 可見光紫外光分光光譜儀 (UV-vis) ....................... 22
2-4-8 動態光散射儀 (DLS) ................................... 22
2-5 防污微膠囊釋放測試 ...................................... 23
2-6 防污劑微膠囊耐溶劑測試 ................................... 24
第三章結果與討論 ........................................... 25
3-1 防污劑之基本性質 ........................................ 25
3-1-1 防污劑之傅立葉轉換紅外線光譜儀分析 ...................... 26
3-1-2 防污劑之氣相色譜質譜分析 ............................... 27
3-1-3 防污劑之熱損失分析 ..................................... 28
3-1-4 防污劑之可見光紫外光分光光譜分析 ........................ 29
3-2 相分離法製備防污微膠囊.................................... 31
3-2-1 均質時間對微膠囊之影響 ................................. 32
3-2-2 DMF 為有機相溶劑對微膠囊之影響 ......................... 36
3-2-3 DMSO 為有機相溶劑對微膠囊之影響 ........................ 39
3-3 以一階段無乳化劑乳化聚合法製備防污微膠囊 .................. 42
3-4 以二階段無乳化劑乳化聚合法製備防污微膠囊 .................. 48
3-4-1 以MMA 單體合成防污微膠囊 .............................. 49
3-4-2 MMA 和St 單體合成防污微膠囊 ........................... 71
3-4-3 St 單體合成防污微膠囊 ................................. 83
第四章結論 ................................................. 87
參考文獻 ................................................... 89

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指導教授

陳暉(Hui Chen)

審核日期

2016-6-15

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