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| 研究生： |
陳彥廷 YEN-TING CHEN |
|---|---|
| 論文名稱： |
由元素矽水解法合成無機二氧化矽奈米顆粒及以RAFT 活自由基聚合法合成用於不飽和聚酯、乙烯基酯及環氧樹脂之奈米級無機二氧化矽/有機高分子核殼型顆粒添加劑 Synthesis of nano-scale colloidal silica from elemental silicon by hydrolysis, and synthesis of nano-scale inorganic silica/organic polymer core-shell particle as additives by RAFT living free radical polymerizations for unsaturated polyester, vinyl ester, and epoxy resins. |
| 指導教授： |
黃延吉
Yan-Jyi Huang |
| 口試委員: |
陳崇賢
Chorng-Shyan Chern 邱文英 Wen-Yen Chiu |
| 學位類別： |
碩士 Master |
| 系所名稱： |
工程學院 - 化學工程系 Department of Chemical Engineering |
| 論文出版年： | 2012 |
| 畢業學年度： | 100 |
| 語文別： | 中文 |
| 論文頁數： | 101 |
| 中文關鍵詞： | 表面改質劑 、無機/有機核殼型顆粒(CSP) 、可逆加成-斷裂鏈轉移RAFT 、不飽和聚酯 、乙烯基酯 、環氧樹脂 、抗體積收縮性 、活高分子 、二氧化矽 |
| 外文關鍵詞： | Silica, modifier, Reversible Addition-Fragmentation Chain Transfer, inorganic/organic core-shell particle (CSP), unsaturated polyester (UP), vinyl ester resins (VER), epoxy (EP), low-profile additives, living polymer |
| 相關次數： | 點閱：416 下載：1 |
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本文以元素矽水解法合成不同奈米粒徑的二氧化矽當作擔體，經由表面改質劑( 4-(Chloromethyl)phenyltrimethoxysilane )改質之後，再利用可逆加成-斷裂鏈轉移之活自由基聚合作用(RAFT)，在二氧化矽表面接枝高分子，形成無機/有機核殼型顆粒(CSP)，可當成不飽和聚酯、乙烯基酯及環氧樹酯的特殊添加劑，以改善熱固性樹脂基材之物性，如抗體積收縮性質及機械性質。
CSP的合成是以二氧化矽當做核心，再以具化學結構Z-C(=S)-S-R之RAFT鏈轉移劑3-Benzylsulfanylthiocarbonylsufanylpropionic Acid (BSPA)，接枝於先經苯甲氯表面改質後的二氧化矽(即Si-Cl)，形成接枝鏈轉移劑之二氧化矽(Si-BSPA)，再以 Si-BSPA 為鏈轉移劑，經由RAFT 溶液聚合途徑聚合有機之丙烯酸甲酯、丙烯酸丁酯單體，形成無機/有機核殼型顆粒(Si-PMA, Si-PBA-b-PMA)。反應中的鏈轉移劑(BSPA)在RAFT聚合作用過程中會形成休眠基團，緩慢的進行聚合作用，可以控制接枝聚合物的分子量及分子量分佈，所得到之核殼顆粒之高分子外殼，並具活高分子(living polymer)之特性。
In the synthesis of the Si-PMA and Si-PBA-b-PMA, the nano-scale colloidal silica was obtained by the hydrolysis of elemental silicon. Then silica was reacted with 4-(chloromethyl)phenyltrimethoxysilane to produce benzyl chloride functionalized silica(Si-Cl) first, followed by reacting with BSPA to make BSPA-grafted silica particle (Si-BSPA). Later, Si-BSPA can be used as a RAFT agent to make Si-poly(methyl acrylate) (i.e. Si-PMA) and Si-PBA-b-PMA via Reversible Addition -Fragmentation Chain Transfer (RAFT) polymerization.
During RAFT polymerization, the CTA chain transfer agent would become a dormant specimen, which may slow down the polymerization rate, and the molecular weight and molecular weight distribution can then be controlled. The Si-PMA has a characteristic of living polymer. By characteristic of living polymer, Si-PMA was utilized as a macro-CTA to mediate chain extension polymerization of butyl acrylate(BA) monomers, and diblock copolymer grafted silica (i.e Si-PBA-b-PMA) was prepared.
The synthesized Si-PMA and Si-PBA-b-PMA, namely, inorganic/ organic core-shell particle (CSP) can be employed as low-profile additives (LPA) for low-shrink unsaturated polyester (UP), vinyl ester resins (VER), and Epoxy (EP) resin.
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