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| 研究生： |
余雅婷 Ya-ting Yu |
|---|---|
| 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 Synthesis of nano-scale colloidal silica from elemental silicon by hydrolysis, and synthesis of nano-scale inorganicsilica/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
none 邱文英 none |
| 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： | 2013 |
| 畢業學年度： | 101 |
| 語文別： | 中文 |
| 論文頁數： | 147 |
| 中文關鍵詞： | 二氧化矽 、表面改質劑 、可逆加成-斷裂鏈轉移RAFT 、無機/有機核殼型顆粒(CSP)，不飽和聚酯 、乙烯基酯 、環氧樹脂 、抗體積收縮性 、機械性質 、活高分子 |
| 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 (LPA), living polymer |
| 相關次數： | 點閱：461 下載：2 |
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本文以元素矽水解法合成不同奈米粒徑(15 nm ~ 60 nm)的二氧化矽為無機/有機核殼型顆粒(CSP)的核心，經表面改質劑( 4-(Chloromethyl)phenyltrimethoxysilane )改質後，利用可逆加成-斷裂鏈轉移之活自由基聚合作用(RAFT)，於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。
將含有化學結構Z-C(=S)-S-R之RAFT鏈轉移試劑3-Benzylsulfanylthiocarbonylsufanylpropionic Acid (BSPA)，接枝於經苯甲氯表面改質後的二氧化矽(即SiO2-Cl)，形成接枝鏈轉移試劑之二氧化矽(SiO2-BSPA)，再以 SiO2-BSPA 為鏈轉移試劑，經由RAFT 溶液聚合途徑聚合有機之丙烯酸甲酯(MA)、甲基丙烯酸環丙氧酯(GMA)及丙烯酸丁酯(BA)單體，形成無機/有機核殼型顆粒( SiO2-PBA-b-PMA 或 SiO2-PBA-b-P(MA-co-GMA))。反應中的鏈轉移試劑(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，可控制接枝聚合物的分子量及分子量分佈，所得到核殼顆粒之高分子外殼，並具活高分子(living polymer)特性。
本研究所合成之無機/有機奈米級核殼顆粒(CSP)，可用作不飽和聚酯(UP)、乙烯基酯(VER)及環氧樹脂(EP)之抗收縮劑(LPA)。本文中亦探討了這些CSP對苯乙烯(St)/VER/CSP三成份系統聚合固化後樣品之機械性質的影響
In the synthesis of the SiO2-PBA-b-PMA and SiO2-PBA-b-P(MA-co-GMA), the nano-scale colloidal silica (15~60nm) was obtained by the hydrolysis of elemental silicon. Then silica was reacted with 4-(chloromethyl)phenyltrimethoxysilane to produce benzyl chloride functionalized silica(SiO2-Cl) first, followed by reacting with BSPA to make BSPA-grafted silica particle (SiO2-BSPA). Later, SiO2-BSPA can be used as a RAFT agent to make SiO2-PBA-b-PMA (or SiO2-PBA-b-P(MA-co-GMA)) 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 SiO2-PMA (or SiO2-PBA-b-P(MA-co-GMA)) has a characteristic of living polymer. By characteristic of living polymer, SiO2-PMA (or SiO2-PBA-b-P(MA-co-GMA)) was utilized as a macro-CTA to mediate chain extension polymerization of butyl acrylate(BA) monomers, and diblock copolymer grafted silica (i.e SiO2-PBA-b-PMA or SiO2-PBA-b-P(MA-co-GMA)) was prepared.
The synthesized SiO2-P(MA-co-GMA) and SiO2-PBA-b-P(MA-co-GMA), 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. The effect of the CSP on the mechanical properties of the Styrene (St)/VER/CSP ternary system after the cure have also been investigated.
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