研究生: |
許毓倫 Yu-Lun Hsu |
---|---|
論文名稱: |
以RAFT活自由基乳化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及次微米級之高分子核殼型添加劑 Synthesis of nano-scale and submicron-scale polymeric core-shell rubber additives RAFT living free radical emulsion 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: | 2011 |
畢業學年度: | 99 |
語文別: | 中文 |
論文頁數: | 340 |
中文關鍵詞: | RAFT活自由基種子乳化聚合 、傳統乳化聚合 、核殼型橡膠添加劑 、不飽和聚酯 、乙烯基酯樹脂 、環氧樹脂 |
外文關鍵詞: | core-shell rubber(CSR), unsaturated polyester resin (UP), epoxy resin (EPR), vinyl ester resin (VER), seeded emulsion polymerizations, reversible addition-fragmentation chain transfer |
相關次數: | 點閱:309 下載:0 |
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本文主要探討以乳化聚合法合成具有不同奈米級顆粒大小和不同外殼組成的通用型核殼橡膠(gp-CSR)及以RAFT聚合法(採用自發性相反轉、無界面活性劑乳化聚合法)合成具有不同奈米級顆粒大小的RAFT型特用核殼橡膠(s-CSR),作為不飽和聚酯樹脂(UP),環氧樹脂(EPR)和乙烯基酯樹脂(VER)的抗體積收縮劑(LPA)及增韌劑。並且合成兩種不同化學結構之傳統UP,包括MA-PG型、MA-PA-PG型UP,及vinyl ester resin (VER)與環氧樹脂(EPR),進而設計出具不同相溶性之苯乙烯(St)/UP(或VER)/gp-CSR(或s-CSR)、EPR/DDM(或DDS)/s-CSR三成份系統。 通用型核殼橡膠(gp-CSR)先以半批次進料方式聚合丙烯酸正丁酯(BA),形成PBA軟質核心,再以批次進料方式聚合甲基丙烯酸甲酯(MMA)及丙烯酸甲酯(MA),分別形成PMMA硬質外殼與PMA軟質外殼,gp-CSR之外殼又添加5 mol%與10 mol%的甲基丙烯酸環丙氧酯(Glycidyl methacrylate, GMA)共單體及交聯劑(EGDMA)進行改質,以合成出具高極性及具特殊官能基基團外殼之gp-CSR,以增加CSR外殼之極性與樹脂基材化學交聯之能力。利用Debye’s eq.及基團貢獻法,計算出UP、EPR、VER與CSR之外殼的偶極矩,以解釋St/UP(或VER)/gp-CSR(或s-CSR)、EPR/DDM(或DDS)/s-CSR三成份系在25℃(St/VER/gp-CSR or s-CSR)及80℃(EPR/DDM/gp-CSR or s-CSR)及95℃(EPR/DDS/gp-CSR or s-CSR) 及110℃(St/VER/gp-CSR or s-CSR)下未反應前之相溶性。再利用掃描式電子顯微鏡(SEM)來觀測St/VER/gp-CSR或EPR/DDM/gp-CSR三成份系統於110℃下聚合固化後樣品被破壞的微觀形態,來了解CSR顆粒大小及化學組成對三成份系統固化過程中之相溶性影響。
Synthesis of acrylic type of core-shell rubbers (gp-CSR) with varied nano-scale and submicron-scale particle size and shell chemical composition. And synthesis of s-CSR by RAFT polymerization via spontaneous phase inversion process and RAFT surfactant-free, batch emulsion polymerization as low-profile additives (LPA) and tougheners for unsaturated polyester resins (UP) ,epoxy resin (EPR) and vinyl ester resin (VER) have been investigated. Two types of conventional nsaturated polyester resin with different chemical structures, namely, MA-PG type of UP and, MA-PA-PG type of UP, epoxy resin (EPR) and vinyl ester resin (VER) ,have also been synthesized so that styrene (St) /UP(or VER) /CSR or EPR/DDM/CSR ternary systems with different miscibility can be designed.
In the synthesis of the core-shell rubber, a semi-batch process was used to synthesize the soft core, which was made from poly(butyl acrylate) (PBA) , whereas a batch process was to employed to synthesize the hard shell , which was composed of poly(methyl crylate) (PMA) . Also, the shell of the gp-CSR was modified with a crosslinking agent, ethylene glycol dimethacrylate (EGDMA). In addition, the shell of gp-CSR has also been modified by introducing glycidyl methacrylate(GMA) as a comonomer to both decrease the molecular polarity and provide the specific functionality for the shell of the CSR.
By using Debye’s equation and the group contribution method, the dipole moments of UP、VER、EPR and the shell component of the CSR can be calculated, which can then explain the phase characteristics of the St/UP(或VER)/gp-CSR(或s-CSR)、EPR/DDM(或DDS)/s-CSR ternary system prior to the reaction at 25℃(St/UP(或VER)/s-CSR)、80℃(EPR/DDM/s-CSR) 、95℃(EPR/DDS/s-CSR) and 110℃(St/VER/gp-CSR).
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