以RAFT活自由基聚合法合成用於不飽和聚脂、乙烯基脂及環氧樹脂之奈米級無機矽膠/有機高分子核殼型顆粒添加劑

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研究生：	謝宇軒 yeu-shiun shieh
論文名稱：	以RAFT活自由基聚合法合成用於不飽和聚脂、乙烯基脂及環氧樹脂之奈米級無機矽膠/有機高分子核殼型顆粒添加劑 Synthesis of nano-scale inorganic silica gel/organic polymer core-shell particle as additives by RAFT living free radical polymerizations for unsaturated polyester, viny 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：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	78
中文關鍵詞：	可逆加成-斷裂鏈轉移、鏈轉移劑、無機/有機核殼型顆粒、不飽和聚酯、抗體積收縮劑
外文關鍵詞：	reversible addition-fragmentation chain transfer, chain transfer agent, inorganic/organic core-shell particle (CSP), unsaturated polyester resin (UP), low-profile additive (LPA).
相關次數：	點閱：494 下載：0
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摘要
本文以可逆加成-斷裂鏈轉移之活自由基聚合作用(RAFT)合成不飽和聚脂的特殊添加劑，無機/有機核殼型顆粒(CSP)，以減少聚合固化後之體積收縮，做為抗體積收縮劑。進行RAFT聚合法之前，吾人須先合成出具化學結構Z-C(=S)-S-R之鏈轉移劑，並以FTIR、1H-NMR及DSC對其進行鑑定，證實合成成功。
將鏈轉移劑BSPA接枝於無機之矽膠表面(即Si-BSPA)之後，再將Si-BSPA經由RAFT途徑聚合有機之丙烯酸甲酯單體，而產生均聚合物接枝於矽膠上，再經由RAFT途徑聚合有機之丙烯酸丁酯，而產生區塊共聚合物接之於矽膠上，形成無機/有機核殼型顆粒(CSP)。反應過程中添加自由之鏈轉移劑在整個聚合作用期間可改善接枝聚合物之分子量及分子量分佈。

關鍵字：可逆加成-斷裂鏈轉移，鏈轉移劑，無機/有機核殼型顆粒，不飽和聚酯，抗體積收縮劑

Abstract
Synthesis of inorganic/organic core-shell particle (CSP) as low-profile additives for unsaturated polyester resins by RAFT living free radical polymerizations has been studied in this work. Before the RAFT polymerization, the chain transfer agent with a chemical structure of Z-C(=S)-S-R was synthesized first. The synthesized chain transfer agent was then characterized by using FTIR、1H-NMR and DSC to confirm its structure.
The chain transfer agent (CTA), namely, BSPA, was bonded onto the inorganic silica particles. The silica-supported BSPA was then used to mediate RAFT polymerization of methyl acrylate to produce homopolymer grafted silica, known as inorganic/organic core-shell particle (CSP). Moreover, the silica-supported PMA was then used to mediate RAFT polymerization of Butyl Acrylate to produce black copolymer grafted silica. It was found that the introduction of a free CTA in solution during polymerization could significantly improve the control on molecular weight and polydispersity of grafted polymers.

Keyword ：reversible addition-fragmentation chain transfer(RAFT) ,chain transfer agent, inorganic/organic core-shell particle (CSP), unsaturated polyester resin (UP), low-profile additive (LPA).

目錄
中文摘要.............................................................................................................	Ⅰ
英文摘要.............................................................................................................	Ⅱ
誌謝.....................................................................................................................	Ⅲ
目錄.....................................................................................................................	IV
圖表索引.............................................................................................................	VII
第一章 緒論......................................................................................................	1
	1-1高分子複合材料.............................................................................	1
	1-2不飽和聚酯......................................................................................	2
	1-3乙烯基酯樹脂..................................................................................	3
	1-4抗收縮劑..........................................................................................	4
	1-5增韌劑..............................................................................................	5
	1-6研究籌範..........................................................................................	7
第二章 文獻回顧...............................................................................................	8
	2-1不飽和聚酯與苯乙烯之交聯共聚合反應.......................................	8
	2-2溶液聚合法......................................................................................	12
	2-3自由基聚合法...................................................................................	13
	2-4活性自由基聚合法...........................................................................	16
	2-5原子轉移自由基聚合法...................................................................	18
	2-6穩定自由基聚合法...........................................................................	20
	2-7可逆加成-斷裂鏈轉移聚合法.........................................................	22
第三章 實驗方法與設備...................................................................................	25
	3-1 實驗藥品.........................................................................................	25
	3-2實驗儀器...........................................................................................	27
	3-3實驗方法..........................................................................................	29
		3-3-1丙烯酸甲酯單體的純化.........................................................	29
		3-3-2AIBN起始劑的純化................................................................	30
		3-3-3冷凍-抽氣-解凍法...................................................................	30
		3-3-4鏈轉移劑之合成反應式.........................................................	30
		3-3-5鏈轉移劑3-benzylsulfanylthiocarbonylsufanylpropionic acid(BSPA)的合成及純化...............................................................	30
		3-3-6矽膠接枝聚合物之合成反應式.............................................	31
		3-3-7矽膠接枝聚合物之合成.........................................................	32
		3-3-7-1活化矽膠粒子......................................................................	32
		3-3-7-2矽膠接枝鏈轉移劑之合成..................................................	33
		3-3-7-3RAFT聚合作用合成矽膠接枝聚合物................................	33


	3-3-7-4胺解分開接枝聚合物.........................................................
3-3-7-5 RAFT聚合再接枝合成區塊共聚合物..............................	34
35
	3-4結構鑑定...........................................................................................	36
		3-4-1傅立葉轉換紅外線光譜儀.....................................................	36
		3-4-2核磁共振光譜儀.....................................................................	37
		3-4-3常壓式熱分析儀.....................................................................	38
		3-4-4熱重分析儀............................................................................	38
		3-4-5凝膠滲透層析儀....................................................................	39
第四章 結果與討論...........................................................................................	40
	4-1鏈轉移劑的合成與結構分析...........................................................	41
		4-1-1鏈轉移劑合成反應探討.........................................................	41
		4-1-2鏈轉移劑之FTIR結構分析....................................................	43
	4-1-3鏈轉移劑之NMR結構分析...................................................	45
	4-1-4鏈轉移劑之DSCR結構分析.................................................	49
	4-2矽膠接枝聚合物之合成與結構分析...............................................	51
	4-2-1矽膠接枝聚合物之反應探討.................................................	51
	4-2-2活化矽膠之結構分析.............................................................	53
	4-2-3-1矽膠接枝鏈轉移劑之結構分析.........................................	55
	4-2-3-2矽膠每克接枝莫爾數計算.................................................	56
	4-2-4矽膠接枝聚丙烯酸甲酯之分析.............................................	64
	4-2-5矽膠接枝聚丙烯酸丁酯區塊丙烯酸甲酯之分析.................	66
	4-3RAFT聚合作用矽膠接枝丙烯酸甲酯之反應探討.........................	73
第五章 結論.......................................................................................................	75
第六章 參可文獻...............................................................................................	77

                                

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