臺灣博碩士論文加值系統

本論文是使用中科院所提供羥基端聚丁二烯，利用原子轉移自由基聚合法和硼烷化學來進行接枝聚合反應。羥基端聚丁二烯為混合式固態推進劑中常用的膠合劑，因為羥基端聚丁二烯的實際應用仍需和其他物質材料進行摻合，才能獲得較好的效果，其中最常用的燃速調節劑為二茂鐵，但是羥基端聚丁二烯與二茂鐵之間並無化學鍵結，容易發生滲移現象和結塊現象，因此會限制混合式固態推進劑的應用性。所以我們利用硼烷化學和原子轉移自由基聚合法使羥基端聚丁二烯的主鏈不變，在側鏈接枝上二茂鐵形成Butacene。
在硼烷化學方面，首先將羥基端聚丁二烯側鏈雙鍵進行氫硼化後在鹼性條件下進行氧化形成側鏈帶羥基之羥基端聚丁二烯，再將其和酸化後的二茂鐵衍生物進行縮合接枝聚合反應，形成接枝共聚物。經過鑑定分析後，再進行各種反應條件(溫度、時間及單體濃度)的探討。
在原子轉移自由基聚合法方面，分成兩個方式來合成接枝共聚物﹕(1)首先是將Chloromethylferrocene和3-Butenylferrocene 利用原子轉移自由基聚合法合成出一長鏈段的Ferrocene聚合物Polybutanylferrocene，利用其末端仍具有活性的性質來作為巨起始劑以進行接枝聚合反應。(2)將羥基端聚丁二烯、Chloromethylferrocene和3-Butenylferrocene均勻混合之後，利用原子轉移自由基聚合法的方法合成接枝共聚物。經過鑑定分析後，再進行各種反應條件(溫度、時間及單體濃度)的探討。
最後，將所合成的接枝共聚物應用在摻合性不良的系統中當作一種調和劑，以增加兩界面間的作用力進而使分散區域減小形成均相的摻合，並利用掃瞄式電子顯微鏡(SEM)來觀察。

There is no chemical bonding between the burn-rate modifier (ferrocene) and the binder (HTPB),if they are mixing together in product. In order to avoid the migration,it must form a effective chemical bonding.must In our study, the graft copolymer would be prepared by atom transfer radical polymerization (ATRP) and borane chemistry. Form the analysis of 1H-NMR, we can calculated the ratio of ferrocene grafted on HTPB. These graft copolymers have been characterized by IR, NMR, TGA and GPC.
The applicability of HTPB is limited by its compatibility with other material. We have employed the graft copolymer in blending system (HTPB and Ferrocene) as compatibilizers. By adding the compatibilizer, the incompatible blends alter their morphology, by decresing the size of the dispersed domains and enhancing the interaction between the phases.

目錄
中文摘要-------------------------------------------------------------------------I
英文摘要-------------------------------------------------------------------------II
謝誌-------------------------------------------------------------------------------III
目錄-------------------------------------------------------------------------------IV
圖索引----------------------------------------------------------------------------V
表索引----------------------------------------------------------------------------VI
第一章緒論
1-1前言--------------------------------------------------------------------1
1-2接枝共聚物-----------------------------------------------------------1
1-3混合式推進劑簡介--------------------------------------------------2
1-3.1膠合劑簡介----------------------------------------------------5
1-3.2燃速調節劑簡介----------------------------------------------5
1-3.3 Butacene的簡介----------------------------------------------7
1-4聚胺基甲酸酯的簡介------------------------------------------------8
第二章硼烷化學及自由基聚合法-----------------------------------------11
2-1 硼烷化學--------------------------------------------------------------11
2-1.1氫硼化反應----------------------------------------------------11
2-1.2 氧化反應------------------------------------------------------12
2-2 自由基聚合法-------------------------------------------------------15
2-2.1 原子轉移自由基聚合法-----------------------------------19
2-2.2 穩定自由基聚合法-----------------------------------------21
2-2.3 可逆性加成-斷裂鏈轉移聚合法-------------------------23
第三章實驗部分-------------------------------------------------------------24
3-1 儀器和藥品----------------------------------------------------------24
3-1.1藥品------------------------------------------------------------24
3-1.2儀器------------------------------------------------------------25
3-2 試劑與單體的純化-------------------------------------------------26
3-2.1 溶劑的純化--------------------------------------------------26
3-2.2 單體與起始共聚物之純化--------------------------------27
3-2.3 玻璃器材等的處理-----------------------------------------28
3-3 起始物的製備-------------------------------------------------------29
3-3.1 製備Ferrocenemethanol-----------------------------------29
3-3.2 製備Chloromethylferrocene------------------------------30
3-3.3 製備3-Butenylferrocene-----------------------------------31
3-3.4 製備Ferrocenecarboxylic acid----------------------------32
3-3.5 製備Polybutanylferrocene---------------------------------33
3-4 利用硼烷化學方法製備Butacene-------------------------------34
3-4.1 氫硼化反應--------------------------------------------------34
3-4.2 氧化反應-----------------------------------------------------35
3-4.3 製備Butacene-----------------------------------------------35
3-5 利用原子轉移自由基聚合法製備Butacene-------------------36
3-5.1 利用Polybutanylferrocene為起始物合成Butancene
----------------------------------------------------------------36
3-5.2 利用Chloromethylferrocene為起始物合成Butancene
----------------------------------------------------------------37
3-6 Butacene的純化-----------------------------------------------------37
3-7 製備PU薄膜--------------------------------------------------------38
3-7.1 PU合成-------------------------------------------------------38
3-7.2 PU薄膜製備-------------------------------------------------39
3-7.3摻合薄膜之製作---------------------------------------------39
第四章結果與討論----------------------------------------------------------53
4-1 動機-------------------------------------------------------------------53
4-2 利用硼烷化學製備Butacene-------------------------------------53
4-1.1不同反應條件的影響---------------------------------------55
4-1.2 接枝共聚物Butacene之分析-----------------------------56
4-3 利用原子轉移自由基聚合法製備Butacene--------------------57
4-3.1利用Polybutanylferrocene為起始物合成Butancene
----------------------------------------------------------------57
4-3.1.1不同反應條件的影響---------------------------------58
4-3.1.2接枝共聚物Butacene之分析-----------------------59
4-3.2 利用Chloromethylferrocene為起始物合成Butancene
----------------------------------------------------------------60
4-3.2.1不同反應條件的影響---------------------------------61
4-3.2.2接枝共聚物Butacene之分析-----------------------62
4-4 Butacene在混摻上的應用-----------------------------------------62
第五章結論-------------------------------------------------------------------80
第六章參考文獻-------------------------------------------------------------81
圖索引
Figure 3-1. The 1H-NMR spectra of HTPB---------------------------------42
Figure 3-2. The FT-IR spectra of HTPB-------------------------------------43
Figure 3-3. The 1H-NMR spectra of Ferrocenemethanol------------------44
Figure 3-4. The 1H-NMR spectra of Chrolomethylferrocene-------------45
Figure 3-5. The 1H-NMR spectra of 3-Butenylferrocene------------------46
Figure 3-6. The 1H-NMR spectra of Ferrocenecarboxyilic acid----------47
Figure 3-7. The 1H-NMR spectra of Polybutanylferrocene ---------------48
Figure 3-8. The 1H-NMR spectra of PUHTPB --------------------------------49
Figure 3-9. The FT-IR spectra of PUHTPB------------------------------------50
Figure 3-10. The 1H-NMR spectra of PUButacene-----------------------------51
Figure 3-11. The FT-IR spectra of PUButacene --------------------------------52
Figure 4-1. The 1H-NMR spectra of HTPB-OH----------------------------69
Figure 4-2. The 1H-NMR spectra of (A) HTPB (B) Butacene via Borane chemistry-----------------------------------------------------------70
Figure 4-3. The TGA spectra of (A) HTPB (B) mixture (C) Butacene via Borane chemistry--------------------------------------------------71
Figure 4-4. The GPC curves of (A) HTPB (B) mixture (C) Butacene via Borane chemistry------------------------------------------------------72
Figure 4-5. The 1H-NMR spectra of (A) HTPB (B) Butacene via ATRP (using Polybutanylferrocene)------------------------------------73
Figure 4-6. The TGA spectra of (A) HTPB (B) mixture (C) Butacene via ATRP. (using Polybutanylferrocene)----------------------------74
Figure 4-7. The GPC curves of (A) HTPB (B) mixture (C) Butacene via ATRP. (using Polybutanylferrocene)----------------------------75
Figure 4-8 The 1H-NMR spectra of (A) HTPB (B) Butacene via ATRP
(using Chloromethylferrocene)----------------------------------76
Figure 4-9. The TGA spectra of (A) HTPB (B) mixture (C) Butacene via ATRP. (using Chloromethylferrocene)--------------------------77
Figure 4-10. The GPC curves of (A) HTPB (B) mixture (C) Butacene via ATRP. (using Chloromethylferrocene)--------------------------78
表索引
Table 1. 反應溫度的影響via Borane chemistry--------------------------64
Table 2. 反應時間的影響via Borane chemistry--------------------------64
Table 3. 單體濃度的影響via Borane chemistry--------------------------65
Table 4. 反應溫度的影響via ATRP (using Polybutanylferrocene)----65
Table 5. 反應時間的影響via ATRP (using Polybutanylferrocene)----66
Table 6. 比例變化的影響via ATRP (using Polybutanylferrocene)----66
Table 7. 反應溫度的影響via ATRP (using Chloromethylferrocene)--67
Table 8. 反應時間的影響via ATRP (using Chloromethylferrocene)--67
Table 9. Chloromethylferrocene比例變化的影響via ATRP (using Chloromethylferrocene)--------------------------------------------68
Table 10. 3-Butenylferrocene比例變化的影響via ATRP (using Chloromethylferrocene)--------------------------------------------68

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