以聚二甲基矽氧烷(KF-6001, Polydimethylsiloxane, PDMS, 1800 g/mol)為雙醇基，先和過量之IPDI進行反應，形成末端-NCO官能基之PU預聚合物(PDMS-NCO)，接著再和aminopropyl triethoxysilane (APTES)反應，形成末端-Si(OH)3之PU 寡聚物(PDMS-APTES)；改質後之PDMS-APTES，分別摻混四乙氧基矽烷(TEOS)或奈米級二氧化矽(Nano-silica)，利用溶膠法，形成含PDMS之PU與奈米矽膠之混成物。探討添加不同量的四乙氧基矽烷或奈米級二氧化矽其所形成的性質差異，並以量測混成物之物理性質如膠含量、對水與乙醇吸收損失率、接觸角及硬度等方面都比原本PDMS-APTES皆有所提升，在UV/vis穿透度，隨添加量而有所下降，在熱性質方面使用熱重分析(TGA)測量，發現其熱安定性皆有所提升;在動態機械分析(DMA)測量，可以發現改質後的軟鍊端Tg比之前PDMS-APTES還要低溫而硬鏈端比之前高溫;最後並利用掃描式電子顯微鏡(SEM)觀察材料截面型態，發現TEOS和Nano-silica等皆均勻分佈PDMS-APTES基材，並無相分離現象發生。

A PDMS-containing PU oligomer with triethoxysilane as the terminal groups that is obtained from NCO-terminated PU prepolymer with aminopropane triethyoxysilane (APTES). This PU prepolymer (PDMS-APTES) is prepared by the reaction of polydimethylsiloxane diol (KF-6001) with excess amount of isophorone diisocyanate (IPDI). PU/silica hybridized composites are obtained by the blending of PU prepolymer (PDMS-APTES) with tetraethoxysilane (TEOS) and nano-silica in various dosages, via a sol-gel processes, respectively. The PU/silica hybrids are evaluated by the measurements of physical properties, such as gel content, water absorption, contact angle, hardness. Even though the thermal stability (TGA) increases and the transmittance of UV/visible spectrum is decreases as increasing nano-silica dosage. That is due to the aggregation occurs when the dosage of nano-silica increases, however, SEM micrographs proves that the dispersion of silica is still in nano-scale.

中摘......................................................I
英摘.....................................................II
圖表目錄.................................................VI
ㄧ、序論..................................................1
1-1 前言..................................................1
1-2 實驗動機..............................................3
二、文獻回顧..............................................4
2-1  聚氨基甲酸乙酯(PU)的介紹.............................4
2-2  有機/無機奈米複合材料................................6
2-3  溶膠-凝膠法(Sol-Gel).................................9
2-4  溶膠-凝膠法之控制變因...............................10
2-5  聚矽氧烷簡介........................................14
    2-5-1歷史發展........................................14
    2-5-2聚二甲基矽氧烷基本性質..........................16
    2-5-3聚二甲基矽氧烷應用..............................19
三、實驗.................................................21
3-1 實驗藥品.............................................21
3-2 儀器.................................................22
3-3 合成步驟.............................................23
    3-3-1 PDMS-NCO合成步驟...............................23
    3-3-2 PDMS-APTES合成步驟.............................24
3-4 由溶膠-凝膠法合成奈米複合材料薄膜....................24
    3-4-1 PDMS-APTES與無機奈米二氧化矽複合材料的合成.....24
    3-4-2 樣品編號命名...................................26
3-5 FT-IR光譜鑑定測......................................27
3-6掃描式電子顯微鏡(SEM) ................................27
3-7薄膜物理性質測試......................................28
    3-7-1膠含量測試(Gel Content).........................28
    3-7-2去離子水浸泡吸水率(Water-Uptake ％)與對水損失率
         (Weight ％ Loss in Water) ..............28        
    3-7-3 95％乙醇溶液浸泡吸收率(Ethanol-Uptake ％)          
         乙醇損失率(Weight ％ Loss in Ethanol)...........29
    3-7-4薄膜接觸角(Contact Angle)測定...................30
3-8 熱重分析(Termalgravimetric Analysis， TGA)測試.......32
3-9動態機械分析(Dynamic Mexhanical Analysis，DMA)........33
3-10可見光穿透度(UV-Transmittance).......................33
3-11 能量光譜儀(Energy Dispersive Spectrometer, EDS).....34
四、結果與討論...........................................35
4-1 PDMS-NCO合成步驟.....................................35
4-2 PDMS-APTES合成步驟...................................35
4-3 PDMS-APTES的物理性質.................................41
    4-3-1 膠含量.......................................................41
    4-3-2水與乙醇對薄膜的吸收損失率......................43
    4-3-3可見光穿透度分析 ......................................................45
    4-3-4 接觸角.........................................48
    4-3-5 薄膜硬度測試...................................50
4-4熱重分析(Thermal Gravity Analysis,TGA) ...............51
4-5薄膜動態機械分析......................................58
4-6掃描式電子顯微鏡(Scanning Electronic Microscopy, SEM).67
4-7 能量質譜儀(Energy Dispersive Spectrometer,EDS)........................................73
五、結論.................................................77
六、參考資料.............................................79

圖 表 目 錄
Scheme I PDMS-NCO 的製備................................................................23
Scheme II PDMS-APTES 的製備............................................................24
Scheme III 利用溶膠-溶劑法制備奈米複合材料薄膜.........................25
Table 3-1 樣品命名.................................................................................26
Table 4-1 PDMS-APTES/TEOS 薄膜之膠含量......................................42
Table 4-2 PDMS-APTES/Nano-silica 薄膜之膠含量.............................42
Table 4-3 PDMS-APTES/TEOS 薄膜之水與乙醇對薄膜吸收損失率..45
Table 4-4 PDMS-APTES/Nano-silica 薄膜之水與乙醇對薄膜吸收損失
率....................................................................................................45
Table 4-5 PDMS-APTES/TEOS 薄膜可見光穿透度…………………..46
Table 4-6 PDMS-APTES/Nano-silica 薄膜可見光穿透度………….…46
Table 4-7 PDMS-APTES/TEOS 薄膜之接觸角......................................49
Table 4-8 PDMS-APTES/Nano-silica 薄膜之接觸角.............................49
Table 4-9 PDMS-APTE/TEOS 薄膜之硬度測試…………………….50
Table 4-10 PDMS-APTES/Nano-silica 薄膜之硬度測試…………...…50
Table 4-11 PDMS-APTES/TEOS 薄膜之熱重分析................................53
Table 4-12 PDMS-APTES/Nano-silica 薄膜之熱重分析.......................53
Table 4-13 PDMS-APTES/TEOS 薄膜之動態機械分析.......................60
Table 4-14 PDMS-APTES/Nano-silica 薄膜之動態機械分析...............60
Table 4-15 PDMS-APTES/TEOS 之薄膜Si 含量....................................73
Table 4-16 PDMS-ATES/Nano-silica 之薄膜Si 含量…………………..73
Figure 2-1 矽烷氧化物之水解縮合反應.................................................10
Figure 2-2 酸性條件下，水解縮合反應機制.........................................11
Figure 2-3 鹼性條件下，水解縮合反應機制.........................................12
Figure 2-4 聚矽氧烷四種基本單位.......................................................14
Figure 3-1 接觸角之模擬圖...................................................................31
Figure 4-1 PDMS 之FT-IR 光譜圖..........................................................35
Figure 4-2 IPDI 之FT-IR 光譜圖.............................................................36
Figure 4-3 PDMS-NCO 之FT-IR 光譜圖................................................37
Figure 4-4 APTES 之FT-IR 光譜圖........................................................38
Figure 4-5 PDMS-APTES 之FT-IR 光譜圖............................................39
Figure 4-6 PDMS-APTES/TEOS 薄膜紫外光穿透度…………..……..47
Figure 4-7 PDMS-APTES/Nano-silica1 薄膜紫外光穿透度………..…47
Figure 4-8 PDMS-APTES/TEOS 薄膜之熱重分析圖............................54
Figure 4-9 PDMS-APTES/TEOS 薄膜之熱重量損失圖……................55
Fugure 4-10 PDMS-APTES/Nano-silica 薄膜之熱重分析圖.................56
Figure 4-11 PDMS-APTES/Nano-silica 薄膜之熱重量損失圖..............57
Figure 4-12 PDMSA-PTES/Nano-silica 薄膜DMA圖............................61
Figure 4-13 PDMS-APTES/Nano-silica 薄膜儲存模數圖......................62
Figure 4-14 PDMS-APTES/Nano-silica 薄膜消耗模數圖......................63
Figure 4-15 PDMS-APTES/TEOS 薄膜DMA圖....................................64
Figure 4-16 PDMS-APTES/TEOS 薄膜儲存模數圖…………………..65
Figure 4-17 PDMS-APTES/TEOS 薄膜消耗模數圖………………….66
Figure 4-18 PDMS-APTES/TEOS or Nano-silica 0phr 薄膜X50,000
SEM 圖.........................................................................................68
Figure 4-19 PDMS-APTES/TEOS 5phr 薄膜50,000 SEM 圖.................68
Figure 4-20 PDMS-APTES/TEOS 10phr 薄膜50,000 SEM 圖…….......69
Figure 4-21 PDMS-APTES/TEOS 15phr 薄膜50,000 SEM 圖...............69
Figure 4-22 PDMS-APTES/TEOS 20phr 薄膜50,000 SEM 圖...............70
Figure 4-23 PDMS-APTES/Nano-silica 5 phr 薄膜50,000 SEM 圖.......70
Figure 4-24 PDMS-APTES/Nano-silica 10 phr 薄膜50,000 SEM 圖.....71
Figure 4-25 PDMS-APTES/Nano-silica 15 phr 薄膜50,000 SEM 圖.....71
Figure 4-26 PDMS-APTES/Nano-silica 20 phr 薄膜50,000 SEM 圖.....72
Figure 4-27 PDMS-ATES/TEOS or Nano-silica 0phr 之EDS 圖…….74
Figure 4-28 PDMS-APTES/TEOS 5phr 之EDS 圖…………………….74
Figure 4-29 PDMS-APTES/TEOS 10phr 之EDS 圖………………...…74
Figure 4-30 PDMS-APTES/TEOS 15phr 之EDS 圖………………...…75
Figure 4-31 PDMS-APTES/TEOS 20phr 之EDS 圖………………...…75
Figure 4-32 PDMS-APTES/Nano-silica 5phr 之EDS 圖…………….…75
Figure 4-33 PDMS-APTES/Nano-silica 10phr 之EDS 圖………….…76
Figure 4-34 PDMS-APTES/Nano-silica 15phr 之EDS 圖………….…76
Figure 4-35 PDMS-APTES/Nano-silica 20phr 之EDS 圖………….…76

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