臺灣博碩士論文加值系統

摘要
本論文的探討重點主要在於導入有機改質型黏土作為晶核劑於高分子共聚物(Copolymer)中，藉以降低物理發泡法(Physical Foaming Process )之泡體體積，並同時提升整體材料之發泡密度。藉由大幅空氣的導入，來調整所生成之奈米複合發泡材料之物理性質。
首先，利用有機改質之蒙脫土(Montmorillonite)導入甲基丙基酸丁酯及苯乙烯之單體混合液，然後進行總體聚合反應(Bulk Polymerization)，並進一步進行物理發泡。所生成之奈米複合發泡材料以穿透式電子顯微鏡觀察黏土在高分子基材之分散情形，以廣角X-ray繞射儀來觀察黏土之層間距，以掃描式電子顯微鏡來觀察發泡體之表面型態，並計算泡體之平均大小及密度。
在性質探討方面，主要是研究材料之熱性質及機械性質。在熱性質的解析方面，以熱重分析儀探討材料之熱穩定性，以微差掃描式熱分析儀觀察材料之軟化點，再以熱傳導係數分析儀量測材料之熱傳導係數，最後以動態機械分析儀分析變溫狀態下之儲存模數之變化。

Abstract
In this study, the organophilic clay used as intercalation agent was prepared by cation exchange method, which is a reaction occurred between the sodium cation of MMT clay and quaternary alkylammonium ions of hexadecyltrimethylammonium bromide. As a typical procedure for the preparation of nanocomposite systems with 0.5, 1.0, 3.0 wt-% clay, an appropriate amount of organophilic clay was first suspended in BMA-St monomer to proceed bulk polymerization. At the end of polymerization, the PBS/clay nanocomposite materials were thus obtained. Subsequently, a series of corresponding nanocomposite foamed materials were prepared by “ Physical Foaming Process ”. The foamed characterization on the structure of the nanocomposite and nanocomposite foams was evaluated by XRD measurements to show changes in the d spacing of the clay and by TEM to image the indivdual clay layers. The cell size & cell density was observed by SEM. TGA、DSC and DMA were employed to investigate the thermal stability of as-prepared specimens. Thermal transport parameters such as the thermal conductivity, thermal diffusively and specific heat were measured by a HOT DISK analyzer under room temperature.

目錄
謝誌.....................................................................I
摘要.....................................................................II
ABSTRACT.................................................................III
目錄.....................................................................IV
圖目錄...................................................................VI
表目錄...................................................................VIII

第一章 緒論..............................................................1
1-1 奈米複合材料之簡介...................................................1
1-1.1 奈米複合材料的發展歷史.............................................2
1-2 高分子材料之簡介.....................................................4
1-2.1 高分子材料的發展趨勢...............................................5
1-2.2 總體聚合法之簡介...................................................7
1-2.3 共聚合之原理 .......................................................8
1-3 無機層狀黏土之簡介...................................................11
1-4 改質劑之簡介.........................................................19
1-5 有機-無機混成材料的種類與特性........................................21
1-6 發泡塑膠之簡介.......................................................28
1-6.1發泡塑膠的成型和定型過程............................................30
1-7奈米複合發泡材料之文獻回顧............................................33
1-8發泡材料隔熱之文獻回顧................................................35
1-9 研究動機.............................................................37



第二章 實驗部分.........................................................39
2-1 實驗藥品.............................................................39
2-2 儀器部分.............................................................41
2-3 實驗步驟.............................................................45
2-3.1鈉型蒙脫土( Na+—Montmorillonite )之親油化..........................45
2-3.2 PBS / Clay奈米複合材料之製備......................................46
2-3.3 PBS / Clay奈米複合發泡材料之製備..................................49

第三章 結果與討論........................................................51
3-1 材料之結構鑑定 .......................................................51
3-1.1 廣角X-ray繞射儀(WAXRD).............................................51
3-1.2穿透式電子顯微鏡(TEM)鑑定...........................................55
3-1.3掃描式電子顯微鏡(SEM)鑑定...........................................57
3-1.4 凝膠色層分析儀(GPC)................................................61
3-2 材料之性質量測 .......................................................63
3-2.1 熱傳導係數分析儀(TPS)..............................................63
3-2.2 微差掃描式熱分析儀(DSC)............................................68
3-2.3 熱重分析儀(TGA)....................................................72
3-2.4 動態機械分析儀(DMA)................................................76

第四章 結論..............................................................85

第五章 參考文獻..........................................................87

圖目錄
圖 1-1 三種不同型態的高分子..............................................5
圖 1-2 矽氧四面體及矽氧四面體晶片示意圖..................................13
圖 1-3 鋁氧八面體及鋁氧八面體晶片示意圖..................................13
圖 1-4 蒙脫石的晶體結構..................................................15
圖 1-5 改質劑對黏土層間的改質............................................21
圖1-6 有機—無機混成材料的製備-1.........................................23
圖1-7 有機—無機混成材料的製備-2.........................................23
圖1-8 分子/黏土混成複合材料的分類-1......................................25
圖1-9 分子/黏土混成複合材料的分類-2......................................25
圖1-10 奈米黏土高分子複合材料的應用......................................27
圖 1-11 泡體結構示意圖 (A) 開孔發泡塑膠 (B) 閉孔發泡塑膠.................29
圖 1-12 泡體的成核與成長機制圖...........................................32
圖 2-1 凝膠色層分析儀裝置簡圖............................................42
圖2-2 PBS/CLAY之研究方法流程圖...........................................48
圖2-3 PBS/CLAY發泡後之研究方法流程圖.....................................50
圖 3-1 CLAY在有機化前後的X-RAY繞射圖譜...................................53
圖 3-2 PBS / CLAY奈米複合材料之廣角X-RAY繞射圖譜.........................54
圖3-3 PBS / CLAY( 3% )奈米複合材料之穿透式電子顯微鏡攝影圖CLBS3 (3萬倍).. 56
圖3-4 PBS / CLAY( 3% )奈米複合材料之穿透式電子顯微鏡攝影圖CLBS3 (5萬倍).. 56
圖3-5 不同比例PBS / CLAY 奈米複合發泡材料之SEM圖.........................58
圖3-6 PBS / CLAY 奈米複合發泡材料之CELL SIZE & DENSITY 折線圖...........59
圖3-7 PBS / CLAY 奈米複合材料與奈米發泡材料之熱傳導與熱擴散曲線圖.......65
圖3-8 不同比例PBS/ CLAY 奈米複合材料之DSC曲線圖..........................71
圖3-9 PBS / CLAY奈米複合材料之TGA圖譜....................................74
圖3-10 PBS / CLAY奈米複合發泡材料之TGA圖譜...............................75
圖 3-11 損失模數與儲存模數的示意圖.......................................77
圖 3-12 PBS / CLAY 奈米複合材料之儲存模數( STORAGE MODULUS ) 趨勢圖......79
圖 3-13 PBS / CLAY 奈米複合材料之 TANΔ趨勢圖.............................80
圖 3-14 PBS / CLAY 奈米複合發泡材料之儲存模數( STORAGE MODULUS ) 趨勢圖.. 81
圖 3-15 PBS / CLAY 奈米複合發泡材料之 TANΔ 趨勢圖........................82

表目錄
表 1-1 黏土礦物的晶體構造分類............................................12
表 1-2 幾種主要黏土礦物的化學組成........................................14
表 1-3 蒙脫土的主要應用領域與用途........................................18
表 1-4 有機/無機複合發泡材料之泡體尺寸及泡體密度數據.....................35
表 2-1 不同比例之PBS / CLAY奈米複合材料製備所需藥品用量表................47
表 3-1 黏土有機化改質前後及PBS / CLAY之廣角X-RAY繞射數據.................53
表 3-2 PBS / CLAY 奈米複合材料之廣角X-RAY繞射數據.......................54
表 3-3 PBS / CLAY 奈米複合發泡材料之CELL SIZE & DENSITY數據.............60
表 3-4 奈米複材與發泡材之平均分子量及分子量分佈.........................62
表 3-5 PBS / CLAY 奈米複合發泡材料之隔熱效率............................65
表 3-6 PBS / CLAY 奈米複合材料與奈米發泡材料之熱傳導與熱擴散詳細數據....66
表 3-7 一般材料的熱傳導參考數據.........................................67
表 3-8 PBS / CLAY 奈米複合材料之TGA , DSC和DMA的詳細數據分析整理........83
表 3-9 PBS / CLAY 奈米複合發泡材料之TGA 和DMA的詳細數據分析整理........84

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