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研究生:吳博軒
研究生(外文):Po-Shuan Wu
論文名稱:三聚氰胺聚磷酸鹽/蒙脫土/尼龍6奈米複合材料製備與物性分析
論文名稱(外文):Preparation and Physical Properties of Melamine Polyphosphate/Montmorillonite/Nylon 6 Nanocomposites
指導教授:吳震裕
指導教授(外文):Jeng-Yue Wu
口試委員:李昌崙袁維勵
口試日期:2013-01-30
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:126
中文關鍵詞:三聚氰胺磷酸尼龍6蒙脫土
外文關鍵詞:melaminephosphoric acidmelamine polyphosphatenylon 6
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本論文合成製備三聚氰胺-聚磷酸鹽MPP(Melamine Polyphosphate) 作為層狀蒙脫土改質劑,乃利用蒙脫土在水中分散之後表面帶有負電荷特性,使MPP與蒙脫土以化學反應結合,製備出MPP/Clay改質蒙脫土。將此MPP/Clay改質蒙脫土透過熔融混煉分散於尼龍6系統中形成奈米複合材料,並探討此複材之熱性質與耐燃性。
透過三聚氰胺與磷酸結合,形成三聚氰胺磷酸鹽MP(Melamine Phosphate),其在酸性環境下,表面胺基帶有正電,能作為合成MPP以及製備MPP/Clay改質蒙脫土前驅物。經由300 ℃高溫處理,使得MP分子之間彼此脫水聚合而生成MPP,由FT-IR分析,MPP可以發現在3133.8 cm-1與2843.7 cm-1為NH3+官能基特徵峰,OH官能基之特徵峰則出現在2696.7 cm-1的位置。而1385.4 cm-1則是為Melamine結構上C-N之振動吸收峰,1282.12 cm-1與1178.8 cm-1為P=O雙鍵之特徵峰。P-OH上之P-O單鍵之振動吸收峰為970.2 cm-1,888.7 cm-1則為P-O-P鍵之振動吸收峰。由此表示成功合成MPP。
MPP/Clay改質蒙脫土之製備則透過三聚氰胺之酸化,使之吸附在蒙脫土表面上,加入磷酸使蒙脫土表面先形成少許MP,之後再添加MP溶液,使得更多MP能有效吸附蒙脫土進而撐開其層間距。XRD分析顯示,此MP/Clay在 1.5 °~8 °之間,並無繞射峰吸收。之後經由高溫聚合形成MPP/Clay改質蒙脫土。由FE-SEM分析,可看出蒙脫土上吸附尺寸小於100 nm之MPP粒子。
而在MPP/Clay改質蒙脫土/尼龍6複材中。由DSC分析,複材中改質蒙脫土並不影響尼龍高分子的熔點改變。而在第一次降溫中發現複材的結晶溫度均提前發生,顯示添加了改質蒙脫土有異相成核作用。TGA分析結果顯示,導入含量為30 wt%改質蒙脫土之尼龍6複合材料,有效提昇其800 ℃時殘餘量達至19.53 wt%。極限氧指數LOI,亦由25.3提昇至37.4,顯示添加MPP/Clay改質蒙脫土能有較佳的難燃特性。而在FESEM分析中可以觀察到MPP/Clay改質蒙脫土/尼龍6複材燃燒後表面碳焦層結構緊密,因此能防止內層高分子繼續燃燒而達到耐燃的目的。


In this study, melamine polyphosphate (MPP) was prepared and served as Clay modifier. The montmorillonite (MMT) with the characteristics of negative surface charge was modified by MPP via chemical reactions in the aqueous solution. The modified montmorillonite (MPP/Clay) was further introduced to Nylon 6 matrix by melt blending method. Thermal properties and flame retardant properties of (MPP/Clay)/Nylon 6 nanocomposites were studied.
The synthesis of MPP was performed by the combination of melamine with phosphoric acid. Melamine phosphate (MP) was first prepared with positive charge in surface that can serve as the modified Clay precursor. After 300 ℃ thermal treatment, the MP molecules went through dehydration polymerization to generate MPP. Fourier transform infrared spectroscopy (FT-IR) indicated melamine polyphosphate wereobserved at 3133.8 cm-1 and 2843.7 cm-1 assigned to the vibration absorption of -NH3+, 2696.7 cm-1assigned to the vibration absorption of O-H groups, 1385.4 cm-1 assigned to the vibration of C-N groups of the triazine rings, 1282.12 cm-1 and 1178.8cm-1 assigned to the vibration of P=O bonds, 970.2cm-1 assigned to the vibration absorptions of P-O in P-O-H groups, and 888.7 cm-1 assigned to the vibration of P-O-P bonds.
The modified montmorillonite (MPP/Clay) was prepared via melamine acidification and adsorb on the MMT surface firstly. Next, phosphoric acid was added to generate MP on the Clay surface. It was observed that the increase of MP concentration could further increase the platelet distance to the extent of featureless XRD pattern (none of peaks). The generated MPP particles with diameter less than 100 nm immobilized on the MMT surface was observed by field emission scanning electronic microscopy (FE-SEM).
After melt blending, the (MPP/Clay)/Nylon 6 nanocomposites were prepared. Differential scanning calorimetry (DSC) results indicated that modified MMT does not affect the melting point of the polymer matrix. Found that the crystallization temperature of the composites occurred early in the first cooling, add modified montmorillonite has heterogeneous nucleation. Thermogravimetric analysis (TGA) showed that the incorporation of modified MMT (30 wt%) significantly enhanced the residue to 19.53 wt% at 800 ℃. Furthermore, LOI (limiting oxygen index) value increases from 25.3 to 37.4 indicating that (MPP/Clay)/Nylon 6 nanocomposites possess excellent flame retardant properties. FESEM analysis can be observed that the post-combustion of the (MPP/Clay)/Nylon 6 nanocomposites forms compact coke layer structure, thus prevents the inner polymer burning further to achieve the derived flame retardant purpose.


目 錄
謝誌............................................... i
中文摘要...........................................ii
英文摘要..........................................iii
目錄...............................................iv
表目錄.............................................vi
圖目錄...........................................viii
一、緒論............................................1
1.1 前言............................................1
1.2 耐燃劑簡介......................................2
1.3 三聚氰胺聚磷酸鹽簡介............................6
1.4 蒙脫土簡介......................................7
1.5 尼龍6簡介.......................................7
1.6 研究目的........................................8
1.7 論文研究架構與流程..............................9
二、文獻回顧.......................................15
2.1三聚氰胺磷酸鹽相關文獻..........................15
2.2三聚氰胺聚磷酸鹽相關文獻........................16
2.3蒙脫土表面改質與吸附高分子相關文獻..............26
2.4三聚氰胺聚磷酸鹽/蒙脫土/尼龍6奈米複材相關文獻...29
2.5三聚氰胺聚磷酸鹽相關專利........................31
三、實驗...........................................35
3.1 實驗儀器.......................................35
3.2 實驗藥品.......................................36
3.3 實驗步驟.......................................37
四、結果與討論.....................................41
4.1三聚氰胺聚磷酸鹽之製備與鑑定分析................42
4.1.1 紅外線光譜之官能基分析( FTIR )............42
4.1.2 熱性質分析( TGA ).........................43
4.1.3 熱性質分析( DTG ).........................45
4.1.4 X光繞射儀分析( XRD )......................45
4.1.5 場發射式電子顯微鏡分析( FESEM )...........46
4.2界面劑( SDS與CTAB )吸附MP之鑑定分析.............46
4.2.1 紅外線光譜之官能基分析( FTIR )............47
4.2.2 熱性質分析( TGA ).........................47
4.2.3 表面電位分析( Zeta potential )............48
4.3蒙脫土吸附三聚氰胺之製備與鑑定分析..............48
4.3.1 熱性質分析( TGA ).........................48
4.3.2 X光繞射儀分析( XRD )......................49
4.4 MPP/Clay改質蒙脫土之製備與鑑定分析.............50
4.4.1 X光繞射儀分析( XRD )......................50
4.4.2 紅外線光譜之官能基分析( FTIR )............51
4.4.3 熱性質分析( TGA ).........................52
4.4.4 場發射式電子顯微鏡分析( FESEM )...........53
4.4.5 Mapping分析...............................53
4.4.6 能量散佈光譜分析( EDS )............. .....54
4.5 MPP/Clay改質蒙脫土/尼龍6奈米複材製備與分析.....54
4.5.1 熱性質分析( TGA ).........................54
4.5.2 熱性質分析( DTG ).........................55
4.5.3 熱性質分析( DSC ).........................56
4.5.4 限氧指數分析( LOI ) ......................57
4.5.5 X光繞射儀分析( XRD )......................58
4.5.6 場發射式電子顯微鏡分析( FESEM ) ..........58
五、結論 ..........................................60
六、參考文獻 ......................................62
附錄(一)、樣品代號說明 .......................... 122
附錄(二)、三聚氰胺吸附於蒙脫土之平衡吸附量、吸附效率
與平衡濃度..............................123
附錄(三)、Langmuir方程式求取平衡參數..............124
附錄(四)、改質蒙脫土中MPP與Clay含量關係計算.......125

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