Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3434
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dc.contributor.advisor戴憲弘zh_TW
dc.contributor.advisorShenghong A. Daien_US
dc.contributor.authorCheng, Chih-Chiaen_US
dc.contributor.author鄭智嘉zh_TW
dc.contributor.other中興大學zh_TW
dc.date2006zh_TW
dc.date.accessioned2014-06-06T05:31:55Z-
dc.date.available2014-06-06T05:31:55Z-
dc.identifier.urihttp://hdl.handle.net/11455/3434-
dc.description.abstract巨環形高分子中間體的合成與開環聚合反應是高分子合成中最受矚目的發展重點之一。至目前為止,有效合成巨環形高分子中間體的方法仍充滿挑戰,但相較於一般線性結構,環狀結構潛在可提供優越物性及加工便利之優點。由於本實驗室近年來致力於碳二亞胺化學(carbodiimide chemistry)及合成異氰酸鹽預聚物(isocyanate prepolymer)之研究,由延伸其領域而發現快速又簡易的方法可製備反應型巨環狀高分子中間體。 本研究率先以窄分子量分佈預聚物進行分子內環化反應,進而成功合成出具高反應性的巨環形碳二亞胺(Macrocyclic CDIs,MC-CDI)。二異氰酸鹽中間體(diisocyanate intermediates)可以簡易地藉由2,4-TDI加入至聚異丙二醇中反應製備而得,並在高度稀釋(high dilution)合成法及1,3-Dmethyl-3-phospholene oxide(DMPO)催化劑下,完成MC-CDI之製備。單純之MC-CDI可藉由液相管柱層析(LC)進行純化分離,純化後可得MC-CDI產率約為40~70%,視巨環之分子量而定。MC-CDI更能進一步合成出高產率的衍生物巨環形醯基尿素(Macrocyclic Acylureas,MC-Acylureas)、末端帶有酸基的巨環形醯基尿素(Acid-Functionalized MC-Acylureas)及巨環形尿素(Macrocyclic Ureas,MC-Ureas)。開環模式反應也證實可經MC-Acylurea之熱反應而轉化成線形產物。 由於巨環形醯基尿素具有熱裂解開環之特性,我們成功地運用末端帶有酸基的巨環形醯基尿素進行開環聚合反應(Ring-Opening Polymerization,ROP),且簡易地製備出具高分子量的線形共聚合物。藉由本次於MC-CDI之研究及新發現,巨環形功能性中間體的性質及應用有更多新的瞭解,也使它們在高分子製程上具有嶄新的應用價值。zh_TW
dc.description.abstractSynthesis and ring-opening polymerization of macrocyclic polymeric intermediates are one of the most highly sought-after targets in polymer synthesis. Synthesis of viable macrocyclic intermediates has been very challenging so far, but potentially the cyclic approach could provide many advantages over linear counterparts in areas of superior physical properties and simplicity in processing. Because of recent research in our laboratory on carbodiimide chemistry and isocyanate prepolymer synthesis, we have found a versatile facile approach of making macro-ring compounds. We like to report the first successful synthesis of reactive macrocyclic carbodiimide (MC-CDI) through intramolecular cyclization of toluene diisocyanate prepolymer as the intermediate. The diisocyanate intermediates were prepared readily by addition 2,4-TDI to polypropylene diols. MC-CDIs were then obtained by cyclization of the prepolymer diisocyanate under high-dilution synthesis using DMPO as the catalyst. MC-CDIs could be purified by LC column and isolated in 40~70% yield for different molecular weight. MC-CDIs were converted into macrocyclic acylureas (MC-Acylureas), acid-functionalized MC-Acylureas and macrocyclic ureas (MC-Ureas) in high yield. The ring-opening reaction of macrocyclic polymer intermediates have also been demonstrated through heating of the MC-Acylurea. The MC-Acylureas have shown to possess ring-opening properties through thermotysis. We have successfully applied their reaction to effect ring-opening polymerization (ROP) of acid-functionalized MC-Aculurea to synthesize for linear copolymers of high molecular-weight. Through our first MC-CDI research and discovery, we not only have advanced new fundamental understandings on these macrocyclic functional intermediates but also have found their novel applications in polymer processing.en_US
dc.description.tableofcontents目 錄 頁碼 中文摘要 .............................................................................. I 英文摘要 .......................................................................................... I I I 誌謝 ................................................................................................... IV 目錄 ............................................................................................... V 表目錄 .............................................................................................. X 圖目錄 ............................................................................................... XI 第一章 序論 ............................................................................... 1 第二章 文獻回顧 .......................................................................... 4 2-1 環形高分子之分子特性 ....................................................... 4 2-2 環形高分子之合成 ................................................................ 6 2-3 以巨環形分子進行開環聚合反應製備高分子材料 ............ 8 2-4 本實驗室之核心技術回顧 ..................................................... 11 2-5 環形碳二亞胺之合成 ............................................................. 18 2-6 環形N-醯基-N,N’-雙取代尿素(Cyclic Acylurea)之合成 23 第三章 實驗 ................................................................................... 25 3-1 實驗藥品 ................................................................................. 27 3-1-1 二異氰酸鹽 (Diisocyanate) ............................................. 27 3-1-2 反應觸媒 (Reactive Catalyst) ......................................... 28 3-1-3 聚二元醇 (Polydiol) ......................................................... 29 3-1-4 有機羰酸 (Carboxylic Acid) ............................................ 31 3-1-5 有機溶劑 (Organic Solvents) .......................................... 33 3-1-6 終止反應試劑 (Blocking Agent) ..................................... 39 3-2 實驗合成 ................................................................................. 40 3-2-1 製備窄分子量分佈且含末端異氰酸鹽官能基之預聚物 40 3-2-1-1預聚物追蹤反應之合成方法 ......................... 41 3-2-1-2製備窄分子量預聚物之合成方法 .................. 42 3-2-2 經由碳二亞胺(CDI)化學路徑進行分子內環化反應 之研究 ............................................................................. 43 3-2-2-1 不同溶劑與溫度的環化反應之研究 ...................... 45 3-2-2-1-1 不同溶劑與溫度下的環化反應之方法 ........... 46 3-2-2-2環化濃度效應之研究 .......................................... 47 3-2-2-2-1在不同濃度下探討環化濃度效應之合成方法 47 3-2-3 巨環形碳二亞胺(MC-CDI)純化之研究 ….................... 49 3-2-3-1 巨環形碳二亞胺(MC-CDI)之合成及純化方法 .... 49 3-2-4 巨環型碳二亞胺(MC-CDI)衍生反應之研究 …............ 51 3-2-4-1以醋酸(Acetic Acid)合成MC-Acylurea之方法 ... 51 3-2-4-2以己二酸(Adipic Acid)合成MC-Acylurea之方法 52 3-2-4-3以TMA(Trimellitic Anhydride)合成MC-Acylurea 之方法 ....................................................................... 53 3-2-4-4末端帶有酸酐官能基的MC-Acylurea 經水解反應 合成末端帶有酸酯官能基的MC-Acylurea之方法 55 3-2-4-5巨環形尿素(MC-Urea)之合成方法 ....................... 56 3-2-5 巨環形衍生物(MC- Derivatives)開環模式反應之研究 57 3-2-5-1 MC-Acylurea開環模式反應之方法 ........................ 57 3-2-6 以巨環形衍生物進行開環聚合反應(Ring-Opening Polymerization)製備線性高分子之初步研究 .............. 59 3-2-6-1以巨環形衍生物進行開環聚合反應之實驗步驟 .... 60 3-3 實驗儀器 ................................................................................. 63 第四章 結果與討論 ........................................................................ 68 4-1 製備窄分子量分佈且含末端異氰酸鹽官能基之預聚物 TPG、400、700及2000結果 ............................................. 68 4-1-1 以TPG與2,4’-TDI進行合成窄分佈預聚物(1)之結果 68 4-1-2 以PPG 400與2,4’-TDI進行合成窄分佈預聚物(2) 之結果 .............................................................................. 72 4-1-3 以PPG 700與2,4’-TDI進行合成窄分佈預聚物(3) 之結果 .............................................................................. 76 4-1-4 以PPG 2000與2,4’-TDI進行合成窄分佈預聚物(4) 之結果 .............................................................................. 80 4-1-5 以不同分子量PPG合成窄分佈預聚物(1~4)之最佳 反應控制條件 ................................................................. 84 4-1-6 以不同分子量PPG鏈長合成窄分佈預聚物之結構鑑定 84 4-2 經由TDI-PPG聚醚胺酯預聚物(Prepolymer)之分子內環 化反應合成碳二亞胺(CDI)之研究 ............................. 90 4-2-1 不同溶劑與溫度的環化反應之結果 .............................. 90 4-2-2 環化濃度效應之研究結果 .......................................... 95 4-3 巨環形碳二亞胺(MC-CDI)之分離及純化之研究結果 98 4-3-1 巨環形碳二亞胺(MC-CDI)純化之結果 ....................... 98 4-3-2 巨環形碳二亞胺(MC-CDI)之結構鑑定 ..................... 102 4-3-2-1巨環形碳二亞胺(MC-CDI)之FTIR鑑定結果 ..... 102 4-3-2-2巨環形碳二亞胺(MC-CDI)之200MHz 1H-NMR 結構鑑定之結果 .................................................... 104 4-3-2-3巨環形碳二亞胺(MC-CDI)之300MHz 13C-NMR 結果 ........................................................................ 109 4-3-2-4巨環形碳二亞胺(MC-CDI)之GPC結果 ............. 112 4-3-2-5巨環形碳二亞胺(MC-CDI TPG)之元素分析 (Element Analysis)結果 ...................................... 116 4-3-2-6巨環形碳二亞胺(MC-CDI TPG)之質譜儀 (Mass Spectrum)分析結果 ................................... 117 4-4 巨環形碳二亞胺(MC-CDI)之熱性質探討 ........................ 118 4-5 巨環型碳二亞胺(MC-CDI)衍生反應之結果 .................... 123 4-5-1 以醋酸合成MC-Acylurea之結果 ................................. 123 4-5-1-2以醋酸在不同溶劑下合成MC-Acylurea之反應 速率探討 ................................................................ 125 4-5-2 以己二酸合成MC-Acylurea之結果 ............................ 133 4-5-3 以苯偏三甲酸酐(TMA)合成MC-Acylurea之結果 ... 137 4-5-4 MC-Urea之合成方法 ................................................... 142 4-6 巨環形衍生物(MC-Derivatives)開環模式反應之結果 153 4-7 巨環形衍生物(MC-Derivatives)進行開環聚合反應製備 線性高分子之初步嘗試結果 .............................................. 157 第五章 結論 .................................................................................. 169 第六章 參考文獻 .......................................................................... 172zh_TW
dc.language.isoen_USzh_TW
dc.publisher化學工程學系所zh_TW
dc.subjectring-opening polymerizationen_US
dc.subject巨環形碳二亞胺zh_TW
dc.subjectmacrocyclic CDIen_US
dc.subjectmacro-cyclic acylureaen_US
dc.subjectprepolymers with narrow-molecular weightsen_US
dc.subjecthigh-dilution synthesisen_US
dc.subjectintramolecular cyclizationen_US
dc.subject開環聚合反應zh_TW
dc.subject巨環型醯基尿素zh_TW
dc.subject窄分子量分佈PU預聚物zh_TW
dc.subject高度稀釋合成zh_TW
dc.subject分子內環化反應zh_TW
dc.titleNovel Reactive Cyclic-Polymer Intermediates:Synthesis, Reaction and Application of Macrocyclic Poly(propylene oxide) Carbodiimides (MC-CDI).en_US
dc.title新穎反應型的環狀高分子中間體:巨環形聚丙烯醚碳二亞胺之合成、反應及應用zh_TW
dc.typeThesis and Dissertationzh_TW
item.languageiso639-1en_US-
item.openairetypeThesis and Dissertation-
item.cerifentitytypePublications-
item.grantfulltextnone-
item.fulltextno fulltext-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
Appears in Collections:化學工程學系所
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