臺灣博碩士論文加值系統

為了模擬室溫硬化型矽橡膠交聯點在鹼催化下行親核性裂解的反應行為，本研究以Tetrakis(trimethylsiloxy)-silane作為室溫硬化型矽橡膠之模式物，研究內容在於探討醇解矽氧鍵結時鹼觸媒濃度、裂解劑濃度及溫度對反應速率的影響，建立反應速率模式，估算反應參數及活化能；並對醇解與胺解同時存在時的裂解行為有系統地探討，最後建立胺解動力模式並與醇解結果作比較。
模式物在鹼性觸媒下醇解反應結果顯示：1.裂解劑與鹼觸媒濃度愈高裂解速率愈快。2.模式物濃度隨反應時間逐漸減少，而反應時間較長時模式物濃度消耗速率趨於平緩，達到平衡。3.裂解產物有再聚合成高分子產物的現象。4.昇溫會增快反應的進行。
由所假設的反應機構及推導的反應速率式，使用擬線性法，配合最小平方誤差法估算不同溫度下醇解反應之反應參數，，並求得活化能為19.244 kJ/mole。醇解反應速率常數在5，30，40及50℃下分別為0.0028，0.0053，0.0075及0.0097 min-1M-2。
探討醇解與胺解競爭裂解模式物的快慢時，由實驗結果顯示醇解為主要的裂解反應，其產物與醇解反應產物一致。
以初始反應模式求得5℃下以乙胺胺解模式物的反應速率常數為0.0061 min-1M-2、8℃為0.0065 min-1M-2、10℃為0.0068 min-1M-2，活化能為14.526 kJ/mole。實驗結果得知反應初期胺解反應比醇解反應快但胺解反應很快趨於平衡。當醇胺競爭反應時，初期以胺解為主，後期以醇解為主反應。

Base catalysts enhanced ethanolysis and aminolysis reactions of room temperature vulcanized polydimethylsiloxane network were studied with the aid of a model compound. Tetrakis(trimethylsiloxy)-silane (M4Q) was chosen as a model compound the PDMS network. Experimental results showed that the rate of disappearance of M4Q decreased with increasing concentrations of base catalyst and ethanol. The reaction rate was increased by increasing the reaction temperature. Products of high molecular weight were also found as the reaction proceeded. Ethanolysis was the main reaction when ethanol and diethylamine coexisted in the reaction system.
The mechanism and rate law of the ethanolysis and aminolysis reactions were proposed. A quasilinearization method was employed to determine the best set of the kinetic parameters of ethanolysis. Initial rate analysis was used to determine the parameters of aminolysis. The reaction constants of ethanolysis reaction at temperatures of 5 ,30 ,40 and 50℃ are 0.0028 ,0.0053 ,0.0075 and 0.0097 min-1M-2, respectively. The reaction constants of aminolysis at temperature 5, 8, and10℃ are 0.0061, 0.0065 and 0.0068 min-1M-2, respectively. The activation energies of the ethanolysis and aminolysis reaction are 19.244 kJ/mole and 14.526 kJ/mole, respectively. The initial rate of aminolysis reaction was faster than that of ethanolysis reaction. However, aminolysis reached equilibrium much faster than ethanolysis.

目錄
中文摘要…………………………………………………….…..Ⅰ
英文摘要………………………………………….……………..Ⅱ
目錄……………………………….……………………………..Ⅲ
表目錄………………………………..………………………….Ⅵ
圖目錄…………………………………..……………………….Ⅶ
第一章 緒論………………………………………………………...1
第二章 文獻回顧…………………………………………………...3
2-1 聚矽氧烷高分子之簡介…………………………………....3
2-2 矽氧烷分子的裂解方法………………………………........9
2-2.1 質子酸裂解反應……………………………………11
2-2.2 類質子酸裂解反應…………………………………12
2-2.3 加鹼裂解反應………………………………………13
2-2.4 胺解反應………………………………………………14
2-2.5 醇解反應……………………………………………....17
第三章 實驗裝置與實驗步驟……………………………………..25
3-1 實驗裝置…………………………………………………...25
3-1.1 實驗材料………………………………………………25
3-1.2 實驗儀器……………………………………………….27
3-2 實驗步驟……………………………………………………28
3-2.1 鹼性觸媒醇解反應…………………………………….28
3-2.2 鹼性觸媒醇解與胺解競爭反應……………………….28
3-2.3 鹼性觸媒胺解反應…………………………………….29
3-3 實驗裝置圖…………………………………………………30
3-3.1 鹼性觸媒醇解反應、鹼性觸媒醇解與胺解競爭反
應之實驗裝置圖……………………………………….30
3-3.2 鹼性觸媒胺解反應之實驗裝置圖…………………….31
3-4 流程圖………………………………………………………32
3-4.1 鹼性觸媒催化下醇解反應、鹼性觸媒催化下醇解
與胺解競爭反應之實驗流程圖………………………..32
3-4.2 鹼性觸媒催化下胺解反應之實驗流程圖…………….34
第四章 結果與討論………………………………………………...35
4-1 模式物醇解與胺解反應的反應機構………………………36
4-1.1 醇解反應機構………………………………………….36
4-1.2 胺解反應機構………………………………………….37
4-2 醇解反應實驗結果…………………………………………39
4-2.1 反應溫度對裂解反應速率之影響……………………39
4-2.2 觸媒濃度對反應速率之影響………………………….40
4-2.3 裂解劑濃度對反應速率之影響……………………….41
4-2.4 醇解反應式之推導…………………………………….42
4-2.5 反應式參數之估算…………………………………….45
4-2.6 醇解反應活化能之估算……………………………….46
4-2.7 醇解反應之理論值與實驗值比較……………….…....48
4-3 醇解與胺解競爭反應實驗結果………………….…………53
4-4 胺解反應實驗結果……………………………….…………55
4-4.1 胺解反應式之推導………………………….………….56
4-4.2 醇解與胺解起始反應速率之比較…….……………59
4-4.3 胺解反應活化能之估算……………….……………….62
4-4.4 醇解或胺解與醇胺競爭反應之理論值與實驗值比較..63
第五章 結論與建議……………………………….…………….…..64
5-1 結論…………………………………………….……………64
5-2 建議………………………………………….………………66
文獻參考 ………………………………………………………………67
附錄 A ………………………………………………………….…..70
附錄 B ………………………………………………………….…..79

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