臺灣博碩士論文加值系統

本研究主要針對π配位體在Cp*Ti(OMe)3/MAO觸媒系統聚合對位性苯乙烯時，對反應機制的影響進行探討 (開始先使用4甲基苯乙烯單體替代，因為GPC分析上的方便) 。實驗結果發現四種π配位體(methylstyrene,β-pinene,1-octene,1-hexene) 搭配氫氣皆可以有效的降低對位聚4甲基苯乙烯的分子量，藉由1H NMR的分析，確定π配位體並無聚合上高分子。
我們發現在苯乙烯之聚合條件下加入β-pinene、 2,5Norbornadiene、Diphenylacetyleney並在無氫氣的條件下聚合對位聚4甲基苯乙烯，可明顯降低聚合物之分子量，此外1H NMR及13C NMR的圖譜，證實此類配位單體的增加會明顯降低聚合物之對位規則性。最後，聚合對位聚苯乙烯(使用2,5Norbornadiene)，得到13C NMR數據與文獻比較得到規則性變化的位置，輔以高分子Tm的降低，推測相關研究的結果證實了sPS之活性的觸媒中心具備可配位配位體之空軌域,而藉由導入不同的配位體參與觸媒之配位可明顯調控聚合物之分子量與立體規則性。

In the study of the metallocene catalysts mediated polymerization of styrene-based polymers, we have found that the addition of the π-coordinated complexes, including methyl styrene, β-pinene 1-octene, 1-hexene, can lead to a substantial decrease of the molecular chain length in the resulting polymers. The 1H NMR analyses of the resulting polymers clearly reveal that these π-coordinated complexes are unable to incorporate into the polymer backbone; thus, the molecular weight reduction is not due to the occurrence of selective chain transfer reaction induced by these π-coordinated complexes. We also found that polymers prepared in the presence of these π-coordinated complexes under hydrogen have a substantially higher stereoregularity (syndiotacticity) than polymers prepared in the presence of these π-coordinated complexes but without hydrogen. These results indicate that these π-coordinated complexes can participate in the styrene polymerization pathway by binding onto the vacant coordination site of the active metallocene catatlysts, and this leads to the generation of a lower reactive catalyst, which produces lower molecular weight polymers with a lower stereoregularity.

第一章 緒論..............................................................................................1
1-1 前言..............................................................................................2
1-2 文獻回顧及原理介紹..................................................................2
1-2-1 聚苯乙烯簡介.........................................................................2
1-2-2 Metallocene觸媒系統簡介....................................................16
1-2-3 鏈轉移反應...........................................................................22
1-2-4 陰離子聚合反應簡介...........................................................24
1-3 研究大綱....................................................................................27
第二章 實驗部份....................................................................................29
2-1 實驗藥品....................................................................................34
2-2 實驗設備與分析儀器................................................................36
2-3 分析儀器原理............................................................................36
2-3-1 調幅式微差掃描熱分析儀................................................41
2-3-2 凝膠滲透層析儀 (Gel Permeation Chromatography, GPC)
............................................................................................44
2-3-3 熱重分析儀........................................................................44
2-3-4 核磁共振儀........................................................................45
2-4 單體與溶劑之純化....................................................................45
2-4-1 甲苯除水純化.....................................................................46
2-4-2 苯乙烯、4-甲基苯乙烯之除水純化...................................47
2-5 藥品配置方式..........................................................................47
2-5-1 有機金屬茂觸媒的配製.....................................................47
2-5-2 甲基氧化鋁（MAO）的配製............................................47
2-6 實驗步驟..................................................................................47
2-6-1 π配位體影響反應機制相關研究研究...............................48
第三章 結果與討論................................................................................53
3-1 以Cp*Ti(OMe)3/MAO觸媒系統中影響聚苯乙烯分子量的相關研究....................................................................................53
3-2 不同π配位體影響對位性4-甲基聚苯乙烯聚合機制之研究55
3-2-1 使用-methylstyrene影響sPMS分子量研究...................56
3-2-2 使用β-pinene影響sPMS分子量研究...............................60
3-2-3 使用1-octene影響sPMS分子量研究...............................63
3-2-4 使用1-hexene影響sPMS分子量研究..............................65
3-2-5 π配位體影響對位性聚4-甲基苯乙烯分子量比較...........68
3-3 以Cp*Ti(OMe)3/MAO觸媒系統在無氫氣下研究................70
3-3-1 選用β-pinene在無氫氣下影響sPMS聚合之研究...........70
3-3-2 選用2,5-Norbornadiene在無氫氣下影響sPMS聚合之研究.........................................................................................74
3-3-3 選用Diphenylacetylene在無氫氣下影響sPMS聚合之研究.........................................................................................77
3-3-4 選用polybutadiene在無氫氣下影響sPMS聚合之研究..79
3-3-5 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之研究.........................................................................................83
3-4 2,5-Norbornadiene影響苯乙烯聚合物之DSC分析..............88
3-5 π配位體影響對位聚4-甲基苯乙烯聚合之機制....................89
3-5-1 Zambelli與Idemitsu的配位原理.....................................89
3-5-2 π配位體影響對位聚4-甲基苯乙烯聚合機制之建構.....90
第四章 結論............................................................................................96
縮寫對照表..............................................................................................99
參考文獻................................................................................................100







圖目錄
圖1-2-1 金屬茂觸媒CpTOMe3 /MAO+AlR3的起始反應機制..........4
圖1-2-2 活化觸媒中心經苯乙烯單體配位之穩定的中間過渡狀態...4
圖1-2-3 聚苯乙烯之鏈成長反應機制...................................................5
圖1-2-4 對位性聚苯乙烯高分子可能的結構.......................................5
圖1-2-5 對位性聚苯乙烯的可能加成方式...........................................6
圖1-2-6 苯乙烯單體加成反應可能的機制...........................................6
圖1-2-7 苯乙烯聚合之β-氫的消去反應機制......................................7
圖1-2-8 苯乙烯聚合之鏈轉移到TMA的反應機制.............................8
圖1-2-9 苯乙烯聚合之鏈轉移到單體的反應機制...............................9
圖1-2-10 苯乙烯聚合之鏈轉移到氫氣的反應機制...............................9
圖1-2-11 苯乙烯聚合之鏈轉移到H-BR2的反應機制.........................10
圖1-2-12 有機茂金屬觸媒對苯乙烯單體進行聚合過程.....................12
圖1-2-13 工程塑膠的電氣性質.............................................................15
圖1-2-14 Ferrocene...............................................................................17
圖1-2-15 MAO對Metallocene觸媒之活化過程................................18
圖1-2-16 MAO的線型及環狀型結構.................................................19
圖1-2-17 氫氣、TIBA對sPS鏈轉移機制............................................22
圖1-2-18 9BBN對sPS的鏈轉移機制.................................................23
圖2-3-1 MDSC與DSC測量Cp之示意圖...........................................38
圖2-3-2 MDSC的加熱方式.................................................................39
圖2-3-3 GPC 層析管截面示意圖.......................................................41
圖2-3-4 利用多種已知絕對分子量的聚苯乙烯標準品(polystyrene standards)對其相對沖提時間(elution time)所做的圖............................43
圖2-3-5 GPC層析系統RI檢測器的校正曲線...................................43
圖2-4-1 甲苯除水純化裝置圖.............................................................45
圖2-4-2 單體、溶劑除水純化裝置圖..................................................46
圖2-6-1 反應裝置圖一.........................................................................48
圖2-6-2 脂肪萃取器.............................................................................52
圖3-1-1 TIBA對分子量影響...............................................................54
圖3-2-1 添加-methylstyrene對sPMS分子量影響之GPC疊圖.....57
圖3-2-2 添加-methylstyrene對sPMS影響之1H NMR圖譜...........59
圖3-2-3 -methylstyrene影響pMS高分子反應路徑示意圖............60
圖3-2-4 添加β-pinene對sPMS分子量影響之GPC疊圖.................62
圖3-2-5 添加β-pinene對sPMS影響之1H NMR圖譜.......................62
圖3-2-6 添加1-octene對sPMS分子量影響之GPC疊圖..................65
圖3-2-7 添加1-octene對sPMS影響之1H NMR圖譜........................66
圖3-2-8 添加1-hexene對sPMS分子量影響之GPC疊圖..................66
圖3-2-9 添加1-hexene對sPMS影響之1H NMR圖譜.......................67
圖3-2-10 π配位體影響pMS高分子反應路徑示意圖........................67
圖3-2-11 π配位體影響分子量線性回歸比較圖.................................68
圖3-2-12 π配位體分子模型圖(圈處為雙鍵)......................................68
圖3-3-1 β-pinene對sPMS分子量影響之GPC疊圖.......................71
圖3-3-2 添加β-pinene在無氫氣下影響sPMS聚合之1H NMR.....72
圖3-3-3 β-pinene在無氫氣下影響sPMS聚合之13C NMR............73
圖3-3-4 2,5-Norbornadiene對sPMS分子量影響之GPC疊圖.......75
圖3-3-5 2,5-Norbornadiene無氫氣下影響sPMS聚合之1H NMR..76
圖3-3-6 2,5-Norbornadiene無氫氣下影響sPMS聚合之13C NMR..76
圖3-3-7 Diphenylacetylene對sPMS分子量影響之GPC疊圖........78
圖3-3-8 Diphenylacetylene無氫氣下影響sPMS聚合之1H NMR...78
圖3-3-9 台橡公司提供之polybutadiene( Mn=15萬) GPC圖...........80
圖3-3-10 PB(Mn=15萬)無氫氣下影響sPMS聚合之1H NMR疊圖.80
圖3-3-11 陰離子聚butadiene( Mn≒600) GPC 圖.............................81
圖3-3-12 PB(Mn=600)無氫氣下影響sPMS聚合之1H NMR疊圖.82
圖3-3-13 2,5-Norbornadiene影響聚苯乙烯GPC排列圖..................84
圖3-3-14 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之
1H NMR疊圖.......................................................................85
圖3-3-15 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之
13C NMR疊圖......................................................................86
圖3-3-16 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之
13C NMR 143~149ppm 疊圖...............................................86
圖3-3-17 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之
13C NMR 41~ 47ppm 疊圖..................................................87
圖3-3-18 選用2,5-Norbornadiene在無氫氣下影響苯乙烯聚合之
13C NMR 40~ 43ppm 疊圖..................................................87

圖3-4-1 syndiotactic polystyrene DSC分析.......................................88
圖3-5-1 Zambelli與Idemitsu的單體配位方式.................................95
圖3-5-2 對位聚4-甲基苯乙烯於氫氣存在下Idemitsu反應路徑圖..............................................................................................................91
圖3-5-3 對位聚4-甲基苯乙烯於氫氣存在下Zambelli反應路徑圖..............................................................................................................91
圖3-5-4 對位聚4-甲基苯乙烯於無氫氣存在下Idemitsu反應路徑圖..............................................................................................................93
圖3-5-5 對位聚4-甲基苯乙烯於無氫氣存在下Zambelli反應路徑圖1............................................................................................................93

圖3-5-6 對位聚4-甲基苯乙烯於無氫氣存在下Zambelli反應路徑圖2............................................................................................................94


































表目錄
表1-2-1 不同型態的聚苯乙烯比較.....................................................11
表1-2-2 sPS 與其它工程塑膠的物性對照.........................................13
表1-1-3 sPS材料幾點主要物理優勢..................................................14
表1-2-2 有機茂金屬觸媒與齊格勒-那達觸媒之比較........................21
表1-2-5 逐步聚合反應與連鎖聚合反應之比較.................................25
表1-2-6 自由基、陽離子、陰離子聚合反應的適用種類..................26
表2-1-1 各種GPC分離管的試用範圍................................................42
表3-2-1 -methylstyrene影響sPMS活性、分子量與PDI的比較...57
表3-2-3 β-pinene影響sPMS活性、分子量與PDI的比較................61
表3-2-5 1-octene影響sPMS活性、分子量與PDI的比較................64
表3-2-7 1-hexene影響sPMS活性、分子量與PDI的比較...............66
表3-3-1 β-pinene 影響sPMS活性、分子量與PDI的比較................71
表3-3-2 2,5-Norbornadiene影響sPMS活性、分子量與PDI的比較.74
表3-3-3 Diphenylacetylene影響sPMS活性、分子量與PDI的比較..77
表3-3-4 兩種PB與觸媒的莫耳數比...................................................82
表3-3-5 添加2,5-Norbornadiene的聚苯乙烯PDI...............................83

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