臺灣博碩士論文加值系統

本研究主要的目的是增韌原本脆性的聚苯乙烯（PS）。一般用來增韌PS的PB橡膠含有碳碳雙鍵，有老化的問題。加上聚合反應過程中會產生交聯，所以增加回收的困難度。本文以EVA取代PB解決以上問題。不過EVA與PS不相容，必須經過接枝共聚合反應，才能改善界面問題。實驗結果顯示，反應後EVA確實有增韌PS的效果，當添加10%EVA時，衝擊能量達到原來PS的5倍。不過Modulus也下降了5倍。
在觀察破裂面時發現，添加的EVA量越高，產生的Craze變形量越大。除了Craze之外，EVA相周圍有Shear Bands，且EVA相也有發生變形。所以增韌的機構主要應該是Craze，其次為Shear Yielding與EVA相的變形。本文也比較不同起始劑所合成的產物，比較機械性質有無差異。結果顯示t-BO起始系統產品的耐衝擊強度較BPO系統的高。此外in-situ方式所合成出來的產品強度也比機械混合來得高。此外，針對EVA接枝位置的釐清、反應條件和接枝效率、接枝度的關係、接枝共聚合物的熱行為，本文也作了一些探討。
本研究的重點除了放在增韌PS的機構外，對於聚合反應時相態的改變與相分離也做了一些探討。例如繪製SM，PS與EVA的三元相圖，利用相圖求出三者之間的interaction parameter，χ。相圖也可實際應用在聚合反應上。實驗結果顯示，當EVA初始濃度為10%時，反應會在兩相體積比接近於1的時候發生相反轉。相反轉也與EVA的分子量有關，當 EVA分子量較小時，較不容易形成相反轉。反應過程中是否達到相反轉對最後產物的機械性質有很大的影響。

Toughening of Polystyrene is the major object of this study. Traditionally, PB (Polybutadiene) is used as impact resistant modifier. The Disadvantages of PB are aging, degradation and recycle problems. In place of PB rubber, we use EVA (ethylene-vinyl acetate copolymer) to overcome these problems. However, EVA is incompatible with PS, giving poor adhesion at the interphase. By grafting PS onto EVA backbone, enhancing the mechanical properties and impact resistance of the PS matrix. When addition of 10% EVA, the impact strength increase five times than PS, but modulus decrease five times, too.
Morphological studies by scanning electron microscopy revealed crazing is the major toughening mechanism, shear yielding and deformation of EVA phase are the next. The t-BO initiation system has better impact resistance results than BPO initiation system.
The clarification of grafting sites on EVA, the effects of reaction condition on grafting efficiency and grafting level, and thermal behavior of graft copolymer (EVA-g-PS) are all discussion in this research.
Thermodynamics for EVA/PS/SM ternary solution is used to create a ternary plot, which can be used to simulate the phase states changes in practical reaction and predict when does the phase inversion occur. From the plot, the interaction parameters can be calculated. Phase inversion took places when the volume ratio of two phases reached unity. The molecular weight of EVA affects the time to reach phase inversion. The phase inversion has great influences on mechanical properties of products.

致謝…………………………………………………………..I
中文摘要……………………………………………………….II
英文摘要……………………………………………………...III
總目錄………………………………………………………...IV
表目錄…………………………………………………….VIII
圖目錄……...…………………………………………………IX
第一章 緒論…………………………………..……………….1
第二章 文獻回顧..…………………………………………….3
2-1以EVA增韌PS的方法………………………………3
2-1.1機械共混法…………………………………………3
2-1.2接枝─共聚共混法…………………………………3
2-2接枝共聚合反應的機構與動力……………………...4
2-3 HIPS之特殊型態的形成及控制……………………..7
2-4橡膠增韌機構（Rubber Toughen Mechanism）……...10
2-4.1早期理論…………………………………………..10
2-4.2多重裂紋理論（Multiple Craze Theory）…………..11
2-4.3剪力屈服理論（Shear Yielding Theory）…………..12
2-4.4孔穴的形成（Cavity Formation）………………….13
2-4.5裂紋及剪力屈服理論……………………………..13
第三章 實驗部份………………………………………….…15
3-1實驗藥品…………………………………………….15
3-2實驗儀器…………………………………………….15
3-3實驗步驟…………………………………………… 16
3-3.1判定EVA的接枝點………………………………..16
3-3.2以Demixing Method測定接枝效率(grafting efficiency)與接枝度(grafting level)16
3-3.3製作SM/PS/EVA三元相圖….…………………17
(A) Binodal Curve的製作………………………..17
(B) (B)Tie Line的製作………………………………17
3-3.4聚合動力與相態變化的觀察….………………….18
3-3.5 HIPS的合成……………………………………….18
(A) 注模成型(Casting)…………………………...18
(B) (B)懸浮聚合(Suspension Polymerization)…...….19
3-3.6拉力試驗(Tensile Test)………………..…………...19
3-3.7 Izod Impact Test…………………………...………19
3-3.8以電子顯微鏡觀察分散相結構(TEM,SEM)拉力及Izod impact測試後的破裂面(SEM) .…………...19 (A)TEM..……………….…………...……...……19
(B)SEM…………………………………………..20
3-3.9破裂面的觀察（SEM）…………………………….20
第四章 結果與討論………………………………………….21
4-1接枝反應發生位置的探討.…………….…………21
4-1.1 IR鑑定…………………………………………….22
4-2反應條件對接枝效率(Grafting Efficiency)與接枝度(Grafting Level)的影響…………………………….23
4-3接枝共聚合物（EVA-g-PS）的熱行為……………….24
4-4 HIPS聚合過程中的相行為的探討…………………25
4-4.1 SM/PS/EVA三元相圖的研究 ………………...25
4-4.2 Binodal Curve與Tie Line的測定…………………25
4-4.3 SM,PS與EVA三元溶液的熱力學……………..27
4-5預聚合階段的相反轉(Phase Inversion)……………32
4-6 EVA橡膠相形態………...…………………………33
4-7拉力、Izod Impact與DMA測試結果………….33
4-7.1 BPO與t-BO起始系統的比較…………………….34
4-7.2 EVA含量對伸長率的影響………………………..35
4-7.3 EVA含量對Modulus的影響……………………...35
4-7.4 EVA分子量對機械性質的影響…………………..37
4-7.5 Melt Blend產物與in-situ Blend產物的比較……..38
4-8增韌機構…………………………………………….39
第五章 結論………………………………………………….41
參考文獻…………………………….………………………..89
自述…………………………………………………………...91

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