不同場合使用的工業橡膠製品常選擇碳黑(Carbon Black)作為補強材料，碳黑與生膠(Raw Gum)親和性相當好，不須特別改質;但白色和彩色膠料則常用陶土(Clay)，滑石粉(Talc)與二氧化矽(Silica)等淺色粉末當填料，其與生膠親和性不佳。且因碳黑來自於石油裂解衍生物，而白煙(SiO2)為天然礦物，以綠色材料為前提考量，故本研究主軸是以高分子材料NBR丁腈橡膠(Acrylonitrile butadiene rubber)作為基材，以白煙(SiO2)替代碳黑，藉由添加矽烷偶合劑在無機材料和高分子材料的複合體系中，期能透過物理和(或)化學作用把二者結合，亦或能通過物理和(或)化學反應，使二者親和性得到改善，發揮最大綜合性能，提升橡膠製品附加價值。主要探討矽烷偶合劑對於硫化膠之機械強度(硬度，抗張強度，伸長率，定伸強度)、耐磨特性、抵抗油品的能力、粉體分散度、混煉加工性等之影響。結果顯示矽烷偶合劑確實能提升橡膠機械強度、耐磨特性、粉體分散度與混煉加工性等。

Carbon black is often chosen as the reinforcing filler in the rubber industry for several purposes. The modification of carbon black is unnecessary due to its high affinity with raw gum. For white or colored compounds, white fillers like clay, talc, and silica are often used, but the affinity between the filler and raw gum is not satisfying. Carbon black is the derivative of petroleum products and white fillers are originally from natural ores. Considering that green materials have been gaining increasing attention, the main purpose in this study is to the silane coupling agents used in acrylonitrile butadiene rubber (NBR) with white fillers. In the composite of inorganic materials and polymers, silane coupling agents provide the interaction between filler and rubber via physical and/or chemical reaction. In this study, the use of silane coupling agents tends to enhance the affinity between the two materials and hence increases the added value of rubber products. The issues to be discussed are as follows: mechanical properties (hardness, tensile strength, elongation, modulus), wear resistance, oil resistance, dispersion of fillers, and processability. The results show that silane coupling agents have significant improvments in mechanical properties, wear resistance, dispersion of filler and processability.

目錄
摘要......................................................................................................................I
Abstract...............................................................................................................II
目錄................................................................................................................... III
表目錄 ............................................................................................................ VI
圖目錄 ........................................................................................................... VII
第一章 緒論......................................................................................................1
1.1 前言.............................................................................................................1
第二章 文獻回顧與相關理論..........................................................................3
2.1 橡膠簡介.....................................................................................................3
2.1.1 橡膠之介紹............................................................................................3
2.1.2 橡膠的發展歷程................................................................................... 4
2.1.3 橡膠的分類........................................................................................... 5
2.1.4 橡膠合成與結構....................................................................................9
2.1.5 橡膠性能..............................................................................................13
2.2 偶合劑簡介...............................................................................................21
2.2.1 偶合劑功能介紹..................................................................................21
2.2.2 偶合劑的分類......................................................................................21
2.2.3 矽烷偶合劑的反應機制......................................................................24
2.2.4 Payne效應...........................................................................................27
2.2.5 矽烷偶合劑的效用..............................................................................29
2.2.6矽烷偶合劑改質橡膠...........................................................................31
2.2.7研究動機...............................................................................................35
第三章 實驗內容............................................................................................36
3.1 實驗藥品...................................................................................................36
3.2 儀器設備...................................................................................................38
3.3儀器測試方法及條件................................................................................40
3.4實驗概述....................................................................................................44
3.5實驗流程....................................................................................................45
第四章 結果與討論........................................................................................47
4.1添加不同含量偶合劑Si-69對NBR硬度影響.......................................47
4.2添加不同含量偶合劑Si-69對NBR抗張強度影響...............................48
4.3添加不同含量偶合劑Si-69對NBR伸長率影響...................................49
4.4添加不同含量偶合劑Si-69對NBR模數(M100)影響...........................50
4.5添加不同含量偶合劑Si-69對NBR磨耗影響.......................................51
4.6添加不同含量偶合劑Si-69對NBR壓縮永久變型影響.......................52
4.7添加不同含量偶合劑Si-69對NBR 最低木尼黏度影響......................53
4.8添加不同含量偶合劑Si-69對NBR 加硫起始點影響.........................54
4.9添加不同含量偶合劑Si-69對NBR 硫化時間影響.............................55
4.10不同比例偶合劑測試數據.....................................................................56
第五章 結論...................................................................................................60
第六章 參考文獻...........................................................................................62

表目錄
表2-1 常用聚合單體............................................................................................9
表2-2 共聚物種類..............................................................................................10
表2-3 微觀結構對Tg的影響..............................................................................12
表2-4 橡膠分類方法..........................................................................................15
表2-5 偶級矩.....................................................................................................18
表2-6 硫化膠的性能作為選擇膠種的依據......................................................19
表2-7 Payne效應在混煉膠的現象與化學解釋.................................................28
表2-8 不同含量偶合劑Si-69對NR磨耗影響....................................................33
表2-9 不同含量偶合劑Si-69對NR壓縮永久變型影響....................................33
表2-10 不同含量偶合劑Si-69對NR木尼黏度影響.....................................34
表3-1 不同比例偶合劑Si-69於NBR配方表......................................................45
表4-1 不同比例偶合劑測試數據......................................................................56

圖目錄
圖2-1 溫度導致剪切模數變化曲線..................................................................6
圖2-2 彈性體的剪切模數和tanδ與溫度的關係示意圖................................7
圖2-3 1,3丁二烯的聚合....................................................................................11
圖2-4 根據ASTM D2000彈性體的耐熱/耐油分類...........................................16
圖2-5 彈性體和TPU與其它材料拉伸強度對比...............................................20
圖2-6 矽烷偶合劑作用示意圖.........................................................................22
圖2-7 矽烷偶合劑參考用量.............................................................................22
圖2-8 silica形成filler-filler交互作用示意圖.......................................24
圖2-9 矽烷偶合劑的反應機制示意圖.............................................................25
圖2-10 Silane與Silica鍵結..............................................................................25
圖2-11 Silane內部鍵結...................................................................................26
圖2-12 已和Silica鍵結的Silane分子與橡膠分子鍵結....................................26
圖2-13 filler-rubber交互作用示意圖.........................................................27
圖2-14 矽烷偶合劑鍵結高分子與無機表面示意圖.......................................29
圖2-15 矽烷與水氣反應示意圖.......................................................................29
圖2-16 矽烷分子遷移至表面缺陷示意圖.......................................................30
圖2-17 不同含量偶合劑Si-69對NR硬度影響.................................................31
圖2-18 不同含量偶合劑Si-69對NR抗張強度影響........................................32
圖2-19 不同含量偶合劑Si-69對NR伸長率影響............................................32
圖2-20 不同含量偶合劑Si-69對NR加硫起始點影響....................................34
圖2-21 不同含量偶合劑Si-69對NR硫化時間影響........................................35
圖3-1 硬度計測試頭外觀................................................................................40
圖3-2 壓縮永久變型試驗示意圖....................................................................42
圖3-3 門尼黏度試驗機模腔............................................................................42
圖3-4 硫變試驗機模腔....................................................................................43
圖4-1 不同含量偶合劑Si-69對NBR硬度影響................................................47
圖4-2 不同含量偶合劑Si-69對NBR抗張強度影響........................................48
圖4-3 不同含量偶合劑Si-69對NBR伸長率影響............................................49
圖4-4 不同含量偶合劑Si-69對NBR模數(M100)影響....................................50
圖4-5 不同含量偶合劑Si-69對NBR磨耗影響................................................51
圖4-6 不同含量偶合劑Si-69對NBR壓縮永久變型影響................................52
圖4-7 不同含量偶合劑Si-69對NBR木尼黏度影響........................................53
圖4-8 不同含量偶合劑Si-69對NBR加硫起始點影響....................................54
圖4-9 不同含量偶合劑Si-69對NBR硫化時間影響........................................55
圖4-10 A配方(Si-69 0phr)抗張強度與伸長率測試曲線..............................57
圖4-11 B配方(Si-69 1.5phr)抗張強度與伸長率測試曲線…....................57
圖4-12 C配方(Si-69 3.0phr)抗張強度與伸長率測試曲線…....................58
圖4-13 D配方(Si-69 4.5phr)抗張強度與伸長率測試曲線.........................58
圖4-14 E配方(Si-69 6.0phr)抗張強度與伸長率測試曲線.........................59

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