- 學位論文
丁苯橡膠官能化及接枝聚合反應之合成研究
Functionalization and graft copolymerization on styrene-butadiene rubber
摘要
本實驗主要使用商業化的丁苯橡膠(聚苯乙烯-丁二烯共聚物， polystyrene-co-1,4butadiene，SBR)做改質及接枝反應為研究重心。因為丁苯橡膠的實際應用仍需和其它物質材料進行摻合，才能獲得較好的性質，由於橡膠黏性很大，所以與其它物質之相容性很差，工業上僅能以混摻方式將兩物質混合，因此大大地限制了丁苯橡膠的應用及使用範圍，本研究希望經由化學方法進行官能化及接枝之改質方法，合成帶有官能基之SBR來改善其相容性。 本實驗中利用硼烷化學(9-BBN)與材料結構中的側鏈端雙鍵進行氫硼化反應行官能化反應，隨後再進行氧化反應，將雙鍵上的含硼共聚物轉換成含羥基的官能性高分子(SBR-OH)。接枝方面使用兩種方法進行接枝聚合反應，第一部份為硼烷化學，第二部份為原子轉移自由基聚合法(ATRP)來進行PMMA接枝聚合反應；第一部分將材料結構中的側鏈端雙鍵進行氫硼化反應，利用硼烷化學在氧氣存在下進行自由基聚合反應接枝聚合PMMA，實驗中改變氧氣添加量、MMA單體添加量、9-BBN添加量變化及反應時間等因素，探討如何將未交聯接枝共聚物的產量經多種變因而提升，以及PMMA接枝量莫耳百分比的影響。第二部份將材料結構中的主鏈上雙鍵改質，經環氧化反應、甲醇開環反應，以及酯化反應接上具有氯官能基，再進行原子轉換自由基聚合反應接枝聚合PMMA。使用1H-NMR與FTIR做結構鑑定分析兩大部份之反應機制，並計算官能化與接枝反應程度，另外利用微差掃描卡計(DSC)和熱重分析儀(TGA)探討官能化與接枝前後產物熱性質的變化，最後再利用掃描式電子顯微鏡分析儀(SEM)觀察加入SBR-g-PMMA做為調和劑後樣品內部結構的差異。
並列摘要
The study focuses on modifying and grafting of commercial Styrene-Butadiene rubber (SBR). SBR rubber is a high adhesive material that is poor compatibility with other materials. The poor compatibility greatly limits the application of SBR rubber in many application areas. Therefore, SBR rubber must incorporate some functional groups or polar monomers in the polymer chains that increase its property. This study hopes that functional groups and PMMA groups introduced onto SBR can increase its polarity and compatibility with polar polymers. In the experiment, hydroboration was carried out by using 9-BBN to react with the double bonds on side chains of the SBR rubber. The functional polymer (SBR-OH) was obtained by the oxidation on the hydroborated side chain of the copolymer. The grafted copolymerization of PMMA onto SBR rubber was prepared by two different methods by borane chemistry and by ATRP method. First method, the hydroborated on the side chain of the copolymer and then grafted PMMA on the copolymer by oxidation. At second method, the PMMA grafted copolymer was prepared by oxidation, ring-open, ester reaction, and ATRP. We discussed the experimental results via the amount of oxygen, MMA and 9-BBN, and reaction time etc. The structure and grafting efficiency of graft copolymers will be characterized and determined by 1H-NMR and FTIR. Additionally, use DSC and TGA to discuss the variation of thermal properties before and after the functionalized or grafted reaction. At last, the graft copolymers can be used as a compatibilizer to improve materials compatibility and the morphology of blends are compared by using SEM.