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  • 學位論文

利用配位聚合法合成官能化聚4-甲基-1-戊烯之研究及滲透蒸發之應用

Study and Pervaporation Application of Synthesizing Functional Poly(4-methyl-1-pentene) via Complex Coordination Polymerization

指導教授 : 江彰吉 李季燃
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摘要


本篇論文主要以改質聚4-甲基-1-戊烯( TPX )作為研究重心,以提升此高分子膜材應用於滲透蒸發之液相分離之效率( TPX是聚4-甲基-1-戊烯的商品名)。首先,以4-甲基-1-戊烯為主單體及另一含兩個未飽和雙鍵之共單體,利用配位聚合反應進行共聚合後再進行官能化反應,期望增加TPX的極性,提升在滲透蒸發上的分離效率。共聚的方式有兩種,其一利用Metallocene均相觸媒系統,(Et(Ind)2ZrCl2/MAO),共聚4-甲基-1-戊烯與5-Ethylidene-2-norbornene ( ENB ),雖有很好的共聚效率,但所合成之TPX不具成膜性。因此,轉於利用Ziegler-Natta異相觸媒系統,( TiCl3-AA/AlEt2Cl ),以4-甲基-1-戊烯單體與1,7-辛二烯共單體進行共聚合反應,發現雖然共聚效率不高,但聚合物不產生交聯且具很好的成膜性。接著將TPX中共單體單位上未反應的烯烴基利用間位氯化過氧苯酸( MCPBA )進行環氧化反應,並以甲醇或四氫鋰化鋁進行開環,而接上-OCH3及-OH等官能基;或利用鹽酸、溴水(Br2 )進行雙鍵的加成鹵化反應,接著利用原子轉移自由基聚合法,接枝Poly(methyl methacrylate acrylonitrile) 。本研究利用核磁共振氫譜圖及紅外線光譜圖進行結構鑑定,熱重分析儀以及示差式掃描分析儀進行熱性質(Td)與玻璃轉移溫度、熔點及結晶性之研究。於滲透蒸發的比較中發現,由甲醇開環官能化之TPX,成功的提升酒精水溶液的分離效率,具有較高的透過率、選擇比及PSI值。

並列摘要


This study focuses on modifying poly(4-methyl-1-pentene) (TPX) and increasing the efficiency of this polymer membrane in separating liquids in pervaporation (PV). TPX is the common name of ploy(4-methyl-1-pentene) . First, the monomer, 4-methyl-1-pentene, was copolymerized with other diene comonomers by complex coordination polymerization and was functionalized. The aim was to increase the polarity of TPX and increase its effectiveness in separating PV. Two catalytic systems were used to prepare the copolymer. One used homogeneous metallocene catalyst (Et(Ind)2ZrCl2/MAO)to copolymerize the 4-methyl-1-pentene and 5-ethylidene-2-norbornene ( ENB ). The copolymerization was efficient, but the action as a membrane was poor. Next, the heterogeneous Ziegler-Natta catalyst system (TiCl3-AA/AlEt2Cl) was used to copolymerize the 4-methyl-1-pentene and 1,7-octadiene. The copolymerization was not excellent but was acceptable. The copolymer did not crosslink, and the ability of to act as a membrane was better. Then, the unreactive vinyl group of the comonomer unit in the TPX was epoxidized using m-chloroperoxybenic acid ( MCPBA ). Finally, methanol or lithium aluminum hydride was used to open the ring and graft the -OCH3 and -OH functional groups. Hydrochloric acid and bromine (Br2) could also be used to perform the addition reaction. Then poly(methylmethacrylate acrylonitrile) was grafted via atomic transfer radical polymerization ( ATRP ). The compound was examined by 1H-NMR ,FT-IR ,TGA and DSC were used to measure the degradation temperature (Td), the glass transition temperature (Tg) and the melt temperature (Tm). The results indicated that the functional TPX of the methanol opened ring increasing the efficiency of separation of the alcohol/water solution. The permeation rate, separation factor and PSI value on the PV, were higher.

參考文獻


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