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標題: 回收聚碳酸酯廢料至雙酚A雙烯丙烯醚
Recycling of PC Waste to Bisphenol A Diallyl Ether.
作者: 蔡佑書
Tsai, You-Shu
關鍵字: Recycling of PC;回收聚碳酸酯;Bisphenol A diallyl ether;Trans-esterification;Allyl Etheration;雙酚A雙烯丙烯醚;酯交換反應;醚化反應
出版社: 化學工程學系所
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本論文已成功地發展一種獨特且同時具有良好的效率,將PC廢料回收成為BPA diallyl ether(BPA-DAE)之不含鹵素新法。我們先以Pd/C為觸媒與丙烯碳酸酯作為我們不含鹵素之試劑,將Phenol和Diphenyl carbonate(DPC)分別轉換至Allyl phenyl ether(APE)。我們研究證實,Phenol與Diallyl carbonate(DAC)或與Allyl acetate在溫和條件(85℃)及觸媒Pd/C和Ph3P催化下,可輕易地轉換至Allyl phenyl ether(APE)。
另一模式反應研究,以操作簡單便利之一鍋化方式,亦可將Diphenyl carbonate(DPC)藉由丙烯醚化反應轉化至APE。此一鍋化新法是在觸媒NaOCH3催化作用下,先將Dimethyl carbonate (DMC)與Allyl alcoho於溫度30℃下,進行酯交換反應,產生主要的碳酸酯產物Allyl methyl carbonate (AMC)和Diallyl carbonate(DAC),再直接加入Diphenyl carbonate (DPC)於溫度70℃下進行酯交換反應,反應一小時後,接著再加入觸媒Pd/C及Ph3P,在溫度85℃下進行丙烯醚化反應,將置換產生之Phenol轉換至Allyl phenyl ether(APE),產率為86%。
進一步將此一鍋化法延伸應用在PC廢料之回收。由於PC廢料以Allyl alcohol分解消化之後,理論上能產生碳酸酯的量僅有酚基的一半,所以在程序設計上先將DMC(0.2mole)與Allyl alcohol(1.06mole)進行酯交換反應,產生主要碳酸酯產物AMC與DAC,接著才加入PC廢料粉末,在溫度90℃下反應,進行消化反應同時也啟動酯交換反應,將PC廢料分解至小分子混合物,反應5小時後,再加入觸媒Pd/C及Ph3P,進行丙烯醚化反應,反應初期產生BPA和BPA-monoallyl ether (BPA-MAE),藉由此方法則最終可將全部轉化為BPA diallyl ether(BPA-DAE)為最終產物,產率69%。經此不含鹵素新法回收之BPA diallyl ether,未來可進一步作為合成之原料,經氧化反應,製備BPA diglycidyl ether(BPA-DGE),可應用於電子級環氧樹脂材料。

In this research, a unique and efficient process for chemical recycling of spent polycarbonate (PC) into bisphenol-A diallylether (BPA-DAE) has been developed. We started our research by working on the conditions of converting phenol and diphenyl carbonate (DPC) individually into allyl phenyl ether (APE) by a palladium catalyzed etheration process with allyl carbonates as our non-halogen reagents. In the model study, we confirmed that phenol could be easily converted into allyl phenyl ether (APE) under mild condition (85 oC) with either mono-allyl carbonates, diallyl carbonate or allyl acetate under the catalysis of Pd/charcoal (10% of Pd/C) and triphenyl phosphine.
In the other model study, the facile one-pot conversion of diphenyl carbonate (DPC) into APE also has been accomplished by the etheration process. In this new one-pot process, dimethyl carbonate (DMC) and excess of allyl alcohol were first treated with trace sodium methoxide to start out a trans-esterification at 30 oC. By doing so, an equilibrium mixture consisting of allyl methyl carbonate (AMC) and diallyl carbonate was produced as the major components. Then, diphenyl carbonate (DPC) was added to the equilibrated solution to start the second trans-esterification at 70 oC. After 1 hour of stirring, the solution was added triphenyl phosphine and Pd/C at 85oC to initiate the etheration process. It was found that DPC became disappeared swiftly and in the meantime all phenol produced in the trans-esterification process was converted into APE in 86% isolated yield.
The successful model process involving trans-esterification and etheration was applied to the recycling of the spent PC. In this effort, DMC (0.2 mole) and powder PC were added into 1.06 molar excess of allyl alcohol and the mixtures were heated to 90 oC to digest PC and start off trans-esterification at the same time. After 5 hours of heating, Pd/C and triphenyl phosphine were added to kick off the etheration step. It was observed that BPA and BPA-mono-allylether (BPA-MAE) originally in the reaction mixture are converted into BPA-DAE as the final major product in 69% calculated yield through this one-pot process.
In the next phase of future research, BPA-DAE product from PC conversion will be used as the raw materials for preparation of BPA-diglycidyl ether (BPA-DGE) for epoxy curing applications.
其他識別: U0005-1808201013470100
Appears in Collections:化學工程學系所

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