Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3528
標題: Catalyst Kinetics and Product Analysis of Anionic Ring-Opening Polymerization
陰離子開環聚合反應之觸媒動力學及產物性質
作者: 蘇一芳
Su, Yi-Fang
關鍵字: 陰離子開環聚合;環氧烷類;1;2-butylene oxide(BO);醯胺;Anionic Ring-Opening Polymerization;oxirane;1;2-環氧丁烷;Amide
出版社: 化學工程學系
摘要: 
利用高溫高壓反應器,針對不同起始劑和環氧烷類(oxirane)進行開環聚合反應,合成結構上含有聚醚(polyether)鏈段的高分子。起始劑種類包括amide、amine/amide、urethane、urea、alcohol等。環氧烷類則包含propylene oxide (PO)及1,2-butylene oxide (BO)。其中已成功合成的產物有:
(一)醯胺型(Amide):
含amide結構之起始劑包括diamide及triamide。分別由diamine與ethyl acetate及triamine與ethyl acetate反應合成。再加入催化劑與BO合成聚醚類的雙子星、星狀親油性高分子。
(二)胺型及醯胺型(Amine/Amide):
3-(Dimethylamino)propylamine(DAP)與ethyl acetate合成親水
性含amide/amine官能基的起始劑。再加入催化劑與BO合成聚
醚類的親油性高分子。
(三) 月尿酯(Urethane)型:
含urethane官能基的起始劑可由propylene carbonate與DAP或由propylene carbonate與ethylene diamine或propylene carbonate與D-230合成。再加入催化劑與BO合成聚醚類的親油性高分子。
(四)Urea
Isophorone diisocyanate(IPDI)與ethanolamine或isophorone diisocyanate與diethylene glycolamine可合成含uera官能基的起始劑。再加入催化劑與BO合成聚醚類的親油性高分子。
(五)醇類(Alcohol)
Allyl alcohol及cis-butene-1,4-diol分別與BO或PO進行開
環聚合反應,合成聚醚類的親油性高分子。
上述反應使用的催化劑包括KOH、NaOH、potassium tert-butoxide((CH3)3COK)等。除了在高溫高壓反應器進行反應外,少數以alcohol官能基為起始劑的聚合反應亦可在玻璃儀器中進行,但是所使用的觸媒則是變成BF3-OEt2(boron trifluoride diethyl ether complex)、AlCl3(aluminum chloride),且所需的反應時間較長。
本研究藉由改變各種反應溫度來觀察反應速率與溫度的關係,並由壓力來判斷反應是否趨於完成。最後並針對鹼性觸媒對於PO、BO開環聚合反應的產物無法合成高分子量的問題詳加探討。

The use of various initiators reacted with oxirane to proceed ring-opening polymerization and synthesize polymers containing polyether segments which ran in autoclave. The initiators included amide, amine/amide, urethane, urea and alcohol. Oxirane included propylene oxide (PO) and 1,2-butylene oxide (BO). Those polymers which have been successfully synthesized were classfied to five groups.
(1) Amide type:
The structure of amide type contained diamide and triamide. Diamide was synthesized by diamine and ethyl acetate. Triamide was synthesized by triamine and ethyl acetate. Then initiators reacted with BO and catalyst to synthesize polyether segments of lipophilic polymers with Gemini and star-like structure.
(2) Amide/Amine type:
The initiators containing amide/amine functional groups were synthesized by 3-(Dimethylamino)propylamine(DAP) and ethyl acetate. Then initiators reacted with BO and catalyst to synthesize polyether segments of lipophilic polymers.
(3) Urethane type:
The initiators could be synthesized by propylene and DAP, propylene carbonate and ethylene diamine, or propylene carbonate and D-230. Then, initiators reacted with BO and catalyst to synthesize polyether segments of lipophilic polymers.
(4) Urea type:
The urea type of initiators could be synthesized by isophorone diisocyanate(IPDI) and ethanolamine, or isophorone diiscyanate and diethylene glycolamine. Then, initiators reacted with BO and catalyst to synthesize polyether segments of lipophilic polymers.
(5) Alcohol type:
The ring-opening polymerization of allyl alcohol or 1,4-butenediol was synthesized polyether segments of lipophilic polymers by reacting with BO or PO.
Potassium hydroxide (KOH), sodium hydroxide (NaOH) and potassium tert-butoxide ((CH3)3COK) were used in those reactions which described before. Most reactions were proceeding in autoclave except some initiators of alcohol type which could be proceeded in glassware but catalyst changed to boron trifluoride diethyl ether complex (BF3-OEt2) and aluminum chloride (AlCl3), and took longer time of reaction.
The objectives of this study are (1) to observe the relationship of rate of reaction and temperature by changing temperature of reaction, (2) to determine the completion of reaction by pressure and (3) to discuss the problem which ring-opening polymerization of PO and BO by base catalyst could not synthesize high molecular weight polymers.
URI: http://hdl.handle.net/11455/3528
Appears in Collections:化學工程學系所

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