Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/49514
標題: 掌性環丁內酯衍生物的不對稱催化合成及開環聚合反應:新材料的開發---重點一子題1:不對稱催化合成環丁內酯及其不對稱催化開環聚合反應研究
Catalytic Asymmetric Synthesis and Ring-Opening Polymerization of Butyrolactones
作者: 林助傑
關鍵字: 化學類, 材料科技
基礎研究
摘要: 摘要因為具生物相容性、滲透性,生物可分解的聚酯與其共聚物的應用廣泛,例如手術縫合線、藥物控制釋放上的媒介等,此類材料特別的使人感興趣。在此類高分子中有一系列的高分子,具光學純度熱塑性的聚環丁內酯具有優良的物理與機械性質,使得此類高分子在生醫材料應用發展上具潛力。有效製備此類高分子的方法是對具光學純度的環丁內酯單體進行開環聚合反應。然而,合成具光學純度環丁內酯的方法是很少的。本子計劃研究的目標包含下列三項:(一)不對稱環氧乙烷羰基化(carbonylation of epoxides)(Scheme 1)。(二)不對稱開環聚合環丁內酯(cyclic -butyrolactones) 催化劑的開發(Scheme 2)。(三)聚環丁內酯共聚物的合成(Scheme 3)。建立具光學純度環丁內酯的合成方法,與聚環丁內酯高分子及其共聚物的合成,開發新的生醫材料。Scheme 1. Catalysts for Asymmetric Carbonylation of EpoxidesOR+ COOR-Butyrolactone (BBL)[Cat.]OR: -CH3, -COOR', -CONHR' etc.OHNXNHOXi) AlMe3ii) BnOHi) AlCl3ii) NaCo(CO)4i) Co(OAc)2ii) NaClONXNOXAlBnOONXNOXAlCo(CO)4ONXNOXCoClScheme 2. Catalysts/Initiators for ROP of -ButyrolactonesOORButyrolacton (BBL)ROOPolybutyrolactone (PBL)n[Cat.]OHNXZ i) MR2ii) BnOH ONXONXMZMZOOPhPhM = Mg or ZnScheme 3.OORROOBBLPBLn[Cat.]ROOnROOnOOOOmOOOOOOm[Cat.]Polybutyrolactone-block-polylactide(PBL-b-PLA)mPolybutyrolactone-block-polycaprolactone(PBL-b-PCL)
Biodegradable polyesters and their copolymers are especially interesting for their variousapplications such as surgical sutures, drug delivery medium for controlled release of drugs due totheir biocompatible and permeable properties. Optical pure polybutyrolactones (PBLs) arepotentially useful as biomedical materials due to their well physical and mechanical properties.The efficient method for obtaining PBLs is ring-opening polymerization of optical purebutyrolactones. However, the synthetic routes of optical pure butyrolactones are rare. Theobjectives of this proposal include (1) Assymmetric carbonylation of epoxides (Scheme 1). (2)Asymmetric polymerization of cyclic -butyrolactones (Scheme 2). (3) Preparation of blockcopolymers containing polybutyrolactones (Scheme 3). This proposal focus on the developmentsuitable catalysts for the preparation of optical pure butyrolactones and polymerization of BLs aswell as development of new biomedical materials.Scheme 1. Catalysts for Asymmetric Carbonylation of EpoxidesOR+ COOR-Butyrolactone (BBL)[Cat.]OR: -CH3, -COOR', -CONHR' etc.OHNXNHOXi) AlMe3ii) BnOHi) AlCl3ii) NaCo(CO)4i) Co(OAc)2ii) NaClONXNOXAlBnOONXNOXAlCo(CO)4ONXNOXCoClScheme 2. Catalysts/Initiators for ROP of -ButyrolactonesOORButyrolacton (BBL)ROOPolybutyrolactone (PBL)n[Cat.]OHNXZ i) MR2ii) BnOH ONXONXMZMZOOPhPhM = Mg or ZnScheme 3.OORROOBBLPBLn[Cat.]ROOnROOnOOOOmOOOOOOm[Cat.]Polybutyrolactone-block-polylactide(PBL-b-PLA)mPolybutyrolactone-block-polycaprolactone(PBL-b-PCL)
URI: http://hdl.handle.net/11455/49514
其他識別: NSC99-2119-M005-001-MY2
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