The reactions of 2,2'-(2-methoxybenzylidene)-bis-(4-methy1-6-tert-butylphenol) with trimethylaluminum::novel efficient catalysts for"living"and "immortal"polymerization of E-caprolactone

國立中興大學90學年度第二學期碩士學士學位論文摘要 論文題目﹕單體、雙體鋁烷氧化合物的合成、結構鑑定及其在聚己內酯、苯乙烯己內酯共聚合物之製備 所組別﹕化 學 研究所 無 機 組 （學號﹕78951113） 研究生﹕薛 茂 霖 指導教授﹕林 助 傑 博士 論文摘要內容﹕ 2當量2-tert-butyl-4-methylphenol與鄰-甲氧基苯甲醛(o-Anisaldehyde)在催化劑量之苯磺酸(benzensulfonic acid)存在下反應形成雙芽2,2’-(2-Methoxybenzylidene)-bis(4-methyl-6-tert-butylphenol) (MEBBP-H2)(1)。化合物(1)和三甲基鋁在非配位能力溶劑(toluene)下反應形成四配位雙體化合物[Al(µ-MEBBP)Me]2 (2)；而在單芽配位基(THF)為溶劑下反應則是形成四配位單體化合物[(MEBBP)Al(CH3)(THF)] (3)。開環聚合(ring-opening polymerization, ROP)反應的四配位雙體起始物[Al(MEBBP)(µ-OBn)]2 (4)可以經由化合物(2)或(3)與苯甲醇反應所獲得。實驗顯示化合物(4)在催化己內酯(ε-caprolactone)的ROP反應有良好的效果，不但具有〝 Living 〞性質，並且有〝 Immortal 〞性質，最多可加入256倍苯甲醇，仍不至於分解。此外，化合物(3)在尾端具有醇基(hydroxyl chain end)的聚苯乙烯存在下，反應形成macroinitiator，進一步合成苯乙烯己內酯共聚合物。目錄 第一章 導論................................................1 第二章 實驗部分 一、儀器...........................................9 二、藥品與溶劑處理.................................10 三、操作技巧.......................................12 四、起始物的合成...................................13 五、錯合物的合成...................................14 六、聚合物的合成...................................19 第三章 結果與討論 一、化合物1-5的成與光譜研究 1. 化合物1、2、3和4的合成與光譜研究..............21 2. 錯化合物5的合成與光譜研究....................25 二、化合物1-5的分子結構 1. 化合物(1)的分子結構解析.......................27 2. 錯化合物(2)和(3)的分子結構解析.................29 3. 錯化合物5分子結構解析........................35 三、開環聚合反應 1. 錯化合物(4)對己內酯的開環聚合反應.............38 2. 聚己內酯(PCL)的分子結構與氫光譜的研究........44 3. 錯合物(3)應用在苯乙烯與己內酯共聚合物 (PS-b-PCL)的合成..............................45 4.苯乙烯己內酯共聚合物(PS-b-PCL)的分子結構......50 第四章 結論...............................................52 參考文獻....................................................54 附錄 錯化合物1的晶體資料........................................57 錯化合物2的晶體資料........................................63 錯化合物3的晶體資料........................................77 錯化合物5的晶體資料........................................84 聚合物之GPC圖譜...........................................91 國立中興大學90學年度第二學期碩士學士學位論文摘要 論文題目﹕單體、雙體鋁烷氧化合物的合成、結構鑑定及其在聚己內酯、苯乙烯己內酯共聚合物之製備 所組別﹕化 學 研究所 無 機 組 （學號﹕78951113） 研究生﹕薛 茂 霖 指導教授﹕林 助 傑 博士 論文摘要內容﹕ 2當量2-tert-butyl-4-methylphenol與鄰-甲氧基苯甲醛(o-Anisaldehyde)在催化劑量之苯磺酸(benzensulfonic acid)存在下反應形成雙芽2,2’-(2-methoxybenzylilidene)bis(6-tert-butyl-4-methylphenol) (MBBMP-H2) (1)。 化合物(1)和三甲基鋁在非配位能力溶劑(toluene)下反應形成四配位雙體化合物[Al(µ-MBBMP)Me]2 (2)；而在單芽配位基(THF)為溶劑下反應則是形成四配位單體化合物[(MBBMP)Al(CH3)(THF)] (3)。開環聚合(ring-opening polymerization, ROP)反應的四配位雙體起始物[Al(MBBMP)(µ-OBn)]2 (4)可以經由化合物(2)或(3)與苯甲醇反應所獲得。實驗顯示化合物(4)在催化己內酯(ε-caprolactone)的ROP反應有良好的效果，不但具有〝 Living 〞性質，並且有〝 Immortal 〞性質，最多可加入256倍苯甲醇，仍不至於分解。此外，化合物(3)在尾端具有醇基(hydroxyl chain end)的聚苯乙烯存在下，反應形成macroinitiator，進一步合成苯乙烯己內酯共聚合物。 表目錄 Table 1. 錯化合物(3)與 [(EDBP)Al Me(THF)] 1H NMR 光譜之比較..........................................23 Table 2. 錯化合物(4)與[Al(EDBP)(μ-OBn)]2 1H NMR 光譜之比較..........................................24 Table 3. 化合物(1)晶體解析資料................................28 Table 4. 錯化合物(2)與[Al(μ-EDBP)Me]2選擇性鍵長之比較.........29 Table 5. 錯化合物(3)與[Al(EDBP)Me(THF)]選擇性鍵長之比較......30 Table 6. 錯化合物2、3晶體解析資料.............................31 Table 7. 錯化合物5晶體解析資料...............................36 Table 8. 化合物4對CL開環聚合反應數據........................39 Table 9. macroinitiator對CL開環聚合反應數據.....................49 圖目錄 Figure 1. 化合物1的分子結構..................................27 Figure 2. 錯化合物2分子結構圖.................................32 Figure 3. 錯化合物3分子結構圖.................................33 Figure 4. 化合物3的分子結構側面圖.............................34 Figure 5. 錯化合物5分子結構圖.................................37 Figure 6. 化合物4在開環聚合反應的線性關係圖...................40 Figure 7. 逐次加入反應中，Entry2、6之GPC比較圖................41 Figure 8. 化合物4在開環聚合反應之1H NMR光譜圖44 Figure 9. 苯乙烯、苯乙烯己內酯共聚合物之GPC比較圖.............48 Figure 10. 苯乙烯、苯乙烯己內酯共聚合物之1H NMR光譜圖........ 5

Synthesis, Characterization and Catalytic Studies of EDBP Supported Lithium, Sodium, Magnesium and Zinc Complexes: Efficient Catalysts for Ring-Opening Polymerization of e-Caprolactone and L-Lactide and Anionic Polymerization of Methyl Methacrylate

Several novel zinc and magnesium aryloxides, [(EDBP)Zn(THF)]2 (1), [(EDBP)Mg(Et2O)]2 (2), and [(EDBP)Mg(THF)]2 (3), have been synthesized by the reaction of 2,2¢-ethylidenebis(4,6-di-tert-butylphenol) (EDBP-H2) with ZnEt2 or MgnBu2 in diethyl ether (Et2O) or tetrahydrofuran (THF), respectively. Experimental results show that 1-3 efficiently catalyze the ring-opening polymerization (ROP) of e-caprolactone (e-CL) and L-lactide (L-LA) in a controlled fashion, yielding polymers with very narrow polydispersity indexes (PDI) in a wide range of monomer-to-initiator ratios. The reaction of EDBP-H2 with nBuLi in THF, Et2O or hexane, gives [(EDBP-H)Li(THF)3] (4), [(EDBP-H)Li(Et2O)3] (5) or [(EDBP-H)Li]3 (6), respectively. However, the reaction of EDBP-H2 with nBuLi in the presence of benzyl alcohol (BnOH) in Et2O or THF produces compound [(EDBP-H)Li(BnOH)]2 (7) or [(EDBP-H)Li(BnOH)(THF)2] (8), respectively. Further reaction of 7 with excess of THF produces 8. Alternatively, 8 can also be prepared by the reaction of benzyl alcohol with 4 in toluene. Experimental results show that 7 and 8 efficiently initiate the ROP of L-lactide in a controlled fashion, yielding polymers with very narrow polydispersity indexes in a wide range of monomer-to-initiator ratios. Moreover, the reaction of EDBP-H2 with 2.2 equiv nBuLi in Et2O affords [(EDBP)Li2(Et2O)]2 (9). Moreover, block copolymers, polystyrene-b-poly(L-lactide), have also been prepared from the ring-opening polymerization of L-latide catalyzed by 2 and 4 using polystyrene as a macroinitiator. The unusual lithium n-butylmagnesium [(EDBP)Mg(m2-nBu)Li(Et2O)]2 (10), sodium n-butylmagnesium [(EDBP)Na(Et2O)MgnBu]2 (13), lithium ethylzinc [(EDBP)Zn(THF)]2[(m2-C2H5)Li(THF)] (14) and lithium-magnesium enolate, {(EDBP)Mg[m2-OC(Mes)CH2]Li(Et2O)}2 (11), and the sodium aggregate, [(EDBP)Na2]4 (12), have been synthesized and structurally characterized. Among them, 10, 11, 13 and 14 have been used as initiators for the polymerization of methyl methacrylate. The dimeric lithium n-butylmagnesium complex 10 was obtained from the reaction of [(EDBP)Li(Et2O)3] (5) with a stoichiometric amount of MgnBu2. Alternatively, 10 can also be prepared by the reaction of [(EDBP)Mg(Et2O)]2 (2) with a stoichiometric amount of nBuLi in Et2O. Furthermore, the reaction of 10 with 2¢,4¢,6¢-trimethylacetophenone (MesC(O)CH3, Mes = 2,4,6-Me3C6H2) produces 11. Reaction of EDBP-H2 with excess sodium metal in Et2O furnishes compound 12. In the presence of a stoichiometric amount of MgnBu2 in Et2O, 12 can be converted to the dimeric sodium-magnesium mixed-metal complex [(EDBP)Na(Et2O)MgnBu]2 (13). Moreover, 14 can be obtained by the reaction of [(EDBP)Li(THF)3] (4) with a stoichiometric amount of ZnEt2. Experimental results show that 10, 11, 13 and 14 efficiently initiate the anionic polymerization of methyl methacrylate.Abstract…………………………………………………………………....1 Chapter 1. Introduction Biodegradable Polymers……………………………………....3 Metal Complexes Supported by Salen Ligands………………5 Metal Complexes Supported by Biphenol Ligands…………...8 References…………………………………………………...11 Chapter 2. Zinc, Magnesium and Lithium Complexes Introduction……………………………………………....….15 Results and Discussion………………………………………17 Synthesis and Spectroscopic Studies of Compounds1-9…....17 Molecular Structure Studies of 1-3………………………….20 Molecular Structure Studies of 4 and 6-9……………….…..24 ROP of e-CL Using Complex 1 as Initiator………………...33 ROP of L-LA Using Complexes 1-3 as catalysts………......37 Proposed Mechanism for ROP of L-LA Catalyzed by 1-3...44 ROP of L-LA Using Complexes 7 and 8 as Initiators…….....46 Proposed Mechanism for ROP of L-LA Catalyzed by 7…...50 Summary………...…………………………..……………....52 Experimental Section…………………………………..…....52 References………………………………..………………….58 Chapter 3. Application for the Synthesis of PS-b-PLLA Introduction………………………………………………….62 Preparation of 4-Hydroxyl-TEMPO-terminated Polystyrene …………………………………………………………….…64 Synthesis of Polystyrene-Poly(L-lactide) Diblock Copolymer ……………………………………………………....…...….67 Summary…...…………………………………………..…....70 Experimental Section…………………………………..…....70 References………………………………..………...………..71 Chapter 4. Mixed- Metal Complexes Introduction………………………………………………….73 Results and Discussion……………………………………....81 Synthesis and Spectroscopic Studies of 10-14……………...81 Molecular structure studies of 10-14………………………..83 Polymerization of MMA Using Complexes 10, 11, 13 and 14 as Initiators…………………………………………………..93 Summary………………………….…..……………………..97 Experimental Section………………………………………..97 References………………………………………………….100 Chapter 5. Conclusion………………………………………………….106 Chapter 6. General Informations NMR Spectra…………………………………....………….109 Gel Permeation Chromatography (GPC)…………………..109 X-ray Crystallographic Studies………..…..…………...….109 Differential Scanning Calorimeter (DSC)…………...…......110 Materials…………………………………………………....110 Reference…………………………………..….……….…...111 Catalog of Scheme, Figures and Tables Scheme 1…………………………………………………………….……18 Scheme 2……………………………………………………………….…45 Scheme 3……………………………………………………………….…51 Scheme 4………………………………………………………………….66 Scheme 5………………………………………………………………….82 Scheme 6……………………………………………………………...…108 Figure 1…………………………………………………………………....21 Figure 2…………………………………………………………………....21 Figure 3……………………………………………………………………25 Figure 4……………………………………………………………………25 Figure 5……………………………………………………………………29 Figure 6……………………………………………………………………29 Figure 7……………………………………………………………………32 Figure 8…………………………………………………………………....36 Figure 9……………………………………………………………………37 Figure 10…………………………………………………………………..42 Figure 11…………………………………………………………………..43 Figure 12…………………………………………………………………..49 Figure 13……………………………………………………………….….49 Figure 14…………………………………………………………………..69 Figure 15…………………………………………………………………..69 Figure 16…………………………………………………………………..85 Figure 17…………………………………………………………………..86 Figure 18…………………………………………………………………..86 Figure 19…………………………………………………………………..87 Figure 20…………………………………………………………………..87 Figure 21…………………………………………………………………..96 Table 1…………………………………………………………………….22 Table 2…………………………………………………………………….22 Table 3…………………………………………………………………….23 Table 4…………………………………………………………………….26 Table 5…………………………………………………………………….26 Table 6…………………………………………………………………….27 Table 7…………………………………………………………………….30 Table 8…………………………………………………………………….30 Table 9…………………………………………………………………….31 Table 10…………………………………………………………………...33 Table 11…………………………………………………………………...35 Table 12…………………………………………………………….…..…40 Table 13………………………………………………………………...…41 Table 14……………………………………………………….…………..48 Table 15………………………………………………………………...…66 Table 16………………………………………………………………...…68 Table 17………………………………………………………………...…88 Table 18………………………………………………………………..….88 Table 19………………………………………………………………...…89 Table 20………………………………………………………………..…90 Table 21………………………………………………………………..…91 Table 22………………………………………………………………..…92 Table 23………………………………………………………………..…9

一種用於進行開環聚合反應的催化劑及其製法

本發明係關於一種可催化化學開環聚合(Ring Opening Polymerization, ROP)反應之催化劑，特別是關於一種具有鎂的芳氧化合物結構的催化劑及其製造方法，以及此種催化劑應用於開環聚合反應的方法。此鎂的芳氧化合物無毒性，不易殘留於聚合反應所生成的聚合物中，可提高聚合物產品的安全性。此外，此種催化劑對於開環聚合反應有極佳之催化效果，與習知的同類型反應而言，使用此催化劑進行開環聚合反應，具有反應溫度低，反應時間短，轉化率高，以及產率高等優點