双官能膦盐催化生物基聚酯的合成任务书

 2022-01-29 06:01

全文总字数:5092字

1. 毕业设计(论文)的内容和要求

1.文献查阅从查阅文献着手,在中国期刊网,维普数据库,超星数字图书馆,美国化学学会(ACS)数据库,CA,SCI等检索资源上查阅有关双官能团膦盐催化生物基聚酯的合成的相关文献。

2.文献阅读及综述阅读与课题相关的文献,了解双官能团膦盐催化生物基聚酯的合成的基本情况、方法和国内外的研究动态,撰写文献综述。

3.明确实验任务,拟定实验方案根据所查阅文献的内容,确定实验内容及方案,拟定科学可行的研究计划。

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2. 实验内容和要求

1. 实验内容本课题拟定合成路线示例如下:以三苯基膦为原料,与丙烯酸反应合3-(三苯基膦)丙酸酯,并催化TMC,L-LA等生物基聚酯的开环聚合。

选取不同位阻、电性的取代基,合成不同种类双官能团膦盐。

选取模板反应,应用控制变量法,探索加入的催化剂、溶剂、温度,浓度等对模板反应产物产率的影响,筛选出最佳反应条件。

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3. 参考文献

(1) McKinlay, C. J.; Waymouth, R. M.; Wender, P. A. Cell-Penetrating, Guanidinium-Rich Oligophosphoesters: Effective and Versatile Molecular Transporters for Drug and Probe Delivery. J. Am. Chem. Soc. 2016, 138 (10), 35103517.(2) Geihe, E. I.; Cooley, C. B.; Simon, J. R.; Kiesewetter, M. K.;Edward, J. A.; Hickerson, R. P.; Kaspar, R. L.; Hedrick, J. L.; Waymouth, R. M.; Wender, P. A. Designed Guanidinium-Rich Amphipathic Oligocarbonate Molecular Transporters Complex,Deliver and Release siRNA in Cells. Proc. Natl. Acad. Sci. U. S. A.2012, 109 (33), 1317113176.(3) Cooley, C. B.; Trantow, B. M.; Nederberg, F.; Kiesewetter, M. K.;Hedrick, J. L.; Waymouth, R. M.; Wender, P. A. Oligocarbonate Molecular Transporters: Oligomerization Based Syntheses and Cell Penetrating Studies. J. Am. Chem. Soc. 2009, 131, 1640116403.(4) Lin, B.; Waymouth, R. M. Urea Anions: Simple, Fast, and Selective Catalysts for Ring-Opening Polymerizations. J. Am. Chem. Soc. 2017, 139, 16451652.(5) Zhang, X.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M. Fast and Selective Ring-Opening Polymerizations by Alkoxides and Thioureas. Nat. Chem. 2016, 8, 10471053.(6) Dharmaratne, N. U.; Pothupitiya, J. U.; Bannin, T. J.; Kazakov, O. I.; Kiesewetter, M. K. Triclocarban: Commercial Antibacterial and Highly Effective H-Bond Donating Catalyst for Ring-Opening Polymerization. ACS Macro Lett. 2017, 6 (4), 421425.(7) Fastnacht, K. V.; Spink, S. S.; Dharmaratne, N. U.; Pothupitiya, J. U.; Datta, P. P.; Kiesewetter, E. T.; Kiesewetter, M. K. Bis- and Tris-Urea H-Bond Donors for Ring-Opening Polymerization: Unprecedented Activity and Control from an Organocatalyst. ACS Macro Lett. 2016, 5 (8), 982986.(8) Xu, S.; Sun, H.; Liu, J.; Xu, J.; Pan, X.; Dong, H.; Liu, Y.; Li, Z.;Guo, K. Internal Lewis Pair Enhanced H-Bond Donor: Boronate-Urea and Tertiary Amine Co-Catalysis in Ring-Opening Polymerization. Polym. Chem. 2016, 7 (44), 68436853.(9) He, X.; Ji, Y.; Jin, Y.; Kan, S.; Xia, H.; Chen, J.; Liang, B.; Wu, H.;Guo, K.; Li, Z. Bifunctional Imidodiphosphoric Acid-Catalyzed Controlled/living Ring-Opening Polymerization of Trimethylene Carbonate Resulting Block, Dihydroxy Telechelic, and Star-Shaped Polycarbonates. J. Polym. Sci., Part A: Polym. Chem. 2014, 52 (7),10091019.(10) Lohmeijer, B. G. G.; Pratt, R. C.; Leibfarth, F.; Logan, J. W.;Long, D. A.; Dove, A. P.; Nederberg, F.; Choi, J.; Wade, C.;Waymouth, R. M.; et al. Guanidine and Amidine Organocatalysts for Ring-Opening Polymerization of Cyclic Esters. Macromolecules 2006,39 (25), 85748583.(11) Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Lundberg, P. N.P.; Dove, A. P.; Li, H.; Wade, C. G.; Waymouth, R. M.; Hedrick, J. L.Exploration, Optimization, and Application of Supramolecular ThioureaAmine Catalysts for the Synthesis of Lactide (Co)polymers.Macromolecules 2006, 39 (23), 78637871.(12) Dove, A. P.; Pratt, R. C.; Lohmeijer, B. G. G.; Waymouth, R. M.;Hedrick, J. L. Thiourea-Based Bifunctional Organocatalysis: Supramolecular Recognition for Living Polymerization. J. Am. Chem. Soc.2005, 127 (40), 1379813799.(13) Kazakov, O. I.; Kiesewetter, M. K. Cocatalyst Binding Effects in Organocatalytic Ring-Opening Polymerization of L -Lactide. Macromolecules 2015, 48 (17), 61216126.(14) Kazakov, O. I.; Datta, P. P.; Isajani, M.; Kiesewetter, E. T.;Kiesewetter, M. K. Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization. Macromolecules 2014, 47 (21),74637468.(15) Koeller, S.; Kadota, J.; Peruch, F.; Deffieux, A.; Pinaud, N.;Pianet, I.; Massip, S.; Leger, J.-M.; Desvergne, J.-P.; Bibal, B. (Thio)Amidoindoles and (Thio)amidobenzimidazoles: An Investigation of Their Hydrogen-Bonding and Organocatalytic Properties in the Ring-Opening Polymerization of Lactide. Chem. - Eur. J. 2010, 16 (14),41964205.(16) Thomas, C.; Bibal, B. Hydrogen-Bonding Organocatalysts for Ring-Opening Polymerization. Green Chem. 2014, 16 (4), 1687.

4. 毕业设计(论文)计划

2020.12.28-2021.2.30查阅文献,熟悉反应原理和实验操作,翻译外文文献,撰写开题报告2021.3.1-2021.3.15确定实验方案,对课题进行初步实验2021.3.16-2021.3.31对前一阶段研究内容进行中期汇报,完成中期自检,确定下一步实验方案2021.4.1-2021.4.15扩展课题研究范围,改进实验方案,对数据整理分析,撰写论文2021.4.16-2021.5.15完善毕业论文,补充数据,定稿

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