基于Ugi反应聚酰胺的制备

doi:10.3969/j.issn.1000-1565.2019.04.007

摘要/Abstract

摘要： 以不同结构的氨基酸、醛、叔丁基异腈为单体,以无水甲醇为溶剂,在室温条件下通过Ugi反应制备出一系列聚酰胺.利用FTIR、¹H NMR、¹³C NMR和GPC等技术系统地表征了聚酰胺的结构,考查了单体投料比、单体浓度、反应时间以及不同结构氨基酸和醛等因素对聚合反应的影响.结果表明,在Ugi反应中,随着聚合时间的延长,聚酰胺的收率逐渐增加,而摩尔质量变化不明显.当氨基酸、醛和叔丁基异腈的投料比(物质的量比)为1∶1.1∶1.1时,聚酰胺的收率较高,摩尔质量最大;同时,5-氨基戊酸和6-氨基己酸分别与异丁醛、叔丁基异腈组成聚合体系时,聚酰胺的摩尔质量分别达到2.02×10⁴ 和1.96×10⁴ g/mol,且收率均超过93.0%.总之,Ugi聚合反应为不同结构与性能聚酰胺材料的制备提供了一种便捷高效的合成方法.

关键词: Ugi反应, 氨基酸, 聚酰胺

Abstract: In this work, a series of polyamides were successfully synthesized at room temperature via Ugi reaction, using amino acids, aldehyde and t-butylisocyanide as monomers in methanol.The structures of the polyamide were characterized by FTIR, ¹H NMR, ¹³C NMR and GPC.The effects of monomer feed ratio, monomer concentration, reaction time and different amino acids and aldehydes on the polymerization were investigated.It was found that the yield of polyamide increases gradually with the polymerization time, while the molecular weight did not change significantly.When the molar ratio of amino acids, aldehyde and t-butylisocyanide is equal to 1∶1.1∶1.1, the yield of polyamides and its molecular weight were the largest.When 5-aminovaleric acid and 6-aminocaproic acid were polymerized with isobutylaldehyde and t-butylisocyanide, respectively, the molecular weights of polyamides were 2.02×10⁴ and 1.96×10⁴ g/mol, their yields are 93%.In conclusion, Ugi reaction provides a convenient and efficient synthetic strategy for the preparation of polyamides with different structures and properties.- DOI:10.3969/j.issn.1000-1565.2019.04.007基于Ugi反应聚酰胺的制备张朋飞^1,2,刘娜¹,赵荣慧^1,3,张琪¹,秦斐¹,邓奎林¹(1.河北大学化学与环境科学学院临床药学办公室,河北保定 071002;2.保定学院生物化工与环境工程学院,河北保定 071000;3.河北大学附属医院临床药学办公室,河北保定 071000)摘要:以不同结构的氨基酸、醛、叔丁基异腈为单体,以无水甲醇为溶剂,在室温条件下通过Ugi反应制备出一系列聚酰胺.利用FTIR、¹H NMR、¹³C NMR和GPC等技术系统地表征了聚酰胺的结构,考查了单体投料比、单体浓度、反应时间以及不同结构氨基酸和醛等因素对聚合反应的影响.结果表明,在Ugi反应中,随着聚合时间的延长,聚酰胺的收率逐渐增加,而摩尔质量变化不明显.当氨基酸、醛和叔丁基异腈的投料比(物质的量比)为1∶1.1∶1.1时,聚酰胺的收率较高,摩尔质量最大;同时,5-氨基戊酸和6-氨基己酸分别与异丁醛、叔丁基异腈组成聚合体系时,聚酰胺的摩尔质量分别达到2.02×10⁴ 和1.96×10⁴ g/mol,且收率均超过93.0%.总之,Ugi聚合反应为不同结构与性能聚酰胺材料的制备提供了一种便捷高效的合成方法.关键词:Ugi反应;氨基酸;聚酰胺中图分类号:O633.2 文献标志码:A 文章编号:1000-1565(2019)04-0372-07Preparation of polyamides based on Ugi reactionZHANG Pengfei^1,2, LIU Na¹, ZHAO Ronghui¹, ZHANG Qi¹, QIN Fei¹, DENG Kuilin¹(1.College of Chemistry & Environmental Science, Hebei University,Baoding 071002, China; 2.College of Biochemical Engineering& Environmental Engineering, Baoding University, Baoding 071000, China;3.Clinical Pharmacy Office, Affiliated Hospital of Hebei University, Baoding 071000,China)Abstract: In this work, a series of polyamides were successfully synthesized at room temperature via Ugi reaction, using amino acids, aldehyde and t-butylisocyanide as monomers in methanol.The structures of the polyamide were characterized by FTIR, ¹H NMR, ¹³C NMR and GPC.The effects of monomer feed ratio, monomer concentration, reaction time and different amino acids and aldehydes on the polymerization were investigated.It was found that the yield of polyamide increases gradually with the polymerization time, while the molecular weight did not change significantly.When the molar ratio of amino acids, aldehyde and t-butylisocyanide is equal to 1∶1.1∶1.1, the yield of polyamides and its molecular weight were the largest.When 5-aminovaleric acid and 6-aminocaproic acid were polymerized with isobutylaldehyde and t-butylisocyanide, respectively, the molecular weights of polyamides were 2.02×10⁴ and 1.96×10⁴ g/mol, their yields are 93%.In conclusion, Ugi reaction provides a convenient and efficient synthetic strategy for the preparation of polyamides with different structures and properties.- 收稿日期:2018-10-18 基金项目:河北大学大学生创新创业训练计划项目(201810075090);河北省重点研发计划自筹项目(18211241) 第一作者:张朋飞(1984—),男,河北保定人,保定学院讲师,河北大学在读博士研究生,主要从事智能聚合物的设计、制备及性能研究.E-mail:zhangpengfei-1984@163.com 通信作者:邓奎林(1968—),男,河北遵化人,河北大学教授,主要从事智能聚合物的设计、制备及性能研究. E-mail:dengkl_hbu@163.com第4期张朋飞等:基于Ugi反应聚酰胺的制备

Key words: Ugi reaction, amino acid, polyamide

中图分类号:

O633.2

张朋飞,刘娜,赵荣慧,张琪,秦斐,邓奎林. 基于Ugi反应聚酰胺的制备[J]. 河北大学学报(自然科学版), 2019, 39(4): 372-378.

ZHANG Pengfei, LIU Na, ZHAO Ronghui, ZHANG Qi, QIN Fei, DENG Kuilin. Preparation of polyamides based on Ugi reaction[J]. Journal of Hebei University (Natural Science Edition), 2019, 39(4): 372-378.

参考文献

[1] 李修明,贾学顺,殷亮.Post-Ugi反应的研究进展[J].有机化学, 2017, 37(9): 2237-2249.DOI:10.6023/cjoc201704026.
[2] YANG B, ZHAO Y, WEI Y, et al.The Ugi reaction in polymer chemistry: syntheses, applications and perspectives[J].Polymer Chemistry, 2015, 6(48): 8233-8239.DOI:10.1039/c5py01398d.
[3] 刘学巍,甘海峰,钱祥均,等.异腈参与的多组分反应研究进展[J].化学通报,2013, 76(2): 107-112.DOI:10.14159/j.cnki.0441-3776.2013.02.013.
[4] 陶磊,赵原,杨斌,等.以多组分点击化学为基础的高分子合成—高分子合成的新机遇[J].高分子学报,2016,(11):1482-1494. DOI:10.11777/j.issn1000-3304.2016.16218.
[5] 王诗琪,付长奎,危岩,等.多组分聚合体系的探索[J].化学进展,2014, 26(7): 1099-1106.DOI:DOI:10.7536 /PC140110.
[6] ZHANG X J, WANG S X, LIU J, et al.Ugi reaction of natural amino acids: A general route toward facile synthesis of polypeptoids for bioapplications[J].ACS Macro Letters, 2016, 5(9): 1049-1054.DOI:10.1021/acsmacrolett.6b00530.
[7] WU H B, YANG B, ZHAO Y, et al.Fluorescent protein-reactive polymers via one-pot combination of the Ugi reaction and RAFT polymerization[J].Polymer Chemistry, 2016, 7(30): 4867-4872.DOI:10.1039/c6py00781c.
[8] YANG B, ZHAO Y, WANG S Q, et al.Synthesis of multifunctional polymers through the Ugi reaction for protein conjugation[J].Macromolecules, 2014, 47(16): 5607-5612.DOI:10.1021/ma501385m.
[9] SAMAD A AL, WINTER J DE, GERBAUX P, et al.Unique alternating peptide-peptoid copolymers from dipeptidesvia Ugi reaction in water[J].Chemical Communications, 2017, 53(90): 12240-12243.DOI:10.1039/c7cc06463b.
[10] HARTWEG M, BECER C R.Direct polymerization of levulinic acid via Ugi multicomponent reaction[J].Green Chemistry, 2016, 18(11): 3272-3277.DOI:10.1039/c6gc00372a.
[11] ICART L P, FERNANDES E, AGüERO L, et al.Fluorescent microspheres of poly(ethylene glycol)–poly(lactic acid)-fluorescein copolymers synthesized by Ugi four-component condensation[J].J App l Polym Sci, 2016, 133(9):42994-43002.DOI:10.1002/app.42994.
[12] SEHLINGER A, MEIER M AR.Passerini and Ugi multicomponent reactionsin polymer science[J].Adv Poly Sci, 2014, 269: 61-86.DOI:10.1007/12_2014_298
[13] 孙同杰,董侠,胡海青,等.聚酰胺/聚苯胺导电复合材料制备方法的研究进展[J].高分子学报,2014(4): 427-440.DOI:10.3724/SP.J.1105.2014.13426.
[14] ALLEN C L, CHHATWAL A R, WILLIAMS J M J.Direct amide formation from unactivated carboxylic acids and amines[J].Chem Commun, 2012, 48(5): 666-668.DOI:10.1039/c1cc15210f.
[15] 冯宗财,余亚文,刘芳,等.主链型偶氮聚酰胺的合成及光致变色性能[J].高分子材料科学与工程,2015, 31(9): 23-27.DOI:10.16865/j.cnki.1000-7555.2015.09.005.
[16] 唐黎明.聚合反应的典型影响因素分析[J].高分子通报,2017(4): 72-76.DOI:10.14028/j.cnki.1003-3726.2017.04.009.
[17] DEV K, RAMAKRISHNA E, MAURYA S W, et al.Ugi three-component reaction of alcohols, amines and isocyanides: A new approach to the synthesis of cyclic amidines[J].Tetrahedron Letters, 2017, 58(12): 1202-1206.DOI:10.1016/j.tetlet.2017.02.021.
[18] YANG B, ZHAO Y, FU C K, et al.Introducing the Ugi reaction into polymer chemistry as a green click reaction to prepare middle-functional block copolymers[J].Polymer Chemistry, 2014, 5: 2704-2708.DOI:10.1039/c4py00001c.
[19] 颜慧琼, 陈秀琼, 李嘉诚, 等.基于Ugi多组分反应的海藻酸酰胺衍生物改性二氧化硅纳米粒子的制备[J].高等学校化学学报, 2016, 37(5): 1018-1024.DOI:10.7503/cjcu20150831.
[20] MARCACCINI S, TORROBA T.The use of the Ugi four-component condensation[J].Nature Protocols, 2007, 2(3): 632-639.DOI:10.1038/nprot.2007.71.
[21] BU H T, KJØ NIKSEN A L, KNUDSEN K D, et al.Rheological and structural properties of aqueous alginate during gelation via the ugi multicomponent condensation reaction[J].Biomacromolecules, 2004, 5(4): 1470-1479.DOI:10.1021/bm049947.
[22] WANG Q, WANG D X, WANG M X, et al.Still unconquered: enantioselective passerini and ugi multicomponent reactions[J].Accounts of Chemical Research, 2018, 51(5): 1290-1300.DOI:10.1021/acs.accounts.8b00105.