二乙基环状赖氨酸单体的合成及其与己内酰胺的共聚合研究  

Synthesis of a Diethyl-protected Cyclic Lysine Monomer and Its Copolymerization withε-Caprolactam

作　　者：毛亚辉 王思棋 李茂盛[1] 陶友华[1,2] Ya-hui Mao;Si-qi Wang;Mao-sheng Li;You-hua Tao(Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026)

机构地区：[1]中国科学院长春应用化学研究所、生态环境高分子材料重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026

出　　处：《高分子学报》2024年第12期1680-1685,共6页Acta Polymerica Sinica

基　　金：国家重点研发计划(项目号2022YFE0130500);国家杰出青年科学基金(基金号22325108);国家自然科学基金(基金号U21A2089,52273015)资助项目.

摘　　要：以廉价丰富的赖氨酸为原料,通过两步简单高效的反应,合成了二乙基环状赖氨酸单体.在此基础上,成功实现了该单体与己内酰胺(ε-CLa)的共聚,制备得到了一种新的己内酰胺共聚物(数均分子量>27.4 kDa).对所得聚合物进行了核磁共振氢谱(1H-NMR)、碳谱(13C-NMR)及扩散排序核磁共振(DOSY-NMR)表征,证实成功得到共聚物.通过调节单体投料比,可以对聚合物中不同共聚组分的含量进行调控,进而对聚合物性能进行调控.相较于尼龙6(ε=21%)而言,共聚物的断裂伸长率有所提升(可达(105±8)%).As potential alternatives to fossil raw materials,bio-based materials have stimulated the exploration of novel monomer architectures and synthesis strategies in polymer science.Herein,we report the synthesis of a novel diethyl-protected cyclic lysine monomer M1 with a seven-membered ring from lysine,which was subsequently copolymerized withε-caprolactam to produce innovative copolyamide.Comprehensive characterizations including nuclear magnetic resonance hydrogen spectra(1H-NMR),carbon spectra(13C-NMR),and diffusion ordered nuclear magnetic resonance spectroscopy(DOSY-NMR)confirmed that the resulting copolymers were homogeneous rather than a blend of multiple polymers.By adjusting the feed ratio of the monomers,it was possible to control the composition of the copolymers and manipulate properties of these copolymers effectively.Furthermore,this synthesis process demonstrated scalability as laboratory-scale production yielding quantities of up to 50 g.The number-average molecular weight of the copolyamide can reach up to 40 kDa,with a high tensile strength and a high elongation at break((105±8)%),indicating that the polymer exhibits exceptional characteristics akin to general polyamides.This work expands the application of lysine,a biological-based molecule,in polyamide general materials.It is expected to reduce the fossil energy dependence of bulk polyamide materials production and lower the full life cycle carbon footprint of related production processes.

关 键 词：赖氨酸 聚酰胺 开环聚合 共聚 

分 类 号：TQ317[化学工程—高聚物工业]