Synthesis of a Diethyl-protected Cyclic Lysine Monomer and Its Copolymerization with <italic style="font-style: italic">ε</italic>-Caprolactam

Ya-hui Mao; Si-qi Wang; Mao-sheng Li; You-hua Tao

doi:10.11777/j.issn1000-3304.2024.24127

您当前的位置：

首页 >

文章列表页 >

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

Research Article | 更新时间：2025-01-10

- Synthesis of a Diethyl-protected Cyclic Lysine Monomer and Its Copolymerization with ε-Caprolactam
  增强出版
- Acta Polymerica Sinica Vol. 55, Issue 12, Pages: 1680-1685(2024)
- 作者机构：
  
  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
- 作者简介：
  
  Si-qi Wang, E-mail: wangsiqi@ciac.ac.cn
  You-hua Tao, E-mail: youhua.tao@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24127
  CLC：
- CSTR：32057.14.GFZXB.2024.7269
- Published：20 December 2024，
  
  Published Online：11 September 2024，
  
  Received：28 April 2024，
  
  Accepted：2024-06-13
- 稿件说明：
移动端阅览
毛亚辉, 王思棋, 李茂盛, 陶友华. 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. 高分子学报, 2024, 55(12), 1680-1685

Mao, Y. H.; Wang, S. Q.; Li, M. S.; Tao, Y. H. Synthesis of a diethyl-protected cyclic lysine monomer and its copolymerization with ε-caprolactam. Acta Polymerica Sinica, 2024, 55(12), 1680-1685
毛亚辉, 王思棋, 李茂盛, 陶友华. 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. 高分子学报, 2024, 55(12), 1680-1685 DOI： 10.11777/j.issn1000-3304.2024.24127. CSTR： 32057.14.GFZXB.2024.7269.

Mao, Y. H.; Wang, S. Q.; Li, M. S.; Tao, Y. H. Synthesis of a diethyl-protected cyclic lysine monomer and its copolymerization with ε-caprolactam. Acta Polymerica Sinica, 2024, 55(12), 1680-1685 DOI： 10.11777/j.issn1000-3304.2024.24127. CSTR： 32057.14.GFZXB.2024.7269.

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(

-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(

H-NMR)、碳谱(

C-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 (

=21%)而言，共聚物的断裂伸长率有所提升(可达(105±8)%).

Abstract

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

with a seven-membered ring from lysine

which was subsequently copolymerized with

-caprolactam to produce innovative copolyamide. Comprehensive characterizations including nuclear magnetic resonance hydrogen spectra (

H-NMR)

carbon spectra (

C-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

Keywords

LysinePolyamideRing-opening polymerizationCopolymerization

references

安泽胜, 陈昶乐, 何军坡, 洪春雁, 李志波, 李子臣, 刘超, 吕小兵, 秦安军, 曲程科, 唐本忠, 陶友华, 宛新华, 王国伟, 王佳, 郑轲, 邹文凯. 中国高分子合成化学的研究与发展动态. 高分子学报, 2019, 50(10), 1083-1132. doi:10.11777/j.issn1000-3304.2019.19136http://dx.doi.org/10.11777/j.issn1000-3304.2019.19136

Andrady A. L.; Neal M. A.Applications and societal benefits of plastics. Philos. Trans. R. Soc. Lond. B Biol. Sci., 2009, 364(1526), 1977-1984. doi:10.1098/rstb.2008.0304http://dx.doi.org/10.1098/rstb.2008.0304

Cywar R. M.; Rorrer N. A.; Hoyt C. B.; Beckham G. T.; Chen E. Y. X.Bio-based polymers with performance-advantaged properties. Nat. Rev. Mater., 2022, 7, 83-103. doi:10.1038/s41578-021-00363-3http://dx.doi.org/10.1038/s41578-021-00363-3

Levi P. G.; Cullen J. M.Mapping global flows of chemicals: from fossil fuel feedstocks to chemical products. Environ. Sci. Technol., 2018, 52(4), 1725-1734. doi:10.1021/acs.est.7b04573http://dx.doi.org/10.1021/acs.est.7b04573

Shafiee S.; Topal E.When will fossil fuel reserves be diminished?Energy Policy, 2009, 37(1), 181-189. doi:10.1016/j.enpol.2008.08.016http://dx.doi.org/10.1016/j.enpol.2008.08.016

Hopewell J.; Dvorak R.; Kosior E.Plastics recycling: challenges and opportunities. Philos. Trans. R. Soc. Lond. B Biol. Sci., 2009, 364(1526), 2115-2126. doi:10.1098/rstb.2008.0311http://dx.doi.org/10.1098/rstb.2008.0311

Weiss M.; Haufe J.; Carus M.; Brandão M.; Bringezu S.; Hermann B.; Patel M. K.A review of the environmental impacts of biobased materials. J. Ind. Ecol., 2012, 16(s1), S169-S181. doi:10.1111/j.1530-9290.2012.00468.xhttp://dx.doi.org/10.1111/j.1530-9290.2012.00468.x

Zhu Y. Q.; Romain C.; Williams C. K.Sustainable polymers from renewable resources. Nature, 2016, 540(7633), 354-362. doi:10.1038/nature21001http://dx.doi.org/10.1038/nature21001

Gallezot P.Conversion of biomass to selected chemical products. Chem. Soc. Rev., 2012, 41(4), 1538-1558. doi:10.1039/c1cs15147ahttp://dx.doi.org/10.1039/c1cs15147a

Ragauskas A. J.; Williams C. K.; Davison B. H.; Britovsek G.; Cairney J.; Eckert C. A.; Frederick W. J.Jr, Hallett J. P.; Leak D. J.; Liotta C. L.; Mielenz J. R.; Murphy R.; Templer R.; Tschaplinski T.The path forward for biofuels and biomaterials. Science, 2006, 311(5760), 484-489. doi:10.1126/science.1114736http://dx.doi.org/10.1126/science.1114736

陈沁, 杜杰毫, 谢海波, 赵宗保, 郑强. 生物基可聚合单体及其聚合物制备与性能研究进展. 高分子学报, 2016, (10), 1330-1358. doi:10.11777/j.issn1000-3304.2016.16154http://dx.doi.org/10.11777/j.issn1000-3304.2016.16154

陈学思, 陈国强, 陶友华, 王玉忠, 吕小兵, 张立群, 朱锦, 张军, 王献红. 生态环境高分子的研究进展. 高分子学报, 2019, 50(10), 1068-1082. doi:10.11777/j.issn1000-3304.2019.19124http://dx.doi.org/10.11777/j.issn1000-3304.2019.19124

Reimschuessel, H. K. Polyamides. In: Buschow, K. H. J.; Cahn, R. W.; Flemings, M. C.; Ilschner, B.; Kramer, E. J.; Mahajan, S.; Veyssière, P., eds. Encyclopedia of Materials: Science and Technology. Oxford: Elsevier, 2001. 7147-7149.

Fangueiro R.; Pereira C. G.; De Araújo M.Applications of polyesters and polyamides in civil engineering. Polyesters and Polyamides. Amsterdam: Elsevier, 2008. 542-592. doi:10.1533/9781845694609.3.542http://dx.doi.org/10.1533/9781845694609.3.542

Winnacker M.; Rieger B.Biobased polyamides: recent advances in basic and applied research. Macromol. Rapid Commun., 2016, 37(17), 1391-1413. doi:10.1002/marc.201600181http://dx.doi.org/10.1002/marc.201600181

Ikeda M.; Takeno, S. Recent advances in amino acid production. In: Inui, M.; Toyoda, K., eds. Microbiology Monographs. Cham: Springer International Publishing, 2020. 175-226. doi:10.1007/978-3-030-39267-3_7http://dx.doi.org/10.1007/978-3-030-39267-3_7

D'Este M.; Alvarado-Morales M.; Angelidaki I.Amino acids production focusing on fermentation technologies—a review. Biotechnol. Adv., 2018, 36(1), 14-25. doi:10.1016/j.biotechadv.2017.09.001http://dx.doi.org/10.1016/j.biotechadv.2017.09.001

Kaleta C.; Schäuble S.; Rinas U.; Schuster S.Metabolic costs of amino acid and protein production in escherichia coli. Biotechnol. J., 2013, 8(9), 1105-1114. doi:10.1002/biot.201200267http://dx.doi.org/10.1002/biot.201200267

Mueller U.; Huebner S.Economic aspects of amino acids production. FaurieR.; ThommelJ.; BatheB.; DebabovV. G.; HuebnerS.; IkedaM.; KimuraE.; MarxA.; MöckelB.; MuellerU.; PfefferleW., eds. Advances in Biochemical Engineering/Biotechnology. Berlin, Heidelberg: Springer Berlin Heidelberg, 2002. 137-170. doi:10.1007/3-540-45989-8_5http://dx.doi.org/10.1007/3-540-45989-8_5

Usuda Y.; Hara Y.; Kojima, H. Toward sustainable amino acid production. In: Yokota, A.; Ikeda, M., eds. Amino Acid Fermentation. Tokyo: Springer Japan, 2017. 289-304. doi:10.1007/10_2016_36http://dx.doi.org/10.1007/10_2016_36

Leinonen I.; Iannetta P. P. M.; Rees R. M.; Russell W.; Watson C.; Barnes A. P.Lysine supply is a critical factor in achieving sustainable global protein economy. Front. Sustain. Food Syst., 2019, 3, 27. doi:10.3389/fsufs.2019.00027http://dx.doi.org/10.3389/fsufs.2019.00027

Félix F. K. D. C.; Letti L. A. J.; Vinícius de Melo Pereira, G.; Bonfim P. G. B.; Soccol V. T.; Soccol C. R.L-lysine production improvement: a review of the state of the art and patent landscape focusing on strain development and fermentation technologies. Crit. Rev. Biotechnol., 2019, 39(8), 1031-1055. doi:10.1080/07388551.2019.1663149http://dx.doi.org/10.1080/07388551.2019.1663149

Sanchez S.; Rodríguez-Sanoja R.; Ramos A.; Demain A. L.Our microbes not only produce antibiotics, they also overproduce amino acids. J. Antibiot., 2018, 71(1), 26-36. doi:10.1038/ja.2017.142http://dx.doi.org/10.1038/ja.2017.142

Lian J. W.; Chen J. L.; Luan S. F.; Liu W.; Zong B. N.; Tao Y. H.; Wang X. H.Organocatalytic copolymerization of cyclic lysine derivative and ε-caprolactam toward antibacterial nylon-6 polymers. ACS Macro Lett., 2022, 11(1), 46-52. doi:10.1021/acsmacrolett.1c00658http://dx.doi.org/10.1021/acsmacrolett.1c00658

Chen J. L.; Dong Y. L.; Xiao C. S.; Tao Y. H.; Wang X. H.Organocatalyzed ring-opening polymerization of cyclic lysine derivative: Sustainable access to cationic poly(ε-lysine) mimics. Macromolecules, 2021, 54(5), 2226-2231. doi:10.1021/acs.macromol.0c02689http://dx.doi.org/10.1021/acs.macromol.0c02689

Tao Y. H.; Chen X. Y.; Jia F.; Wang S. X.; Xiao C. S.; Cui F. C.; Li Y. Q.; Bian Z.; Chen X. S.; Wang X. H.New chemosynthetic route to linear ε-poly-lysine. Chem. Sci., 2015, 6(11), 6385-6391. doi:10.1039/c5sc02479jhttp://dx.doi.org/10.1039/c5sc02479j

Views

167

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Preparation and Properties of (Imino-1,4-cyclohexylenemethylene-1,4-cyclohexyleneimino dodecanedicarboxyl)-co-(iminohexyleneiminohexanedicarboxyl) Copolymers

Synthesis and Properties of Polycaprolactone and Polycarbonate-based Polyurethanes

Study of the Organobase Catalyzed Synthesis of Diphenyl Silicone Rubbers and Their Damping Property

Tailoring Properties and Performance of Polyamide Composite Nanofiltration Membranes by LiCl-added Interfacial Polymerization

Related Author

Zhong-liang Peng

Dan-qing Yi

Yu-cai Ke

Yong-mei Ma

Yi Wei

Fo-song Wang

Sheng-juan Ma

Hui-qun Liu

Related Institution

College of Material Science and Engineering, Central South University

Institute of Chemistry, Chinese Academy of Sciences

College of Material Science and Engineering, Beijing Institute of Fashion Technology

School of Materials Science and Engineering, Tianjin University

College of Polymer Science and Engineering, Qingdao University of Science and Technology

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802024621
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰

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

DOI：10.11777/j.issn1000-3304.2024.24127

摘要

Abstract

关键词

Keywords

references