Controllable Ring-opening Polymerization of <italic style="font-style: italic">δ</italic>-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems

Xin-Yu Liu; Liang Zhu; Su-Yun Jie; Bo-Geng Li

doi:10.1007/s10118-024-3127-3

Your Location：

Home >

Browse articles >

Controllable Ring-opening Polymerization of δ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems

RESEARCH ARTICLE | Updated：2024-08-06

- Controllable Ring-opening Polymerization of δ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems
- Chinese Journal of Polymer Science Vol. 42, Issue 8, Pages: 1103-1110(2024)
- Affiliations：
  
  State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China
- Author bio：
  
  jiesy@zju.edu.cn
- Funds：
- DOI：10.1007/s10118-024-3127-3
  CLC：
- Published：01 August 2024，
  
  Published Online：25 April 2024，
  
  Received：25 January 2024，
  
  Revised：18 March 2024，
  
  Accepted：20 March 2024
- Accepted：
Scan for full text
Liu, X. Y.; Zhu, L.; Jie, S. Y.; Li, B. G. Controllable ring-opening polymerization of δ-valerolactone catalyzed by quinolinyl-urea/MTBD systems. Chinese J. Polym. Sci. 2024, 42, 1103–1110

Xin-Yu Liu, Liang Zhu, Su-Yun Jie, et al. Controllable Ring-opening Polymerization of δ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems. [J]. Chinese Journal of Polymer Science 42(8):1103-1110(2024)
Liu, X. Y.; Zhu, L.; Jie, S. Y.; Li, B. G. Controllable ring-opening polymerization of δ-valerolactone catalyzed by quinolinyl-urea/MTBD systems. Chinese J. Polym. Sci. 2024, 42, 1103–1110 DOI： 10.1007/s10118-024-3127-3.

Xin-Yu Liu, Liang Zhu, Su-Yun Jie, et al. Controllable Ring-opening Polymerization of δ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems. [J]. Chinese Journal of Polymer Science 42(8):1103-1110(2024) DOI： 10.1007/s10118-024-3127-3.

摘要

A series of quinolinyl-urea catalysts were synthesized and evaluated to be highly active in the ring-opening polymerization of δ-VL in combination with MTBD. Linear PVLs with narrow molecular weight distribution were obtained and the “living”/controllable characteristic of ROP was verified by the kinetic and chain extension experiments.

Abstract

Due to their excellent biocompatibility and biodegradability

aliphatic polyesters are widely used in the biomedical

packaging and agricultural fields

which are usually accessed by the ring-opening polymerization (ROP) of lactones and the catalysts particularly play an important role. Herein a series of quinolinyl-urea catalysts have been synthesized

via

the reaction between isocyanate and aminoquinoline with an amino group at different substitution positions and characterized. In combination with 7-methyl-1

7-triazabicyclo[4

]

dec-5-ene (MTBD) as a cocatalyst and benzyl alcohol (BnOH) as an initiator

1-(3

5-bis(trifluoromethyl)phenyl)-3-(quinolin-3-yl)urea (

3-QU

) was observed to be most active for the ROP of

-valerolactone (

-VL). The polymerization conditions were optimized by varying the type of organic base

catalyst concentration and reaction temperature. By changing the ratio of [M

]

/[I

]

linear polyvalerolactones (PVLs) with different molecular weights and narrow molecular weight distribution wer

e prepared. The kinetic and chain extension experiments were carried out to prove the “living”/controllable feature. And the NMR experiments were used to support the proposal of possible mechanism.

关键词

Keywords

Quinolinyl-ureaRing-opening polymerizationPVL

references

Geyer R.; Jambeck J. R.; Law K. L. Production, use, and fate of all plastics ever made.Science2017,3, e1700782..

Webb H. K.; Arnott J.; Crawford R. J.; Ivanova, E. P. Plastic degradation and its environmental implications with special reference to poly(ethylene terephthalate).Polymers2012,5, 1−18..

Duis K.; Coors A. Microplastics in the aquatic and terrestrial environment: sources (with a specific focus on personal care products), fate and effects.Environ. Sci. Eur.2016,28, 2..

Schneiderman D. K.; Hillmyer M. A. Aliphatic polyester block polymer design.Macromolecules 2016 ,49, 2419−2428..

Larranaga A.; Lizundia E. A review on the thermomechanical properties and biodegradation behaviour of polyesters.Eur. Polym. J.2019,121, 109296..

Brannigan R. P.; Dove A. P. Synthesis, properties and biomedical applications of hydrolytically degradable materials based on aliphatic polyesters and polycarbonates.Biomater. Sci. 2017 ,5, 9−21..

Hillmyer M. A.; Tolman W. B. Aliphatic polyester block: renewable, degradable, and sustainable.Acc. Chem. Res.2014,47, 2390−2396..

Chiulan I.; Frone A.; Brandabur C.; Panaitescu D. M. Recent advances in 3D printing of aliphatic polyesters.Bioengineering2018,5, 2..

Arrieta M.; Samper M.; Aldas M.; López J. On the use of PLA-PHB blends for sustainable food packaging applications.Materials2017,10, 1008..

Pascouau C.; Wirotius A. L.; Carlotti S. Functional polyestersviaring-opening copolymerization ofα-hydroxy-γ-butyrolactone andε-caprolactone: La[N(SiMe3)2]3as an efficient coordination-insertion catalyst.Eur. Polym. J.2023,185, 111793..

Kim S. H.; Kim S. H.; Jung Y. TGF-β3encapsulated PLCL scaffold by a supercritical CO2-HFIP co-solvent system for cartilage tissue engineering.J. Control. Release2015,206, 101−107..

Haas S.; Hain N.; Raoufi M.; Handschuh-Wang, S.; Wang, T.; Jiang, X.; Schönherr, H. Enzyme degradable polymersomes from hyaluronic acid-block-poly(ε-caprolactone) copolymers for the detection of enzymes of pathogenic bacteria.Biomacromolecules2015,16, 832−841..

Cha K. J.; Lih E.; Choi J.; Joung, Y. K.; Ahn, D. J.; Han, D. K. Shape-memory effect by specific biodegradable polymer blending for biomedical applications.Macromol. Biosci.2014,14, 667−678..

Sinha V. R.; Bansal K.; Kaushik R.; Kumria, R.; Trehan, A. Poly-ε-caprolactone microspheres and nanospheres: an overview.Int. J. Pharm.2004,278, 1−23..

Lam, C. X.; Teoh, S. H.; Hutmacher, D. W. Comparison of the degradation of polycaprolactone and polycaprolactone-(β-tricalcium phosphate) scaffolds in alkaline medium.Polym. Int.2007,56, 718−728..

Joshi, P.; Madras, G. Degradation of polycaprolactone in supercritical fluids.Polym. Degrad. Stabil.2008,93, 1901−1908..

Pena, J.; Corrales, T.; Izquierdo-Barba, I.; Doadrio, A.; Vallet-Regi, M. Long term degradation of poly(ε-caprolactone) films in biologically related fluids.Polym. Degrad. Stabil.2006,91, 1424−1432..

Dana, H. R.; Ebrahimi, F. Synthesis, properties, and applications of polylactic acid-based polymers.Polym. Eng. Sci.2023,63, 22−43..

Kamber, N. E.; Jeong, W.; Waymouth, R. M.; Pratt, R. C.; Lohmeijer, B. G. G.; Hedrick, J. L. Organocatalytic ring-opening polymerization.Chem. Rev.2007,107, 5813−5840..

Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth, R. M. Organocatalysis: opportunities and challenges for polymer synthesis.Macromolecules2010,43, 2093−2107..

Nzahou Ottou, W. N.; Sardon, H.; Mecerreyes, D.; Vignolle, J.; Taton, D. Update and challenges in organo-mediated polymerization reactions.Prog. Polym. Sci.2016,56, 64−115..

Hu, S.; Zhao, J.; Zhang, G.; Schlaad, H. Macromolecular architectures through organocatalysis.Prog. Polym. Sci.2017,74, 34−77..

Bossion, A.; Heifferon, K. V.; Meabe, L.; Zivic, N.; Taton, D.; Hedrick, J. L.; Long, T. E.; Sardon, H. Opportunities for organocatalysis in polymer synthesisviastep-growth methods.Prog. Polym. Sci.2019,90, 164−210..

Xu, J.; Wang, X.; Liu, J.; Feng, X.; Gnanou, Y.; Hadjichristidis, N. Ionic H-bonding organocatalysts for the ring-opening polymerization of cyclic esters and cyclic carbonates.Prog. Polym. Sci.2022,125, 101484..

Zhang, X.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M. Fast and selective ring-opening polymerizations by alkoxides and thioureas.Nature Chem.2016,8, 1047−1053..

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, 982−986..

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, 421−425..

Lin B.; Waymouth, R. M. Urea anions: simple, fast, and selective catalysts for ring-opening polymerizations.J. Am. Chem. Soc.2017,139, 1645−1652..

Jain, I.; Malik, Payal. Advances in urea and thiourea catalyzed ring opening polymerization: a brief overview.Eur. Polym. J.2020,133, 109791..

Hewawasam, R. S.; Kalana,U. L. D. I.; Dharmaratne, N. U.; Wright, T. J.; Bannin, T. J.; Kiesewetter E. T.; Kiesewetter, M. K.Macromolecules 2019 ,52, 9232–9237..

Du,F.; Zheng, Y.; Yuan, W.; Shan, G.; Bao, Y.; Jie S.; Pan, P. Solvent-free ring-opening polymerization of lactones with hydrogen-bonding bisurea catalyst.J. Polym. Sci., Part A: Polym. Chem.2018,57, 90−100..

Zaky, M. S.; Guichard, G.; Taton, D. Structural effect of organic catalytic pairs based on chiral amino(thio)ureas and phosphazene bases for the isoselective ring-opening polymerization of racemic lactide.Macromolecules2023,56, 3607−3616..

Feng, R.; Jie, S.; Braunstein P.; Li, B. G. Pyridyl-urea catalysts for the solvent-free ring-opening polymerization of lactones and trimethylene carbonate.Eur. Polym. J.2019,121, 109293..

Feng, R.; Jie, S.; Braunstein P.; Li, B.-G. High molecular-weight cyclic polyesters from solvent-free ring-opening polymerization of lactones with a pyridyl-urea/MTBD.Macromol. Chem. Phys.2020,221, 2000075..

Feng, R.; Jie, S.; Braunstein P.; Li, B. G. Gradient copolymers ofε-caprolactone andδ-valerolactoneviasolvent-free ring-opening copolymerization with a pyridyl-urea/MTBD system.J. Polym. Sci.2020,58, 2108−2115..

Ji, C.; Jie, S.; Braunstein P.; Li, B. G. Fast and controlled ring-opening polymerization ofδ-valerolactone catalyzed by benzoheterocyclic urea/MTBD catalysts.Catal. Sci. Technol.2020,10, 7555−7565.

Ji, C.; Jie, S.; Li, B. G. Ring-opening copolymerization of L-lactide andδ-valerolactone catalyzed by benzoxazolyl urea catalyst/MTBD.Acta Polymerica Sinica(in Chinese)2022,53, 488−496..

Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Waymouth, R. M.; Hedrick, J. L. Triazabicyclodecene: A simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters.J. Am. Chem. Soc.2006,128, 4556−4557..

Simón L.; Goodman, J. M. The mechanism of TBD-catalyzed ring-opening polymerization of cyclic esters.J. Org. Chem.2007,72, 9656−9662..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Triclosan-conjugated, Lipase-responsive Polymeric Micelles for Eradication of Staphylococcal Biofilms

Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides

Related Author

Yan-Qiang Huang

Yuan-Feng Li

Yong Liu

Lin-Qi Shi

Feng Ren

Zhuang-Zhuang Liang

Ming-Xin Niu

Chen-Yang Hu

Related Institution

State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials of Ministry of Education, and Institute of Polymer Chemistry, College of Chemistry, Nankai University

Wenzhou Institute, University of Chinese Academy of Sciences

Translational Medicine Laboratory, the First Affiliated Hospital of Wenzhou Medical University

Guangxi Technology Innovation Cooperation Base of Prevention and Control Pathogenic Microbes with Drug Resistance, Youjiang Medical University for Nationalities

Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

⁰

Controllable Ring-opening Polymerization of δ-Valerolactone Catalyzed by Quinolinyl-Urea/MTBD Systems

DOI：10.1007/s10118-024-3127-3

摘要

Abstract

关键词

Keywords

references