Controlled Polymerization of Methyl Methacrylate and Styrene <italic style="font-style: italic">via</italic> Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions

Yong-Peng Miao; Jing Lyu; Hai-Yang Yong; Sigen A; Yong-Sheng Gao; Wen-Xin Wang

doi:10.1007/s10118-019-2236-x

Your Location：

Home >

Browse articles >

Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions

ARTICLE | Updated：2021-02-18

- Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions
- Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions
- Chinese Journal of Polymer Science 2019年37卷第6期页码：591-597
- Affiliations：
  
  a.School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
  b.Charles Institute of Dermatology, School of Medicine, University College Dublin, Dublin 4, Ireland
  c.School of Mechanical and Materials Engineering, University College Dublin, Dublin 4, Ireland
- Author bio：
  
  yongsheng.gao@ucdconnect.ie (Y.S.G.)
  wenxin.wang@ucd.ie (W.X.W.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 51573129), Science Foundation Ireland (SFI) Principal Investigator Award (No. 13/IA/1962), Investigator Award (No. 12/IP/1688), and Health Research Board (No. HRA-POR-2013-412).
- DOI：10.1007/s10118-019-2236-x
  中图分类号：
- 收稿：2018-11-26，
  
  修回：2019-1-22，
  
  录用：2019-1-28，
  
  网络首发：2019-03-11，
  
  纸质出版：2019-06
- Accepted：
Scan QR Code
Citation: Miao, Y. P.; Lyu, J.; Yong, H. Y.; A, S.; Gao, Y. S.; Wang, W. X. Controlled polymerization of methyl methacrylate and styrene via Cu(0)-mediated RDRP by selecting the optimal reaction conditions. Chinese J. Polym. Sci. 2019, 37, 591–597

Yong-Peng Miao, Jing Lyu, Hai-Yang Yong, et al. Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions[J]. Chinese Journal of Polymer Science, 2019, 37(6): 591-597. DOI: 10.1007/s10118-019-2236-x.
Citation: Miao, Y. P.; Lyu, J.; Yong, H. Y.; A, S.; Gao, Y. S.; Wang, W. X. Controlled polymerization of methyl methacrylate and styrene via Cu(0)-mediated RDRP by selecting the optimal reaction conditions. Chinese J. Polym. Sci. 2019, 37, 591–597 DOI： 10.1007/s10118-019-2236-x.

Yong-Peng Miao, Jing Lyu, Hai-Yang Yong, et al. Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions[J]. Chinese Journal of Polymer Science, 2019, 37(6): 591-597. DOI: 10.1007/s10118-019-2236-x. DOI：

摘要

Abstract

Cu(0)-mediated reversible deactivation radical polymerization (Cu(0)-mediated RDRP) has been demonstrated as an excellent technique to control the polymerization of multiple vinyl monomers (

e.g.

acrylates

methacrylates

and styrene). However

the complexity of the reaction mechanism and multi-component system nature make it challenging to choose the appropriate conditions and consider the factors of achieving controllable polymerization when switching from one monomer to others with different reactivities. Herein

by polymerizing two examplary monomers: methyl methacrylate (MMA) and styrene

via

Cu(0)-mediated RDRP under different conditions

we have found that the reaction parameters (

e.g.

initiator

ligand

solvent

and deactivator) play a crucial role in regulating two equilibriums: (i) mutual conversion of different copper species which determines the relative concentration of Cu(I) and Cu(II)

and (ii) polymerization equilibrium which is the combination of activation/deactivation

propagation and termination processes. We have demonstrated that by taking both the mutual conversion of different copper species and the polymerization equilibrium into account

the optimal reaction conditions could be selected

and the well-controlled Cu(0)-mediated RDRPs of methyl methacrylate and styrene were achieved with narrow molecular weight distributions and predicted molecular weight.

关键词

Keywords

references

Braunecker, W. A.; Matyjaszewski, K . Controlled/living radical polymerization: Features, developments, and perspectives . Prog. Polym. Sci. , 2007 . 32 93 - 146 . DOI: 10.1016/j.progpolymsci.2006.11.002 http://doi.org/10.1016/j.progpolymsci.2006.11.002 .

Anastasaki, A.; Nikolaou, V.; Haddleton, D. M . Cu(0)-mediated living radical polymerization: Recent highlights and applications: A perspective . Polym. Chem. , 2016 . 7 1002 - 1026 . DOI: 10.1039/C5PY01916H http://doi.org/10.1039/C5PY01916H .

Georges, M. K.; Veregin, R. P. N.; Kazmaier P. M.; Hamer, G. K . Narrow molecular weight resins by a free-radical polymerization process . Macromolecules , 1993 . 26 2987 - 2988 . DOI: 10.1021/ma00063a054 http://doi.org/10.1021/ma00063a054 .

Hawker, C. J.; Barclay G. G.; Dao, J . Radical crossover in nitroxide mediated " living” free radical polymerizations . J. Am. Chem. Soc. , 1996 . 118 11467 - 11471 . DOI: 10.1021/ja9624228 http://doi.org/10.1021/ja9624228 .

Wang, J. S.; Matyjaszewski, K . " Living”/controlled radical polymerization. Transition-metal-catalyzed atom transfer radical polymerization in the presence of a conventional radical initiator . Macromolecules , 1995 . 28 7572 - 7573 . DOI: 10.1021/ma00126a041 http://doi.org/10.1021/ma00126a041 .

Krys, P.; Matyjaszewski, K . Kinetics of atom transfer radical polymerization . Eur. Polym. J. , 2017 . 89 482 - 523 . DOI: 10.1016/j.eurpolymj.2017.02.034 http://doi.org/10.1016/j.eurpolymj.2017.02.034 .

Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H . Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process . Macromolecules , 1998 . 31 5559 - 5562 . DOI: 10.1021/ma9804951 http://doi.org/10.1021/ma9804951 .

Matyjaszewski, K.; Tsarevsky, N. V.; Braunecker, W. A.; Dong, H.; Huang, J.; Jakubowski, W.; Kwak, Y.; Nicolay, R.; Tang, W.; Yoon, J. A . Role of Cu 0 in controlled/" living” radical polymerization . Macromolecules , 2007 . 40 7795 - 7806 . DOI: 10.1021/ma0717800 http://doi.org/10.1021/ma0717800 .

Percec, V.; Guliashvili, T.; Ladislaw, J. S.; Wistrand, A.; Stjerndahl, A.; Sienkowska, M. J.; Monteiro, M. J.; Sahoo, S . Ultrafast synthesis of ultrahigh molar mass polymers by metal-catalyzed living radical polymerization of acrylates, methacrylates, and vinyl chloride mediated by SET at 25 °C . J. Am. Chem. Soc. , 2006 . 128 14156 - 14165 . DOI: 10.1021/ja065484z http://doi.org/10.1021/ja065484z .

Anastasaki, A.; Nikolaou, V.; Nurumbetov, G.; Wilson, P.; Kempe, K.; Quinn, J. F.; Davis, T. P.; Whittaker, M. R.; Haddleton, D. M . Cu(0)-mediated living radical polymerization: A versatile tool for materials synthesis . Chem. Rev. , 2016 . 116 835 - 877 . DOI: 10.1021/acs.chemrev.5b00191 http://doi.org/10.1021/acs.chemrev.5b00191 .

Zhang, N.; Samanta, S. R.; Rosen B. M.; Percec, V . Single electron transfer in radical ion and radical-mediated organic, materials and polymer synthesis . Chem. Rev. , 2014 . 114 5848 - 5958 . DOI: 10.1021/cr400689s http://doi.org/10.1021/cr400689s .

Rose, B. M.; Jiang, X.; Wilson, C. J.; Nguyen, N. H.; Monteiro, M. J.; Percec, V . The disproportionation of Cu(I)X mediated by ligand and solvent into Cu(0) and Cu(II)X 2 and its implications for SET-LRP . J. Polym. Sci., Part A: Polym. Chem. , 2010 . 47 5606 - 5628 . .

Matyjaszewski, K.; Coca, S.; Gaynor, S. G.; Wei, M.; Woodworth, B. E . Zerovalent metals in controlled/" living” radical polymerization . Macromolecules , 1997 . 30 7348 - 7350 . DOI: 10.1021/ma971258l http://doi.org/10.1021/ma971258l .

Wang, Y.; Zhong, M.; Zhu, W.; Peng, C. H.; Zhang, Y.; Konkolewicz, D.; Bortolamei, N.; Isse, A. A.; Gennaro, A.; Matyjaszewski, K . Reversible-deactivation radical polymerization in the presence of metallic copper. Comproportionation-disproportionation equilibria and kinetics . Macromolecules , 2013 . 46 3793 - 3802 . DOI: 10.1021/ma400149t http://doi.org/10.1021/ma400149t .

Peng, C.; Zhong, M.; Wang, Y.; Kwak, Y.; Zhang, Y.; Zhu, W.; Tonge, M.; Buback, J.; Park, S.; Krys, P.; Konkolewicz, D.; Gennaro, A.; Matyjaszewski, K . Reversible-deactivation radical polymerization in the presence of metallic copper. Activation of alkyl halides by Cu 0 . Macromolecules , 2013 . 46 3803 - 3815 . DOI: 10.1021/ma400150a http://doi.org/10.1021/ma400150a .

Zhong, M.; Wang, Y.; Krys, P.; Konkolewicz, D.; Matyjaszewski, K . Reversible-deactivation radical polymerization in the presence of metallic copper. Kinetic simulation . Macromolecules , 2013 . 46 3816 - 3827 . DOI: 10.1021/ma4001513 http://doi.org/10.1021/ma4001513 .

Konkolewicz, D.; Wang, Y.; Zhong, M.; Krys, P.; Isse, A. A.; Gennaro, A.; Matyjaszewski, K . Reversible-deactivation radical polymerization in the presence of metallic copper. A critical assessment of the SARA ATRP and SET-LRP mechanisms . Macromolecules , 2013 . 46 8749 - 8772 . DOI: 10.1021/ma401243k http://doi.org/10.1021/ma401243k .

Konkolewicz, D.; Wang, Y.; Krys, P.; Zhong, M.; Isse, A. A.; Gennaro, A.; Matyjaszewski, K . SARA ATRP or SET-LRP. End of controversy? . Polym. Chem. , 2014 . 5 4396 - 4417 . DOI: 10.1039/c4py00564c http://doi.org/10.1039/c4py00564c .

Harrisson, S.; Couvreur, P.; Nicolas, J . Comproportionation versus disproportionation in the initiation step of Cu(0)-mediated living radical polymerization . Macromolecules , 2012 . 45 7388 - 7396 . DOI: 10.1021/ma301034t http://doi.org/10.1021/ma301034t .

Tom, J.; Hornby, B.; West, A.; Harrisson, S.; Perrier, S . Copper(0)-mediated living radical polymerization of styrene . Polym. Chem. , 2010 . 1 420 - 422 . DOI: 10.1039/b9py00382g http://doi.org/10.1039/b9py00382g .

West, A. G.; Hornby, B.; Tom, J.; Ladmiral, V.; Harrisson, S.; Perrier, S . Origin of initial uncontrolled polymerization and its suppression in the copper(0)-mediated living radical polymerization of methyl acrylate in a nonpolar solvent . Macromolecules , 2011 . 44 8034 - 8041 . DOI: 10.1021/ma201568h http://doi.org/10.1021/ma201568h .

Gao, Y.; Zhao, T.; Wang, W . Is it ATRP or SET-LRP? Part I: Cu 0 & Cu II /PMDETA-mediated reversible-deactivation radical polymerization . RSC Adv. , 2014 . 4 61687 - 61690 . DOI: 10.1039/C4RA11477A http://doi.org/10.1039/C4RA11477A .

Gao, Y.; Zhao, T.; Zhou, D.; Greiser, U.; Wang, W . Insights into relevant mechanistic aspects about the induction period of Cu 0 /Me 6 TREN-mediated reversible-deactivation radical polymerization . Chem. Commun. , 2015 . 51 14435 - 14438 . DOI: 10.1039/C5CC05189D http://doi.org/10.1039/C5CC05189D .

Boyer, C.; Corrigan, N. A.; Jung, K.; Nguyen, D.; Nguyen, T. K.; Adnan, N. N. M.; Oliver, S.; Shanmugam, S.; Yeow, J . Copper-mediated living radical polymerization (atom transfer radical polymerization and copper(0) mediated polymerization): From fundamentals to bioapplications . Chem. Rev. , 2016 . 116 1803 - 1949 . DOI: 10.1021/acs.chemrev.5b00396 http://doi.org/10.1021/acs.chemrev.5b00396 .

Wang, W.; Zhao, J.; Zhou, N.; Zhu, J.; Zhang, W.; Pan, X.; Zhang, Z.; Zhu, X . Reversible deactivation radical polymerization in the presence of zero-valent metals: From components to precise polymerization . Polym. Chem. , 2014 . 5 3533 - 3546 . DOI: 10.1039/C3PY01398G http://doi.org/10.1039/C3PY01398G .

Nanda, A. K.; Matyjaszewski, K . Effect of [bpy]/[Cu(I)] ratio, solvent, counterion, and alkyl bromides on the activation rate constants in atom transfer radical polymerization . Macromolecules , 2003 . 36 599 - 604 . DOI: 10.1021/ma021418f http://doi.org/10.1021/ma021418f .

Tang, W.; Matyjaszewski, K . Effects of initiator structure on activation rate constants in ATRP . Macromolecules , 2007 . 40 1858 - 1863 . DOI: 10.1021/ma062897b http://doi.org/10.1021/ma062897b .

Tang, W.; Matyjaszewski, K . Effect of ligand structure on activation rate constants in ATRP . Macromolecules , 2006 . 39 4953 - 3357 . DOI: 10.1021/ma0609634 http://doi.org/10.1021/ma0609634 .

Zhang, Y.; Wang, Y.; Peng, C. H.; Zhong, M.; Zhu, W.; Konkolewicz, D.; Matyjaszewski, K . Copper-mediated CRP of methyl acrylate in the presence of metallic copper: Effect of ligand structure on reaction kinetics . Macromolecules , 2012 . 45 78 - 86 . DOI: 10.1021/ma201963c http://doi.org/10.1021/ma201963c .

Horn, M.; Matyjaszewski, K . Solvent effects on the activation rate constant in atom transfer radical polymerization . Macromolecules , 2013 . 46 3350 - 3357 . DOI: 10.1021/ma400565k http://doi.org/10.1021/ma400565k .

Braunecker, W. A.; Tsarevsky, N. V.; Gennaro, A.; Matyjaszewski, K . Thermodynamic components of the atom transfer radical polymerization equilibrium: Quantifying solvent effects . Macromolecules , 2009 . 42 6348 - 6360 . DOI: 10.1021/ma901094s http://doi.org/10.1021/ma901094s .

Lligadas, G.; Percec, V . Alkyl chloride initiators for SET-LRP of methyl acrylate . J. Polym. Sci., Part A: Polym. Chem. , 2008 . 46 4917 - 4926 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

Matyjaszewski, K.; Göbelt, B.; Paik, H. J.; Horwitz, C. P . Tridentate nitrogen-based ligands in Cu-based ATRP: A structure-activity study . Macromolecules , 2001 . 34 430 - 440 . DOI: 10.1021/ma001181s http://doi.org/10.1021/ma001181s .

Matyjaszewski, K . Atom transfer radical polymerization (ATRP): Current status and future perspectives . Macromolecules , 2012 . 45 4015 - 4039 . DOI: 10.1021/ma3001719 http://doi.org/10.1021/ma3001719 .

Zebende, G.; da Silva Filho, A . Detrended multiple cross-correlation coefficient . Phys. A Stat. Mech. its Appl. , 2018 . 510 91 - 97 . DOI: 10.1016/j.physa.2018.06.119 http://doi.org/10.1016/j.physa.2018.06.119 .

Whitfield, R.; Anastasaki, A.; Jones, G. R.; Haddleton, D. M . Cu(0)-RDRP of styrene: Balancing initiator efficiency and dispersity . Polym. Chem. , 2018 . 9 4395 - 4403 . DOI: 10.1039/C8PY00814K http://doi.org/10.1039/C8PY00814K .

Jones, G. R.; Whitfield, R.; Anastasaki, A.; Risangud, N.; Simula, A.; Keddie, D. J.; Haddleton, D. M . Cu(0)-RDRP of methacrylates in DMSO: Importance of the initiator . Polym. Chem. , 2018 . 9 2382 - 2388 . DOI: 10.1039/C7PY01196B http://doi.org/10.1039/C7PY01196B .

Whitfield, R.; Anastasaki, A.; Nikolaou, V.; Jones, G. R.; Engelis, N. G.; Discekici, E. H.; Fleischmann, C.; Willenbacher, J.; Hawker, C. J.; Haddleton, D. M . Universal conditions for the controlled polymerization of acrylates, methacrylates and styrene via Cu(0)-RDRP . J. Am. Chem. Soc. , 2017 . 139 1003 - 1010 . DOI: 10.1021/jacs.6b11783 http://doi.org/10.1021/jacs.6b11783 .

Wang, W.; Zhang, Z.; Wu, Y.; Zhu, J.; Cheng, Z.; Zhou, N.; Zhang, W.; Zhu, X . Ligand-free Cu(0)-mediated controlled radical polymerization of methyl methacrylate at ambient temperature . J. Polym. Sci., Part A: Polym. Chem. , 2012 . 50 711 - 719 . DOI: 10.1002/pola.25081 http://doi.org/10.1002/pola.25081 .

Hornby, B. D.; West, A. G.; Tom, J. C.; Waterson, C.; Harrisson, S . Copper(0)-mediated living radical polymerization of methyl methacrylate in a non-polar solvent . Macromol. Rapid Commun. , 2010 . 31 1276 - 1280 . DOI: 10.1002/marc.v31:14 http://doi.org/10.1002/marc.v31:14 .

浏览量

458

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

One-pot and One-step Cu(0)-mediated Reversible-Deactivation Radical Polymerization of N-Isopropylacrylamide (NIPAM) in Water

Continuous Synthesis of Main-Chain-type Fluorinated Graft Copolymers via Successive Flow START Polymerization and Cu(0)-Mediated RDRP

Enhanced Segment Mobility Promotes Stereocomplex Crystallization in Polymer Blends via Elevated Segmental Miscibility

Advances in Polymer-based Circularly Polarized Luminescent Materials

Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions

Controlled Polymerization of Methyl Methacrylate and Styrene via Cu(0)-Mediated RDRP by Selecting the Optimal Reaction Conditions

DOI：10.1007/s10118-019-2236-x

摘要

Abstract

关键词

Keywords

references