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Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter

Qiao Xu ,  Yi-Feng Zhu ,  Zhao Yuan ,  Hua-Dong Tang

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Citation:  Qiao Xu, Yi-Feng Zhu, Zhao Yuan, Hua-Dong Tang. Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter[J]. Chinese Chemical Letters, 2015, 26(6): 773-778. doi: 10.1016/j.cclet.2015.03.012 shu

Atom transfer radical polymerization of methyl acrylate, methyl methacrylate and styrene in the presence of trolamine as a highly effective promoter

    • 通讯作者: Hua-Dong Tang,
摘要: Transition metal-mediated atom transfer radical polymerization (ATRP) is a "living"/controlled radical polymerization. Recently, there has been widely increasing interest in reducing the high costs of catalyst separation and post-polymerization purification in ATRP. In this work, trolamine was found to significantly enhance the catalytical performance of CuBr/N,N,N',N'-tetrakis(2-pyridylmethyl) ethylenediamine (CuBr/TPEN) and CuBr/tris[2-(dimethylamino) ethylamine] (CuBr/Me6TREN). With the addition of 25-fold molar amount of trolamine relative to CuBr, the catalyst loadings of CuBr/TPEN and CuBr/Me6TREN were dramatically reduced from a catalyst-to-initiator ratio of 1 to 0.01 and 0.05, respectively. The polymerizations of methyl acrylate, methyl methacrylate and styrene still showed first-order kinetics in the presence of trolamine and produced poly(methyl acrylate), poly(methyl methacrylate) and polystyrene with molecular weights close to theoretical values and low polydispersities. These results indicate that trolamine is a highly effective and versatile promoter for ATRP and is promising for potential industrial application.

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    1. [1] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine)ruthenium( II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization,Macromolecules 28 (1995) 1721-1723.[1] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine)ruthenium( II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization,Macromolecules 28 (1995) 1721-1723.

    2. [2] J.S. Wang, K. Matyjaszewski, Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes, J. Am. Chem. Soc. 117 (1995) 5614-5615.[2] J.S. Wang, K. Matyjaszewski, Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes, J. Am. Chem. Soc. 117 (1995) 5614-5615.

    3. [3] Y. Shi, Z.F. Fu, Y.D. Zhang, S.K. Jiao, Synthesis of comb like poly(methyl methacrylate) by atom transfer radical polymerization with poly(ethyl 2-bromoacrylate) as macroinitiator, Chin. Chem. Lett. 14 (2003) 1289-1292.[3] Y. Shi, Z.F. Fu, Y.D. Zhang, S.K. Jiao, Synthesis of comb like poly(methyl methacrylate) by atom transfer radical polymerization with poly(ethyl 2-bromoacrylate) as macroinitiator, Chin. Chem. Lett. 14 (2003) 1289-1292.

    4. [4] Y. Yi, X.H. Wan, X.H. Fan, R. Dong, Q.F. Zhou, Synthesis of a novel hybrid liquidcrystalline rod-coil diblock copolymer, J. Polym. Sci. Polym. Chem. 41 (2003) 1799-1806.[4] Y. Yi, X.H. Wan, X.H. Fan, R. Dong, Q.F. Zhou, Synthesis of a novel hybrid liquidcrystalline rod-coil diblock copolymer, J. Polym. Sci. Polym. Chem. 41 (2003) 1799-1806.

    5. [5] X.D. Tang, L.C. Gao, X.H. Fan, Q.F. Zhou, Effect of spacer length on the liquid crystalline property of azobenzene-containing ABA-type triblock copolymers via ATRP, Chin. Chem. Lett. 18 (2007) 1129-1132.[5] X.D. Tang, L.C. Gao, X.H. Fan, Q.F. Zhou, Effect of spacer length on the liquid crystalline property of azobenzene-containing ABA-type triblock copolymers via ATRP, Chin. Chem. Lett. 18 (2007) 1129-1132.

    6. [6] X.D. Tang, L.C. Gao, X.H. Fan, Q.F. Zhou, Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP, Chin. Chem. Lett. 19 (2008) 237-240.[6] X.D. Tang, L.C. Gao, X.H. Fan, Q.F. Zhou, Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP, Chin. Chem. Lett. 19 (2008) 237-240.

    7. [7] K. Matyjaszewski, M.J. Ziegler, S.V. Arehart, D. Greszta, T. Pakula, Gradient copolymers by atom transfer radical copolymerization, J. Phys. Org. Chem. 13 (2000) 775-786.[7] K. Matyjaszewski, M.J. Ziegler, S.V. Arehart, D. Greszta, T. Pakula, Gradient copolymers by atom transfer radical copolymerization, J. Phys. Org. Chem. 13 (2000) 775-786.

    8. [8] Y.J. Xu, C.Y. Pan, Block and star-block copolymers by mechanism transformation. 3. S-(PTHF-PSt)4 and S-(PTHF-PSt-PMMA)4 from living CROP to ATRP, Macromolecules 33 (2000) 4750-4756.[8] Y.J. Xu, C.Y. Pan, Block and star-block copolymers by mechanism transformation. 3. S-(PTHF-PSt)4 and S-(PTHF-PSt-PMMA)4 from living CROP to ATRP, Macromolecules 33 (2000) 4750-4756.

    9. [9] X.D. Tang, X.H. Fan, X.F. Chen, Q.F. Zhou, Progress of atom transfer radical polymerization (ATRP) applied to the synthesis of star polymers, Prog. Chem. 17 (2005) 1089-1095 (in Chinese).[9] X.D. Tang, X.H. Fan, X.F. Chen, Q.F. Zhou, Progress of atom transfer radical polymerization (ATRP) applied to the synthesis of star polymers, Prog. Chem. 17 (2005) 1089-1095 (in Chinese).

    10. [10] S.G. Gaynor, S. Edelman, K. Matyjaszewski, Synthesis of branched and hyperbranched polystyrenes, Macromolecules 29 (1996) 1079-1081.[10] S.G. Gaynor, S. Edelman, K. Matyjaszewski, Synthesis of branched and hyperbranched polystyrenes, Macromolecules 29 (1996) 1079-1081.

    11. [11] M.R. Leduc, C.J. Hawker, J. Dao, J.M.J. Fréchet, Dendritic initiators for "living" radical polymerizations: a versatile approach to the synthesis of dendritic-linear block copolymers, J. Am. Chem. Soc. 118 (1996) 11111-11118.[11] M.R. Leduc, C.J. Hawker, J. Dao, J.M.J. Fréchet, Dendritic initiators for "living" radical polymerizations: a versatile approach to the synthesis of dendritic-linear block copolymers, J. Am. Chem. Soc. 118 (1996) 11111-11118.

    12. [12] Y.L. Zhao, C.F. Chen, F. Xi, Synthesis of well-defined dendritic-linear diblock and triblock copolymers by controlled free radical polymerization, Chin. Chem. Lett. 13 (2002) 217-218.[12] Y.L. Zhao, C.F. Chen, F. Xi, Synthesis of well-defined dendritic-linear diblock and triblock copolymers by controlled free radical polymerization, Chin. Chem. Lett. 13 (2002) 217-218.

    13. [13] C.H. Hu, A.Q. Zhang, Atom transfer radical polymerization of methyl methacrylate initiated by p-chloromethylstyrene copolymers, Fine Chem. 23 (2006) 298-301 (in Chinese).[13] C.H. Hu, A.Q. Zhang, Atom transfer radical polymerization of methyl methacrylate initiated by p-chloromethylstyrene copolymers, Fine Chem. 23 (2006) 298-301 (in Chinese).

    14. [14] F. Simal, A. Demonceau, A.F. Noels, Highly efficient ruthenium-based catalytic systems for the controlled free-radical polymerization of vinyl monomers, Angew. Chem. Int. Ed. 38 (1999) 538-540.[14] F. Simal, A. Demonceau, A.F. Noels, Highly efficient ruthenium-based catalytic systems for the controlled free-radical polymerization of vinyl monomers, Angew. Chem. Int. Ed. 38 (1999) 538-540.

    15. [15] K. Matyjaszewski, S. Coca, C.B. Jasieczek, Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of glycidyl acrylate, Macromol. Chem. Phys. 198 (1997) 4011-4017.[15] K. Matyjaszewski, S. Coca, C.B. Jasieczek, Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of glycidyl acrylate, Macromol. Chem. Phys. 198 (1997) 4011-4017.

    16. [16] K. Matyjaszewski, S.M. Jo, H.J. Paik, D.A. Shipp, An Investigation into the CuX/2, 2'-Bipyridine (X = Br or Cl) mediated atom transfer radical polymerization of acrylonitrile, Macromolecules 32 (1999) 6431-6438.[16] K. Matyjaszewski, S.M. Jo, H.J. Paik, D.A. Shipp, An Investigation into the CuX/2, 2'-Bipyridine (X = Br or Cl) mediated atom transfer radical polymerization of acrylonitrile, Macromolecules 32 (1999) 6431-6438.

    17. [17] X.D. Tang, X.C. Liang, N.F. Han, Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP, Chin. Chem. Lett. 20 (2009) 1353-1356.[17] X.D. Tang, X.C. Liang, N.F. Han, Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP, Chin. Chem. Lett. 20 (2009) 1353-1356.

    18. [18] K. Matyjaszewski, T. Pintauer, S. Gaynor, Removal of copper-based catalyst in atom transfer radical polymerization using ion exchange resins, Macromolecules 33 (2000) 1476-1478.[18] K. Matyjaszewski, T. Pintauer, S. Gaynor, Removal of copper-based catalyst in atom transfer radical polymerization using ion exchange resins, Macromolecules 33 (2000) 1476-1478.

    19. [19] Y.Q. Shen, H.D. Tang, S.J. Ding, Catalyst separation in atom transfer radical polymerization, Prog. Polym. Sci. 29 (2004) 1053-1078.[19] Y.Q. Shen, H.D. Tang, S.J. Ding, Catalyst separation in atom transfer radical polymerization, Prog. Polym. Sci. 29 (2004) 1053-1078.

    20. [20] J.H. Xia, T. Johnson, S.G. Gaynor, K. Matyjaszewski, J. De Simone, Atom transfer radical polymerization in supercritical carbon dioxide, Macromolecules 32 (1999) 4802-4805.[20] J.H. Xia, T. Johnson, S.G. Gaynor, K. Matyjaszewski, J. De Simone, Atom transfer radical polymerization in supercritical carbon dioxide, Macromolecules 32 (1999) 4802-4805.

    21. [21] J.V. Nguyen, C.W. Jones, Design, behavior, and recycling of silica-supported CuBrbipyridine ATRP catalysts, Macromolecules 37 (2004) 1190-1203.[21] J.V. Nguyen, C.W. Jones, Design, behavior, and recycling of silica-supported CuBrbipyridine ATRP catalysts, Macromolecules 37 (2004) 1190-1203.

    22. [22] W. Jakubowski, K. Min, K. Matyjaszewski, Activators regenerated by electron transfer for atom transfer radical polymerization of styrene, Macromolecules 39 (2006) 39-45.[22] W. Jakubowski, K. Min, K. Matyjaszewski, Activators regenerated by electron transfer for atom transfer radical polymerization of styrene, Macromolecules 39 (2006) 39-45.

    23. [23] K. Matyjaszewski, W. Jakubowski, K. Min, et al., Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents, Proc. Natl. Acad. Sci. U. S. A. 103 (2006) 15309-15314.[23] K. Matyjaszewski, W. Jakubowski, K. Min, et al., Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents, Proc. Natl. Acad. Sci. U. S. A. 103 (2006) 15309-15314.

    24. [24] D.M. Haddleton, A.M. Heming, D. Kukulj, D.J. Duncalf, A.J. Shooter, Atom transfer polymerization of methyl methacrylate. Effect of acids and effect with 2-bromo-2-methylpropionic acid initiation, Macromolecules 31 (1998) 2016-2018.[24] D.M. Haddleton, A.M. Heming, D. Kukulj, D.J. Duncalf, A.J. Shooter, Atom transfer polymerization of methyl methacrylate. Effect of acids and effect with 2-bromo-2-methylpropionic acid initiation, Macromolecules 31 (1998) 2016-2018.

    25. [25] K.Matyjaszewski, S. Coca, S.G. Gaynor,M.L.Wei, B.E.Woodworth, Zerovalentmetals in controlled/"living" radical polymerization,Macromolecules 30 (1997) 7348-7350.[25] K.Matyjaszewski, S. Coca, S.G. Gaynor,M.L.Wei, B.E.Woodworth, Zerovalentmetals in controlled/"living" radical polymerization,Macromolecules 30 (1997) 7348-7350.

    26. [26] K. Min, H.F. Gao, K. Matyjaszewski, Preparation of homopolymers and block copolymers in miniemulsion by ATRP using activators generated by electron transfer (AGET), J. Am. Chem. Soc. 127 (2005) 3825-3830.[26] K. Min, H.F. Gao, K. Matyjaszewski, Preparation of homopolymers and block copolymers in miniemulsion by ATRP using activators generated by electron transfer (AGET), J. Am. Chem. Soc. 127 (2005) 3825-3830.

    27. [27] K. Min, W. Jakubowski, K. Matyjaszewski, AGET ATRP in the presence of air in miniemulsion and in bulk, Macromol. Rapid Commun. 27 (2006) 594-598.[27] K. Min, W. Jakubowski, K. Matyjaszewski, AGET ATRP in the presence of air in miniemulsion and in bulk, Macromol. Rapid Commun. 27 (2006) 594-598.

    28. [28] Y.X. Wang, X.L. Li, F.F. Du, et al., Use of alcohols as reducing agents for synthesis of well-defined polymers by AGET-ATRP, Chem. Commun. 48 (2012) 2800-2802.[28] Y.X. Wang, X.L. Li, F.F. Du, et al., Use of alcohols as reducing agents for synthesis of well-defined polymers by AGET-ATRP, Chem. Commun. 48 (2012) 2800-2802.

    29. [29] Y.T. Luo, J.M. Zhuang, X.R. Lin, et al., Study of rate-accelerating of aluminum hydroxide, boric acid, and (2-methylpropyl) boronic acid for atom transfer radical polymerization of styrene, J. Xiamen Univ. 47 (2008) 63-66 (in Chinese).[29] Y.T. Luo, J.M. Zhuang, X.R. Lin, et al., Study of rate-accelerating of aluminum hydroxide, boric acid, and (2-methylpropyl) boronic acid for atom transfer radical polymerization of styrene, J. Xiamen Univ. 47 (2008) 63-66 (in Chinese).

    30. [30] H. Zhang, D.M. Xu, K.D. Zhang, Effect of inhibitors on atom transfer radical polymerization of MMA, Chin. J. Chem. 23 (2005) 913-917.[30] H. Zhang, D.M. Xu, K.D. Zhang, Effect of inhibitors on atom transfer radical polymerization of MMA, Chin. J. Chem. 23 (2005) 913-917.

    31. [31] H.D. Tang, Y.Q. Shen, B.G. Li, M. Radosz, Tertiary amine-enhanced activity of ATRP catalysts CuBr/TPMA and CuBr/Me6TREN, Macromol. Rapid Commun. 29 (2008) 1834-1838.[31] H.D. Tang, Y.Q. Shen, B.G. Li, M. Radosz, Tertiary amine-enhanced activity of ATRP catalysts CuBr/TPMA and CuBr/Me6TREN, Macromol. Rapid Commun. 29 (2008) 1834-1838.

    32. [32] H.D. Tang, N. Arulsamy, M. Radosz, et al., Highly active copper-based catalyst for atom transfer radical polymerization, J. Am. Chem. Soc. 128 (2006) 16277-16285.[32] H.D. Tang, N. Arulsamy, M. Radosz, et al., Highly active copper-based catalyst for atom transfer radical polymerization, J. Am. Chem. Soc. 128 (2006) 16277-16285.

    33. [33] H.D. Tang, M. Radosz, Y.Q. Shen, CuBr2/N,N,N',N'-tetra-[(2-pyridal)methyl] ethylenediamine/tertiary amine as a highly active and versatile catalyst for atomtransfer radical polymerization via activator generated by electron transfer, Macromol. Rapid Commun. 27 (2006) 1127-1131.[33] H.D. Tang, M. Radosz, Y.Q. Shen, CuBr2/N,N,N',N'-tetra-[(2-pyridal)methyl] ethylenediamine/tertiary amine as a highly active and versatile catalyst for atomtransfer radical polymerization via activator generated by electron transfer, Macromol. Rapid Commun. 27 (2006) 1127-1131.

    34. [34] J. Queffelec, S.G. Gaynor, K. Matyjaszewski, Optimization of atom transfer radical polymerization using Cu(I)/tris(2-(dimethylamino)ethyl)amine as a catalyst, Macromolecules 33 (2000) 8629-8639.[34] J. Queffelec, S.G. Gaynor, K. Matyjaszewski, Optimization of atom transfer radical polymerization using Cu(I)/tris(2-(dimethylamino)ethyl)amine as a catalyst, Macromolecules 33 (2000) 8629-8639.

    35. [35] X. Huang, M.J. Wirth, Surface initiation of living radical polymerization for growth of tethered chains of low polydispersity, Macromolecules 32 (1999) 1694-1696.[35] X. Huang, M.J. Wirth, Surface initiation of living radical polymerization for growth of tethered chains of low polydispersity, Macromolecules 32 (1999) 1694-1696.

    36. [36] J.H. Xia, S.G. Gaynor, K. Matyjaszewski, Controlled/"living" radical polymerization. Atom transfer radical polymerization of acrylates at ambient temperature, Macromolecules 31 (1998) 5958-5959.[36] J.H. Xia, S.G. Gaynor, K. Matyjaszewski, Controlled/"living" radical polymerization. Atom transfer radical polymerization of acrylates at ambient temperature, Macromolecules 31 (1998) 5958-5959.

    37. [37] J.F. Weiss, G. Tollin, J.T. Yoke, Reactions of triethylamine with copper halides. II. Internal oxidation-reduction of dichlorobis(triethylamine)copper(II), Inorg. Chem. 3 (1964) 1344-1348.[37] J.F. Weiss, G. Tollin, J.T. Yoke, Reactions of triethylamine with copper halides. II. Internal oxidation-reduction of dichlorobis(triethylamine)copper(II), Inorg. Chem. 3 (1964) 1344-1348.

    38. [38] M.T. Caudle, V.L. Pecoraro, Mechanism for the reduction of the mixed-valent MnIIIMnIV[2-OHsalpn]2+ complex by tertiary amines, Inorg. Chem. 39 (2000) 5831-5837.[38] M.T. Caudle, V.L. Pecoraro, Mechanism for the reduction of the mixed-valent MnIIIMnIV[2-OHsalpn]2+ complex by tertiary amines, Inorg. Chem. 39 (2000) 5831-5837.

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  • 发布日期:  2015-03-27
  • 收稿日期:  2014-12-31
  • 网络出版日期:  2015-02-27
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