CuSO4-CATALYZED SELF-INITIATED RADICAL POLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AS AN INTRINSICALLY REDUCING INIMER

Yan Sun Guang-qun Zhai

Citation:  Yan Sun, Guang-qun Zhai. CuSO4-CATALYZED SELF-INITIATED RADICAL POLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AS AN INTRINSICALLY REDUCING INIMER[J]. Chinese Journal of Polymer Science, 2013, 31(8): 1161-1172. doi: 10.1007/s10118-013-1317-5 shu

CuSO4-CATALYZED SELF-INITIATED RADICAL POLYMERIZATION OF 2-(N,N-DIMETHYLAMINO)ETHYL METHACRYLATE AS AN INTRINSICALLY REDUCING INIMER

  • 基金项目:

    This work was financially supported by the National Natural Science Foundation of China (No. 20674033), Natural Science Foundation of Jiangsu Province (No. BK2008142) and Scientific Research Foundation for the Returned Overseas Chinese Scholars (State Education Ministry).

摘要: Since tertiary amines (C-H) can be oxidized by peroxides and transition metal cations in high oxidation states into C radicals to initiate vinylic polymerizations of methacrylates, Cu2+ and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) form a polymerizable redox initiating pair, in which DMAEMA serves as an intrinsically reducing inimer. CuSO4-catalyzed aqueous self-initiated radical polymerizations of DMAEMA were successfully performed at ambient temperature via a continuous Cu2+-tertiary amine redox initiation based on catalyst regeneration in the presence of O2. The polymerization kinetics was monitored by gas chromatography and the structure of PDMAEMA was characterized by gel-permeation chromatography, nuclear magnetic resonance spectroscopy, laser light scattering and online intrinsic-viscosity analysis. Both the monomer conversion and the molecular weight of PDMAEMA increase with the reaction while the molecular weight distribution maintains rather broad, as the Cu2+-DMAEMA redox-initiation leads to linear PDMAEMA chains with terminal methacryloxyl moieties, and the Cu2+-PDMAEMA redox-initiation results in branched chains. The branched topology forms and develops only for the high-MW components of the PDMAEMA. Our results provide a facile strategy to prepare branched polymers from such commercially available intrinsically reducing inimers using a negligible concentration of regenerative air-stable catalysts.

English


    1. [1]

      Misra, G.S. and Bajpai, U[J].D.N., Prog. Polym. Sci.1982, 8:61-[2]Sarac, A.S., Prog. Polym. Sci., 1999, 24: 1149[3]Sato, T., Takada, M[J].and Otsu T., Makromol. Chem.1971, 148:239-[4]Sato, T., Kita, S[J].and Otsu, T., Makromol. Chem.1975, 176:561-[5]Imoto, M., Otsu, T[J].and Ota, T., Makromol. Chem.1955, 16:10-[6]Feng, X.D., Guo, X[J].Q. and Qiu, K.Y., Makromol. Chem.1988, 189:77-[7]Dyer, D.J., Feng, J.X., Schmidt, R., Wong, V.N., Zhao, T.F. and Yagci, Y., Macromolecules, 2004, 37: 7072[8]Hofeer, M., Moszner, N[J].and Liska, R., J. Polym. Sci. Part A: Polym. Chem.2008, 46:6916-[9]Pappas, S.P., in “Photoinitiated Polymerization in Comprehensive Polymer Science Vol. 4” ed. by Eastmond, G.C., Ledwith, A., Russo, S. and Sigwalt, P., Elsevier, Pergamon Press Oxford, 1989, p. 338[10]Zhang, Z.Y., Zu, C.X., Qiao, L.Y. and Li, F.M., Acta Polym. Sin.(in Chinese), 1990, (5): 623[11]Si, K., Guo, X.Q. and Qiu, K.Y., Macromol. Reps., 1995, 32: 1149[12]Fréchet, J.M.J., Henmi, M., Gitsov, I., Aoshima, S., Leduc, M. and Grubbs, R.B., Science, 1995, 269: 1080[13]Liu, Y.H., Li, J[J].B., Yang, L.Y. and Shi, Z.Q., J. Macromol. Sci.-Pure. Appl. Chem.2003, 40:1107-[14]Zhang, X., Liu, W.H., Chen, Y.M., Gong, A.J., Chen, C.F. and Xi, F., Polym. Bull., 1999, 43: 29[15]Nikishin, G.I., Svitanko, I.V. and Troyansky, E.I., J. Chem. Soc. Perkin. Trans. II, 1983, 5: 595[16]Menon, C.C. and Kapur, S[J].L., J. Polym. Sci.1961, 54:45-[17]Song, J., Zhai, G.Q., Jiang, B.B. and Chen, J.H., Scientia Sinica Chemica, 2010, 40(11): 1619[18]Song, J., Ni, J., Jiang, B.B., Chen, J.H. and Zhai, G.Q., Acta Polym. Sin. (in Chinese), 2011, (12): 85[19]Min, K., Gao, H[J].and Matyjaszewski, K., J. Am. Chem. Soc.2005, 127:3825-[20]Jakubowski, W. and Matyjaszewski, K., Macromolecules, 2005 38: 4139[21]Jakubowski, W., Min, K[J].and Matyjaszewski, K., Macromolecules.2006, 39:39-[22]Jakubowski, W. and Matyjaszewski, K[J]., Angew. Chem. Int. Ed.2006, 45:4482-[23]Matyjaszewski, K., Jakubowski, W., Min, K., Tang, W., Huang, J.Y., Braunecker, W.A. and Tsarevsky, N.V., PNAS, 2006, 103: 15309[24]Kwak, Y.W. and Matyjaszewski, K[J]., Polym. Int.2009, 58:242-[25]Tang, H.D., Radosz, M[J].and Shen, Y.Q., Macromol. Rapid. Comm.2006, 27:1127-[26]Tang, H.D., Shen, Y[J].Q., Li, B.G. and Radosz, M., Macromol. Rapid. Comm.2008, 29:1834-[27]Hu, Z.Q., Shen, X.R., Qiu, H.Y., Lai, G.Q., Wu, J.R. and Li, W.Q., Eur. Polym. J., 2009, 45: 2313[28]Chen, H., Liu, D[J].L., Song, Y.T., Qu, R.J. and Wang, C.H., J. Polym. Sci. Part A: Polym. Chem.2009, 47:3202-[29]Chen, H., Wang, C.H., Liu, D.L., Song, Y.T., Qu, R.J., Sun, C.M. and Ji, C.N., J. Polym. Sci. Part A: Polym. Chem., 2010, 48: 128[30]Dong, H.C. and Matyjaszewski, K[J]., Macromolecules.2008, 41:6868-[31]Zhan, Y., Ni, C.Y., Xia, Y.G., Chen, H.F., Zhai, G.Q. and Kong, L.Z., Acta Polym. Sin.(in Chinese), 2010, (2): 185[32]Gao, J., Zhai, G[J].Q. and Song, Y., J. Appl. Polym. Sci.2008, 107:3548-[33]Pantoustier, N., Moins, S[J]., Wautier, M., Degée, P. and Dubois, P., Chem. Comm.2003, 3:340-[34]Weimer, M.W., Fréchet, J[J].M.J. and Gitsov, I., J. Polym. Sci. Part A: Poly. Chem.1998, 36:955-3.0.CO;2-K' target='_blank'>[35]Yang, H.J., Jiang, B.B., Huang, W.Y., Zhang, D.L., Kong, L.Z., Chen, J.H., Liu, C.L., Gong, F.H., Yu, Q. and Yang, Y., Macromolecules, 2009, 42: 5976[36]Wang, W.J., Wang, D.M., Li, B.G. and Zhu, S.P., Macromolecules, 2010, 43: 4062[37]Mori, H., Walther, A[J]., André, X., Lanzendörfer, M.G. and Müller, A.H.E., Macromolecules.2004, 37:2054-[38]Mori, H., Delphine, C[J].S., Lechner, H., Zhang, M.F. and Müller, A.H.E, Macromolecules.2002, 35:9270-[39]Jayanthi, S., Kishore, K[J].Macromolecules.1993, 26:1985-

  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  908
  • HTML全文浏览量:  79
文章相关
  • 发布日期:  2013-08-05
  • 收稿日期:  2012-10-08
  • 修回日期:  2012-12-11
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章