화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.20, No.2, 419-425, March, 2014
DOI10.1016/j.jiec.2013.04.036  Export Citation
Synthesis of 4-arms hydroxy-functionalized PMMA-b-PE through combining free radical polymerization with coordination polymerization
Yaping Sheng, Haibing Huang, Mengshan Yu, Xinli Zhang, Lu Cheng, Zhi Liu, Wei Liu, Qigu Huang†, Jianjun Yi1, and Wantai Yang
  • State Key Laboratory of Chemical Resource Engineering and Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China
  • 1Lab for Synthetic Resin Research Institution of Petrochemical Technology, China National Petroleum Corporation, Beijing 100083, China
E-mail:
The copolymerization of MMA with ethylene was promoted by metallocene complex in the presence of initiator tetra(2,3-epoxy propoxy)silane (Is), reducing agent Zn and cocatalyst MAO, combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one-pot to produce 4-arms hydroxy-functionalized PMMA-b-PE. The effects of polymerization conditions such as temperature, time, ethylene pressure and Al/Ti molar ratio on the polymerization performance were investigated. 4-Arms hydroxy-functionalized PMMA-b-PE was obtained by solvent extraction and determined by GPC, MALLS, DSC, FT-IR, WAXD and 1H(13C) NMR. The DSC result indicated that the 4-arms hydroxy-functionalized PMMA-b-PE had one Tg at 87.0 ℃ and one Tm at 117.0 8C which attributed to Tg of PMMA segment and Tm of PE segment, respectively. The microstructure of 4-arms hydroxy-functionalized PMMA-b-PE was further confirmed by WAXD, FT-IR, and 13C NMR analysis. These results demonstrated that the obtained 4-arms block copolymer consisted of PMMA segment and crystalline PE segment.
Keywords:Free radical polymerization;Coordination polymerization;One-pot strategy;Block copolymer;4-Arms hydroxy-functionalized copolymer
  1. Cai Y, Tang Y, Armes SP, Macromol, 37, 9728 (2004)
  2. Cai Y, Armes SP, Macromol, 38, 271 (2005)
  3. Gao H, Matyjaszewski K, J. Am. Ceram. Soc., 129, 11828 (2007)
  4. Zhao YL, Higashihara T, Sugiyama K, Hirao A, J. Am. Chem. Soc., 127(41), 14158 (2005)
  5. Shibata T, Kanaoka S, Aoshima S, J. Am. Chem. Soc., 128(23), 7497 (2006)
  6. Zhang K, Ye Z, Ramesh S, Macromol, 42, 2313 (2009)
  7. Asandei AD, Moran IW, J. Am. Chem. Soc., 126(49), 15932 (2004)
  8. Asandei AD, Chen Y, Macromol, 39, 7549 (2006)
  9. Asandei AD, Saha G, J. Polym. Sci. A: Polym. Chem., 44(3), 1106 (2006)
  10. Ma LF, Liu WJ, Yi JJ, Wang HL, Huang QG, Gao KJ, Yang WT, J. Appl. Polym. Sci., 120(6), 3171 (2011)
  11. Wang H, Kong Y, Ma L, Sheng Y, Huang Q, Yang W, Acta Polym. Sin., 4, 423 (2010)
  12. Catalyst system: CpTiCl3/Zn/Is/MMA = 8/12/1/300; monomer: MMA (3 mL); radical polymerization of MMA was carried out at 90 8C for 2.5 h in 1,4-dioxane (IE = 0.68, Mn = 0.27 104, MWD = 1.51). When the experiment was performed in a 300 mL glass Schlenk, the mixture color was changed into lime-green, demonstrating the formation of metallocene complex radical CpTi(III)Cl2
  13. Huang QG, Chen LG, Lin SG, Wu Q, Zhu FM, Shiyan, Fu ZF, Yang WT, Polymer, 47(2), 767 (2006)
  14. Kong YA, Yi JJ, Dou XL, Liu WJ, Huang QG, Gao KJ, Yang WT, Polymer, 51(17), 3859 (2010)
  15. Ma LF, Wang HL, Yi JJ, Huang QG, Gao KJ, Yang WT, J. Polym. Sci. A: Polym. Chem., 48(2), 417 (2010)
  16. Ma L, Sheng Y, Huang Q, Li J, Yang W, J. Polym. Sci. A: Polym. Chem., 46(2), 33 (2008)
  17. Zhang XL, Liu Z, Yi JJ, Li FJ, Huang HB, Liu W, Zhen HP, Huang QG, Gao KJ, Yang WT, J. Polym. Sci. A: Polym. Chem., 50(10), 2068 (2012)
  18. Ma L, Huang Q, Song H, Yang W, Acta Po, 7, 689 (2009)
  19. Sheng Y, Bi T, Lv M, Huang Q, Wu Y, Yang W, Acta Polym., 2, 179 (2008)
  20. Aaltonen, Seppala PJ, Eur. Polym. J., 31, 79 (1995)
  21. Huang QG, Wu Q, Zhu FM, Lin SG, J. Polym. Sci. A: Polym. Chem., 39(23), 4068 (2001)
  22. Liu Z, Zhang X, Huang H, Yi J, Liu W, Liu W, Zhen H, Huang Q, Gao K, Zhang M, Yang W, J. Ind. Eng. Chem., 18(6), 2217 (2012)
  23. Huang Q, Zhu F, Wu Q, Lin S, Polym. Int., 50, 45 (2001)
  24. Huang Q, Chen L, Ma L, Fu Z, Yang W, Eur. Polym. J., 41, 2909 (2005)
  25. Oliva L, Izzo L, Longo P, Macromol. Rapid Commun., 17(10), 745 (1996)
  26. Ricardo GL, Frank DA, Christophe B, Prog. Polym. Sci, 419 (2007)
  27. Izzo L, Oliva L, Proto A, Trofa M, Macromol. Chem. Phys., 200, 1086 (1999)
  28. Zhang H, Nomura K, J. Am. Chem. Soc., 127(26), 9364 (2005)
  29. Luo YJ, Baldamus J, Hou ZM, J. Am. Chem. Soc., 126(43), 13910 (2004)