Synthesis of high molecular weight poly(styrene-b-methyl methacrylate) using a plug flow reactor system by anionic polymerization

Jeong-Su Kim; Jeong-Ohk Kweon; Jeong-Hye Lee; Si-Tae Noh

Macromolecular Research, Vol.23, No.1, 100-110, January, 2015

DOI10.1007/s13233-015-3008-2 Export Citation

Synthesis of high molecular weight poly(styrene-b-methyl methacrylate) using a plug flow reactor system by anionic polymerization

Jeong-Su Kim, Jeong-Ohk Kweon, Jeong-Hye Lee, and Si-Tae Noh^†

Department of Chemical Engineering, ERICA, Hanyang University, Ansan, Gyeonggi, 426-791, Korea

E-mail:

Sequential anionic polymerizations of styrene and methyl methacrylate and 2-vinylpyridine in tetrahydrofuran (THF) were conducted in a plug flow reactor system with a static mixer. Polymers [polystyrene (PS), M n : 120×10^(3) g·mol-1, M w /M n : 1.08), poly(methyl methacrylate) (PMMA, M n : 28×10^(3) g·mol-1, M w /M n : 1.09), poly(2-vinylpyridine) (P2VP, M n : 53×10^(3) g·mol-1, M w /M n : 1.08), and PS-b-PMMA (M n : 117×10^(3) g·mol-1, M w /M n : 1.12)] with a precisely controlled high molecular weight were obtained using a 1,1-diphenylhexyllithium initiator in a plug flow reactor system. PS-b-PMMA, PMMA, and P2VP were obtained in the presence of LiCl. The molecular weight distribution, which was related to the mixing efficiency of the static mixer, decreased with increasing flow rate. Additionally, the molecular weight of the polymers could be adjusted by varying the flow rates.

Keywords:plug flow reactor;continuous reactor;static mixer;block copolymer;anionic polymerization;polystyrene;poly(2-vinylpyridine);poly(methyl methacrylate);poly(styrene-b-methyl methacrylate)

[References]

Ruzette AV, Leibler L, Nat. Mater., 4(1), 19 (2005)
Walheim S, Schaffer E, Mlynek J, Steiner U, Science, 283(5401), 520 (1999)
Glusker DL, Stiles E, Yoncoskie B, J. Polym. Sci., 49, 297 (1961)
Glusker DL, Lysloff I, Stiles E, J. Polym. Sci., 49, 315 (1961)
Teyssie P, Baran J, Dubois P, Jerome R, Wang JS, Yu JM, Yu YS, Zundel T, Macromol. Symp., 132, 303 (1998)
Teyssie P, Fayt R, Hautekeer JP, Jacobs C, Jerome R, Leemans L, Varshney SK, Makromol. Chem. Macromol. Symp., 32, 61 (1990)
Nakamura N, Yoshino A, Takahashi K, Bull. Chem. Soc. Jpn., 67, 26 (1994)
Quirk RP, Corona-Galvan S, Macromolecules, 34(5), 1192 (2001)
Gilman H, Gaj BJ, J. Org. Chem., 22, 1165 (1957)
Tonhauser C, Nataello A, Lowe H, Frey H, Macromolecules, 45(24), 9551 (2012)
Wilms D, Klos J, Frey H, Macromol. Chem. Phys., 209, 343 (2008)
Wilms D, Wurm F, Klos J, Lowe H, Frey H, Chim. Oggi, 26, 32 (2008)
Geacintov C, Smid J, Szwarc M, J. Am. Chem. Soc., 83, 1253 (1961)
Lohr G, Schulz GV, Makromol. Chem., 77, 240 (1964)
Wurm F, Wilms D, Klos J, Lowe H, Frey H, Macromol. Chem. Phys., 209, 1106 (2008)
Nagaki A, Tomida Y, Yoshida J, Macromolecules, 41(17), 6322 (2008)
Nagaki A, Takahashi Y, Akahori K, Yoshida J, Macromol. React. Eng., 6, 467 (2012)
Nagaki A, Miyazaki A, Tomida Y, Yoshida J, Chem. Eng. J., 167(2-3), 548 (2011)
Nagaki A, Tomida Y, Miyazaki A, Yoshida J, Macromolecules, 42(13), 4384 (2009)
Nagaki A, Miyazaki A, Yoshida J, Macromolecules, 43(20), 8424 (2010)
Iida K, Chastek TQ, Beers KL, Cavicchi KA, Chun J, Fasolka MJ, Lab. Chip., 9, 339 (2009)
Kim JS, Lee JH, Kweon JO, Noh ST, Macromol. Res., 22(3), 248 (2014)
Fetters LJ, Firer EM, Polymer, 18, 306 (1977)
Rembaum A, Indictor N, Siao SP, J. Polym. Sci., 56, 17 (1962)
Quirk RP, Yoo T, Lee Y, Kim J, Lee B, Adv. Polym. Sci., 153, 67 (2000)
Anderson BC, Andrews GD, Arthur P, Jacobson HW, Melby LR, Playtis AJ, Sharkey WH, Macromolecules, 14, 1599 (1981)
Fayt R, Forte R, Jacobs C, Jerome R, Ouhadi T, Teyssie P, Varshney SK, Macromolecules, 20, 1442 (1987)
Kunkel D, Muller AHE, Janata M, Lochmann L, Makromol. Chem. Macromol. Symp., 60, 315 (1992)
Scherble J, Stark B, Stuhn B, Kressler J, Budde H, Horing S, Schubert DW, Simon P, Stamm M, Macromolecules, 32(6), 1859 (1999)
Quirk RP, Ma JJ, Polym. Int., 24, 197 (1991)
Bayer T, Pysall D, Wachsen O, in Microreaction Technology: Industrial Prospects, Ehrfeld W, Ed., Springer Berlin Heidelberg, Berlin, pp 165-170. (2000)
Freyss D, Rempp P, Benoit H, J. Polym. Sci. Polym. Lett., 2, 217 (1964)
Zune C, Dubois P, Grandjean J, Kriz J, Dybal J, Lochmann L, Janata M, Vlcek P, Jerome R, Macromolecules, 32(17), 5477 (1999)
Weidisch R, Michler GH, Fischer H, Arnold M, Hofmann S, Stamm M, Polymer, 40(5), 1191 (1999)
Hadjichristidis N, Pispas S, Floudas G, Block Copolymers: Synthetic Strategies, Physical Properties, and Applications, John Wiley & Sons (2003)

[Related Articles]

[1] Ruzette AV, Leibler L, Nat. Mater., 4(1), 19 (2005)

[2] Walheim S, Schaffer E, Mlynek J, Steiner U, Science, 283(5401), 520 (1999)

[3] Glusker DL, Stiles E, Yoncoskie B, J. Polym. Sci., 49, 297 (1961)

[4] Glusker DL, Lysloff I, Stiles E, J. Polym. Sci., 49, 315 (1961)

[5] Teyssie P, Baran J, Dubois P, Jerome R, Wang JS, Yu JM, Yu YS, Zundel T, Macromol. Symp., 132, 303 (1998)

[6] Teyssie P, Fayt R, Hautekeer JP, Jacobs C, Jerome R, Leemans L, Varshney SK, Makromol. Chem. Macromol. Symp., 32, 61 (1990)

[7] Nakamura N, Yoshino A, Takahashi K, Bull. Chem. Soc. Jpn., 67, 26 (1994)

[8] Quirk RP, Corona-Galvan S, Macromolecules, 34(5), 1192 (2001)

[9] Gilman H, Gaj BJ, J. Org. Chem., 22, 1165 (1957)

[10] Tonhauser C, Nataello A, Lowe H, Frey H, Macromolecules, 45(24), 9551 (2012)

[11] Wilms D, Klos J, Frey H, Macromol. Chem. Phys., 209, 343 (2008)

[12] Wilms D, Wurm F, Klos J, Lowe H, Frey H, Chim. Oggi, 26, 32 (2008)

[13] Geacintov C, Smid J, Szwarc M, J. Am. Chem. Soc., 83, 1253 (1961)

[14] Lohr G, Schulz GV, Makromol. Chem., 77, 240 (1964)

[15] Wurm F, Wilms D, Klos J, Lowe H, Frey H, Macromol. Chem. Phys., 209, 1106 (2008)

[16] Nagaki A, Tomida Y, Yoshida J, Macromolecules, 41(17), 6322 (2008)

[17] Nagaki A, Takahashi Y, Akahori K, Yoshida J, Macromol. React. Eng., 6, 467 (2012)

[18] Nagaki A, Miyazaki A, Tomida Y, Yoshida J, Chem. Eng. J., 167(2-3), 548 (2011)

[19] Nagaki A, Tomida Y, Miyazaki A, Yoshida J, Macromolecules, 42(13), 4384 (2009)

[20] Nagaki A, Miyazaki A, Yoshida J, Macromolecules, 43(20), 8424 (2010)

[21] Iida K, Chastek TQ, Beers KL, Cavicchi KA, Chun J, Fasolka MJ, Lab. Chip., 9, 339 (2009)

[22] Kim JS, Lee JH, Kweon JO, Noh ST, Macromol. Res., 22(3), 248 (2014)

[23] Fetters LJ, Firer EM, Polymer, 18, 306 (1977)

[24] Rembaum A, Indictor N, Siao SP, J. Polym. Sci., 56, 17 (1962)

[25] Quirk RP, Yoo T, Lee Y, Kim J, Lee B, Adv. Polym. Sci., 153, 67 (2000)

[26] Anderson BC, Andrews GD, Arthur P, Jacobson HW, Melby LR, Playtis AJ, Sharkey WH, Macromolecules, 14, 1599 (1981)

[27] Fayt R, Forte R, Jacobs C, Jerome R, Ouhadi T, Teyssie P, Varshney SK, Macromolecules, 20, 1442 (1987)

[28] Kunkel D, Muller AHE, Janata M, Lochmann L, Makromol. Chem. Macromol. Symp., 60, 315 (1992)

[29] Scherble J, Stark B, Stuhn B, Kressler J, Budde H, Horing S, Schubert DW, Simon P, Stamm M, Macromolecules, 32(6), 1859 (1999)

[30] Quirk RP, Ma JJ, Polym. Int., 24, 197 (1991)

[31] Bayer T, Pysall D, Wachsen O, in Microreaction Technology: Industrial Prospects, Ehrfeld W, Ed., Springer Berlin Heidelberg, Berlin, pp 165-170. (2000)

[32] Freyss D, Rempp P, Benoit H, J. Polym. Sci. Polym. Lett., 2, 217 (1964)

[33] Zune C, Dubois P, Grandjean J, Kriz J, Dybal J, Lochmann L, Janata M, Vlcek P, Jerome R, Macromolecules, 32(17), 5477 (1999)

[34] Weidisch R, Michler GH, Fischer H, Arnold M, Hofmann S, Stamm M, Polymer, 40(5), 1191 (1999)

[35] Hadjichristidis N, Pispas S, Floudas G, Block Copolymers: Synthetic Strategies, Physical Properties, and Applications, John Wiley & Sons (2003)