On-Line Monitoring of Reaction Temperatures During Anionic Polymerization of Poly(styrene-b-methyl methacrylate) and Poly(styrene-b-2-vinyl pyridine) with a 1,1-Diphenylhexyl Lithium Initiator in THF

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

Macromolecular Research, Vol.22, No.3, 248-256, March, 2014

DOI10.1007/s13233-014-2039-4 Export Citation

On-Line Monitoring of Reaction Temperatures During Anionic Polymerization of Poly(styrene-b-methyl methacrylate) and Poly(styrene-b-2-vinyl pyridine) with a 1,1-Diphenylhexyl Lithium Initiator in THF

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

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

E-mail:

Poly(styrene-b-methyl methacrylate) and poly(styrene-b-2-vinyl pyridine) block copolymers with narrow molecular weight distributions (1.05≤MWD≤1.17) were achieved via a pre-cooled monomer addition method using a diphenyl hexyl lithium initiator in tetrahydrofuran under sequential isothermal conditions. The styrene block was polymerized at -25 and -15 ℃, and the second block copolymerization of PS-b-PMMA and PS-b-P2VP was carried out at -78 ℃. A module-type reactor system was constructed under an inert atmosphere, which could monitor the temperature and torque during polymerization. Monomers for the second block were cooled and maintained at approximately -30 ℃ to control the exothermic reaction temperatures while being added to the reactor. The exothermic reaction temperature could be minimized (ΔTRMAX ≤+11 ℃) by the addition of the pre-cooled monomer.

Keywords:anionic polymerization;poly(styrene-b-methyl methacrylate) block copolymer;poly(styrene-b-2-vinyl pyridine) block copolymer;1,1-diphenylalkyl lithium;reactor for anionic polymerization.

[References]

Edwards EW, Muller M, Stoykovich MP, Solak HH, de Pablo JJ, Nealey PF, Macromolecules, 40(1), 90 (2007)
Kim BH, Jeong SJ, Shin DO, Park SH, Lee HM, Xia G, Koo JM, Kim SO, Electron. Mater. Lett., 3, 147 (2007)
Moon HS, Shin DO, Kim BH, Jin HM, Lee SM, Lee MG, Kim SO, J. Mater. Chem., 22, 6307 (2012)
Hillmyer MA, Adv. Polym. Sci., 190, 137 (2005)
Bates FS, Fredrickson GH, Annu. Rev. Phys. Chem., 41, 525 (1990)
Black CT, Ruiz R, Breyta G, Cheng JY, Colburn ME, Guarini KW, Kim CH, Zhang Y, IBM J. Res. Dev., 51, 605 (2007)
Olson DA, Chen L, Hillmyer MA, Chem. Mater., 20, 869 (2008)
Gilman H, Gaj BJ, J. Org. Chem., 22, 1167 (1957)
Saban M, Liebermann G, Jay A, Shi AC, Ro N, Dale W, Forgione P, Can. J. Chem. Eng., 78(2), 320 (2000)
Okamoto A, Watanabe E, Mita I, J. Polym. Sci. Part A: Polym. Chem., 17, 2483 (1979)
Comyn J, Glasse MD, J. Polym. Sci. Part A: Polym. Chem., 21, 209 (1983)
Comyn J, Glasse MD, J. Polym. Sci. Part A: Polym.Chem., 21, 227 (1983)
Glasse MD, Prog. Polym. Sci., 9, 133 (1983)
Quirk RP, Yoo TJ, Lee YJ, Kim JG, Lee BJ, Adv.Polym. Sci., 153, 67 (2000)
Hsieh HL, Quirk RP, in Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 279 (1996)
Anderson BC, Andrew GD, Arthur PJ, 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, Macromol. 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)
Mecerreyes D, Dubois P, Jerome R, Hedrick JL, Macromol. Chem. Phys., 200, 156 (1999)
Quirk RP, Monroy VM, in Kirk-Othmer Encyclopedia of Chemical Technology, Initiators, J. I. Kroschwits, Ed., Wiley, New York, 14, 461 (2007)
Glusker DL, Stiles E, Yonkoskie B, J. Polym. Sci., 49, 297 (1961)
Glusker DL, Lysloff I, Stiles E, J. Polym. Sci., 49, 315 (1961)
Nakamura N, Yoshino A, Takahashi K, Bull. Chem. Soc.Jpn., 67, 26 (1994)
Quirk RP, Corona-Galvan S, Macromolecules, 34(5), 1192 (2001)
Ogle CA, Strickler FH, Gordon B, Macromolecules., 26, 5803 (1993)
Mohan YM, Raghunadh V, Sivaram S, Baskaran D, Macromolecules, 45(8), 3387 (2012)
Hsieh HL , McKinney OF, J. Polym. Sci. Part C: Polym.Lett., 4, 843 (1966)
Gold L, J. Chem. Phys., 28, 91 (1958)
Fetters LJ, in Encyclopedia of Polymer Science and Engineering, Monodisperse Polymers., J. I. Kroschwitz, Ed., Wiley, New York, 10, 19 (1987)
Rempp P, Franta E, Herz JE, Adv. Polym. Sci., 86, 145 (1988)
Fetters LJ, Firer EM, Polymer., 18, 306 (1977)
Quirk RP, Chen WC, J. Polym. Chem. Ed., 22, 2993 (1984)
Panek EJ, Whitesides GM, J. Am. Chem. Soc., 94, 8768 (1972)
Catala JM, Riess G, Brossas J, Makromol. Chem., 178, 1249 (1977)
Ohata M, Isono Y, Polymer., 34, 1546 (1993)
Ohata M, Ikeda S, Akatani SI, Isono Y, Macromolecules., 25, 5131 (1992)
Kang NG, Changez M, Lee JS, Macromolecules, 40(24), 8553 (2007)

[Referenced By]

[Related Articles]

[1] Edwards EW, Muller M, Stoykovich MP, Solak HH, de Pablo JJ, Nealey PF, Macromolecules, 40(1), 90 (2007)

[2] Kim BH, Jeong SJ, Shin DO, Park SH, Lee HM, Xia G, Koo JM, Kim SO, Electron. Mater. Lett., 3, 147 (2007)

[3] Moon HS, Shin DO, Kim BH, Jin HM, Lee SM, Lee MG, Kim SO, J. Mater. Chem., 22, 6307 (2012)

[4] Hillmyer MA, Adv. Polym. Sci., 190, 137 (2005)

[5] Bates FS, Fredrickson GH, Annu. Rev. Phys. Chem., 41, 525 (1990)

[6] Black CT, Ruiz R, Breyta G, Cheng JY, Colburn ME, Guarini KW, Kim CH, Zhang Y, IBM J. Res. Dev., 51, 605 (2007)

[7] Olson DA, Chen L, Hillmyer MA, Chem. Mater., 20, 869 (2008)

[8] Gilman H, Gaj BJ, J. Org. Chem., 22, 1167 (1957)

[9] Saban M, Liebermann G, Jay A, Shi AC, Ro N, Dale W, Forgione P, Can. J. Chem. Eng., 78(2), 320 (2000)

[10] Okamoto A, Watanabe E, Mita I, J. Polym. Sci. Part A: Polym. Chem., 17, 2483 (1979)

[11] Comyn J, Glasse MD, J. Polym. Sci. Part A: Polym. Chem., 21, 209 (1983)

[12] Comyn J, Glasse MD, J. Polym. Sci. Part A: Polym.Chem., 21, 227 (1983)

[13] Glasse MD, Prog. Polym. Sci., 9, 133 (1983)

[14] Quirk RP, Yoo TJ, Lee YJ, Kim JG, Lee BJ, Adv.Polym. Sci., 153, 67 (2000)

[15] Hsieh HL, Quirk RP, in Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 279 (1996)

[16] Anderson BC, Andrew GD, Arthur PJ, Jacobson HW, Melby LR, Playtis AJ, Sharkey WH, Macromolecules., 14, 1599 (1981)

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

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

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

[20] Mecerreyes D, Dubois P, Jerome R, Hedrick JL, Macromol. Chem. Phys., 200, 156 (1999)

[21] Quirk RP, Monroy VM, in Kirk-Othmer Encyclopedia of Chemical Technology, Initiators, J. I. Kroschwits, Ed., Wiley, New York, 14, 461 (2007)

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

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

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

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

[26] Ogle CA, Strickler FH, Gordon B, Macromolecules., 26, 5803 (1993)

[27] Mohan YM, Raghunadh V, Sivaram S, Baskaran D, Macromolecules, 45(8), 3387 (2012)

[28] Hsieh HL , McKinney OF, J. Polym. Sci. Part C: Polym.Lett., 4, 843 (1966)

[29] Gold L, J. Chem. Phys., 28, 91 (1958)

[30] Fetters LJ, in Encyclopedia of Polymer Science and Engineering, Monodisperse Polymers., J. I. Kroschwitz, Ed., Wiley, New York, 10, 19 (1987)

[31] Rempp P, Franta E, Herz JE, Adv. Polym. Sci., 86, 145 (1988)

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

[33] Quirk RP, Chen WC, J. Polym. Chem. Ed., 22, 2993 (1984)

[34] Panek EJ, Whitesides GM, J. Am. Chem. Soc., 94, 8768 (1972)

[35] Catala JM, Riess G, Brossas J, Makromol. Chem., 178, 1249 (1977)

[36] Ohata M, Isono Y, Polymer., 34, 1546 (1993)

[37] Ohata M, Ikeda S, Akatani SI, Isono Y, Macromolecules., 25, 5131 (1992)

[38] Kang NG, Changez M, Lee JS, Macromolecules, 40(24), 8553 (2007)