Amphiphilic Norbornene-Based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared by Living Ring Opening Metathesis Polymerization

Su-Dong Park; Wentao Xu; Chanhong Chung; Younghwan Kwon

Macromolecular Research, Vol.16, No.2, 155-162, February, 2008

Su-Dong Park, Wentao Xu¹, Chanhong Chung¹, and Younghwan Kwon^{1, †}

Korea Electrotechnology Research Institute, Changwon, Gyeongnam 641-600, Korea
¹Department of Chemical Engineering, Daegu University, Gyeongsan, Gyeongbuk 712-714, Korea

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We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the RuCl2 (=CHPh)(PCy3)2/CH2Cl2/20 ℃ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBECOOH-b-NBEPOSS) copolymers was confirmed by 1H-NMR, 13C-NMR spectroscopy and GPC.

Keywords:polyhedral oligomeric silsesquioxane;ring-opening metathesis polymerization;block copolymer;living polymerization;sequential monomer addition

[References]

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Bielawski CW, Grubbs RH, Prog. Polym. Sci, 32, 1 (2007)
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Tegou E, Bellas V, Gogolides E, Argitis P, Microelectron. Eng., 73-74, 238 (2004)
Gonsalves KE, Merhari L, Wu HP, Hu YQ, Adv. Mater., 13(10), 703 (2001)
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Haddad TS, Mather PT, Jeon HG, Chun SB, Phillips SH, Mat. Res. Soc. Symp. Proc., CC2.6.1, 628 (2000)
Kwon Y, Kim KH, Macromol. Res., 14(4), 424 (2006)
Grubbs RH, Tumas W, Science, 243, 907 (1989)
Buchmeiser MR, Chem. Rev., 100(4), 1565 (2000)
Ahmed SR, Kofinas P, Macromolecules, 35(9), 3338 (2002)
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Saunders RS, Cohen RE, Wong SJ, Schrock RR, Macromolecules, 25, 2055 (1992)

[Referenced By]

[1] Rempp P, Franta E, Herz JE, Adv. Polym. Sci., 88, 145 (1988)

[2] Kennedy JP, Ivan B, Designed Polymers by Carbocationic Macromolecular Engineering, Hanser, Germany (1991)

[3] Hatada K, Kitayama T, Vogl O, Et AL, Macromolecular Design of Polymeric Materials, Marcel Dekker, New York (1996)

[4] Kwon Y, Faust R, Adv. Polym. Sci., 167, 107 (2004)

[5] Szwarc M, Nature, 178, 1168 (1956)

[6] Ivin KJ, Mol CJ, Olefin Metathesis and Metathesis Polymerization, Academic Press, London (1997)

[7] Grubbs RH, Tetrahedron, 60, 7117 (2004)

[8] Shrock RR, Hoveyda AH, Angew. Chem.-Int. Edit., 42, 4592 (2003)

[9] Bielawski CW, Grubbs RH, Prog. Polym. Sci, 32, 1 (2007)

[10] Kim KM, Chujo Y, J. Polym. Sci. A: Polym. Chem., 39(22), 4035 (2001)

[11] Xie P, Zhang RB, Polym. Adv. Technol., 8, 649 (1997)

[12] Zhang CX, Bunning TJ, Laine RM, Chem. Mater., 13, 3653 (2001)

[13] Choi J, Harcup J, Yee AF, Zhu Q, Laine RM, J. Am. Chem. Soc., 123(46), 11420 (2001)

[14] Sanchez C, Soler-Illia G, Ribot F, Lalot T, Mayer CR, Cabuil V, Chem. Mater., 13, 3061 (2001)

[15] Zheng L, Farris RJ, Coughlin EB, Macromolecules, 34(23), 8034 (2001)

[16] Nyman MD, Desu SB, Peng CH, Chem. Mater., 5, 1636 (1993)

[17] Tegou E, Bellas V, Gogolides E, Argitis P, Microelectron. Eng., 73-74, 238 (2004)

[18] Gonsalves KE, Merhari L, Wu HP, Hu YQ, Adv. Mater., 13(10), 703 (2001)

[19] Pyun J, Matyjaszewski K, Macromolecules, 33(1), 217 (2000)

[20] Pyun J, Matyjaszewski K, Wu J, Kim GM, Chun SB, Mather PT, Polymer, 44(9), 2739 (2003)

[21] Haddad TS, Mather PT, Jeon HG, Chun SB, Phillips SH, Mat. Res. Soc. Symp. Proc., CC2.6.1, 628 (2000)

[22] Kwon Y, Kim KH, Macromol. Res., 14(4), 424 (2006)

[23] Grubbs RH, Tumas W, Science, 243, 907 (1989)

[24] Buchmeiser MR, Chem. Rev., 100(4), 1565 (2000)

[25] Ahmed SR, Kofinas P, Macromolecules, 35(9), 3338 (2002)

[26] Ahmed SR, Bullock SE, Cresce AV, Kofinas P, Polymer, 44(17), 4943 (2003)

[27] Bullock SE, Kofinas P, Macromolecules, 37(5), 1783 (2004)

[28] Saunders RS, Cohen RE, Wong SJ, Schrock RR, Macromolecules, 25, 2055 (1992)