Bulk and Thermal Characteristics of Poly(ethylene oxide)-Polystyrene Multiblock Copolymers

Sung YK; Kim YJ; Grainger DW; Okano T; Kim SW

Korea Polymer Journal, Vol.1, No.1, 14-20, April, 1993

Sung YK, Kim YJ, Grainger DW, Okano T, Kim SW

Phase-separated multiblock copolymers of poly(ethylene oxide) (PEO) and poly styrene (PS) had been synthesized by reacting functionalized telechelic oligomers of each block to create repeating urethane linkages between blocks. Block lengths were varied to change copolymer composition and these effects on bulk and thermal properties were examined. The multiblock copolymers were characterized by Fourier transform infrared analysis, ¹H nuclear magnetic resonance spectroscopy and ultraviolet absorption spectroscopy. Thermal analysis using differential scanning calorimetry and thermogravimetric analysis showed that the melting temperature, enthalpy of fusion, and entropy of fusion of the PEO blocks increased with increasing PEO content. The glass transition temperature of the PS component was shifted compared to PS homopolymers. These results are interpreted in terms of a model for PEO-PS copolymers based on various degrees of phase-separated and phase-mixed structure. The activation energies determined for the decomposition of the homopolymers and block copolymers are 198.4 KJ/mol for PEO and 193.9 KJ/mol for PS, respectively

[References]

Cooper SL, Estes GM, Multiphase Polymers, Adv. Chem. Ser. No. 176, ACS, Washington, D.C. (1969)
Noshay A, McGrath JE, Block Copolymers: Overview and Critical Survey, Academic Press, New York (1977)
Matsuo M, Sagaye S, Micromorphological Behavior of Block and Graft Copolymers, G.E. Molau, Ed., Plenum, New York, pp. 1-20 (1971)
Grainger D, Okano T, Kim SW, Surface Characteristics of Poly(ethyleneoxide)-Polystyrene Multiblock Copolymers, in Advances in Biomedical Polymers, C. Gebelein, Ed., Plenum, New York, p. 229 (1987)
VanLeemput R, Stein R, J. Polym. Sci. A: Polym. Chem., 2, 4039 (1964)
O'Malley JJ, Crystal RG, Erhardt PF, Synthesis and Thermal Transition Properties of Styrene-Ethylene Oxide Block Copolymers, in Block Polymers, S.L. Aggarwal, Ed., Plenum Press, New York, pp. 163-178 (1970)
Lombardi G, For Better Thermal Analysis: International Confederation for Thermal Analysis (1977)
Li X, Hsu SL, J. Polym. Sci. B: Polym. Phys., 22, 1331 (1984)
Kambe Y, Polym. Prepr., 32, 3861 (1980)
Buckly CP, Kovacs AJ, Chain Folding in POlymer Crystals: Evidence from Microscopy and Colorimetry of Poly(ethylene oxide), in Structure of Crystaline Polymers, I.H. Hall, Ed., Elsevier Appl. Sci., London, p. 272 (1984)
Flory PJ, Principles of Polymer Chemistry, Cornell University Press, Ithaca, New York (1953)
Katine IA, Anasagasti MS, Peleteiro MC, Vaenciano R, Eur. Polym. J., 23, 907 (1987)
Beech DR, Booth C, Pickles CJ, Sharpe RR, Waring JR, Polymer, 13, 246 (1972)
Ke B, J. Polym. Sci., 50, 79 (1961)
Price C, Evans KA, Booth C, Polymer, 16, 196 (1975)
Mandelkern L, J. Appl. Phys., 26, 443 (1955)
Jaffe M, Wuderlich B, Kolloid Z.Z. Polym., 216, 203 (1967)
Grainger DW, Okano T, Kim SW, Castner DG, Ratner BD, Briggs D, Sung YK, J. Biomed. Mater. Res., 24, 547 (1990)
Fortune LR, Malcolm GM, J. Phys. Chem., 64, 934 (1960)
Orhan EH, Yilgor I, Baysal BM, Polymer, 18, 286 (1987)
Ichihara S, Komatsu A, Hata T, Polym. J., 2, 644 (1971)
Grassie N, Scott G, POlymer Degradation and Stabilization, Cambridge University Press, Cambridge, p. 25 (1985)
Jellinek HHG, Degradation and Stabilization of Polymers, Elsevier Science Publishers, New York, p. 39 (1983)
Madorsky SL, Strauss S, J. Polym. Sci., 36, 183 (1959)
Ozawa T, Bull. Chem. Soc. Jpn., 38, 1881 (1965)

[Referenced By]

[1] Cooper SL, Estes GM, Multiphase Polymers, Adv. Chem. Ser. No. 176, ACS, Washington, D.C. (1969)

[2] Noshay A, McGrath JE, Block Copolymers: Overview and Critical Survey, Academic Press, New York (1977)

[3] Matsuo M, Sagaye S, Micromorphological Behavior of Block and Graft Copolymers, G.E. Molau, Ed., Plenum, New York, pp. 1-20 (1971)

[4] Grainger D, Okano T, Kim SW, Surface Characteristics of Poly(ethyleneoxide)-Polystyrene Multiblock Copolymers, in Advances in Biomedical Polymers, C. Gebelein, Ed., Plenum, New York, p. 229 (1987)

[5] VanLeemput R, Stein R, J. Polym. Sci. A: Polym. Chem., 2, 4039 (1964)

[6] O'Malley JJ, Crystal RG, Erhardt PF, Synthesis and Thermal Transition Properties of Styrene-Ethylene Oxide Block Copolymers, in Block Polymers, S.L. Aggarwal, Ed., Plenum Press, New York, pp. 163-178 (1970)

[7] Lombardi G, For Better Thermal Analysis: International Confederation for Thermal Analysis (1977)

[8] Li X, Hsu SL, J. Polym. Sci. B: Polym. Phys., 22, 1331 (1984)

[9] Kambe Y, Polym. Prepr., 32, 3861 (1980)

[10] Buckly CP, Kovacs AJ, Chain Folding in POlymer Crystals: Evidence from Microscopy and Colorimetry of Poly(ethylene oxide), in Structure of Crystaline Polymers, I.H. Hall, Ed., Elsevier Appl. Sci., London, p. 272 (1984)

[11] Flory PJ, Principles of Polymer Chemistry, Cornell University Press, Ithaca, New York (1953)

[12] Katine IA, Anasagasti MS, Peleteiro MC, Vaenciano R, Eur. Polym. J., 23, 907 (1987)

[13] Beech DR, Booth C, Pickles CJ, Sharpe RR, Waring JR, Polymer, 13, 246 (1972)

[14] Ke B, J. Polym. Sci., 50, 79 (1961)

[15] Price C, Evans KA, Booth C, Polymer, 16, 196 (1975)

[16] Mandelkern L, J. Appl. Phys., 26, 443 (1955)

[17] Jaffe M, Wuderlich B, Kolloid Z.Z. Polym., 216, 203 (1967)

[18] Grainger DW, Okano T, Kim SW, Castner DG, Ratner BD, Briggs D, Sung YK, J. Biomed. Mater. Res., 24, 547 (1990)

[19] Fortune LR, Malcolm GM, J. Phys. Chem., 64, 934 (1960)

[20] Orhan EH, Yilgor I, Baysal BM, Polymer, 18, 286 (1987)

[21] Ichihara S, Komatsu A, Hata T, Polym. J., 2, 644 (1971)

[22] Grassie N, Scott G, POlymer Degradation and Stabilization, Cambridge University Press, Cambridge, p. 25 (1985)

[23] Jellinek HHG, Degradation and Stabilization of Polymers, Elsevier Science Publishers, New York, p. 39 (1983)

[24] Madorsky SL, Strauss S, J. Polym. Sci., 36, 183 (1959)

[25] Ozawa T, Bull. Chem. Soc. Jpn., 38, 1881 (1965)