Phase-Selective Curing of Poly(p-Methylstyrene-b-Butadiene-b-p-Methylstyrene)

  • Roderic P. Quirk
  • Michael T. Sarkis
  • Dale J. Meier

Abstract

The preparation, properties and phase-selective crosslinking reactions of poly(p-methylstyrene-b-butadiene-b-p-methylstyrene), PMS-BD-PMS, have been examined. The PMS-BD-PMS triblock copolymer was synthesized anionically by sequential monomer addition. The ability to selectively crosslink the poly(p-methylstyrene) end-block segments was examined by curing with various polymers containing hydroperoxide end groups. Both polystyrene hydroperoxide, PSO2H, and poly(p-methylstyrene) hydroperoxide, PMSO2H, were found to significantly increase tensile stress at break and the percent elongation-at-break of the PMS-BD-PMS triblock copolymer. In addition, the modified triblock copolymer was insoluble in toluene, heptane and methyl ethyl ketone. When unfunctionalized styrene homopolymer was added the effects were quite different. These results have been compared to the unselective, non-phase-selective peroxide, dicumyl peroxide, which dramatically decreases the elastomeric properties of the triblock copolymer after curing. In addition, the specificity of this effect has been investigated by carrying out equivalent experiments with an analogous poly(styrene-b-butadiene-b-styrene), PS-BD-PS, triblock copolymer. No enhancement of tensile properties was observed on the treatment. of the PS-BD-PS triblock copolymer with PS02H, followed by curing. The phase-selective curing of PMS-BD-PMS resulted in a product with better tensile properties at 70ºC than that observed for the corresponding uncured PMS-BD-PMS and PS-BD-PS triblock copolymers.

Keywords

Block Copolymer Triblock Copolymer Methyl Ethyl Ketone Dynamic Mechanical Thermal Analyzer Thermoplastic Elastomer 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. (1).
    M. Morton, Anionic Polymerization: Principles and Practice, Academic Press, New York, 1983.Google Scholar
  2. (2).
    R.N. Young, R.P. Quirk and L.J. Fetters, Adv. Polym. Sci., 56, 1 (1984).CrossRefGoogle Scholar
  3. (3).
    M. Szwarc, Adv. Polym. Sci., 49, 1 (1983).CrossRefGoogle Scholar
  4. (4).
    S. Bywater, Prog. Polym. Sci., 4, 27 (1974).CrossRefGoogle Scholar
  5. (5).
    S. Bywater, Anionic Polymerization in Encyclopedia of Polymer Science and Engineering, 2nd Ed., Wiley-Interscience, New York, Vol. 2, 1985, p. 1.Google Scholar
  6. (6).
    M. Szwarc, Carbanions, Living Polymers and Electron Transfer Processes, Interscience, New York, 1968.Google Scholar
  7. (7).
    M. Morton and L.J. Fetters, Rubber Chem. Technol., 48, 359 (1975).CrossRefGoogle Scholar
  8. (8).
    A. Noshay and J.E. McGrath, Block Copolymers: Overview and Critical Survey, Academic Press, New York, 1977.Google Scholar
  9. (9).
    J.C. Falk and M.A. Benedetto in Macromolecular Synthesis, E.M. Pearce, Ed., Wiley-Interscience, 1982, Vol. 8, p. 61.Google Scholar
  10. (10).
    L.J. Fetters and M. Morton, Macromolecules, 2, 453 (1969).ADSCrossRefGoogle Scholar
  11. (11).
    A. Hirai, K. Yamaguchi, K. Takenaka, K. Suzuki and S. Nakahama, Makromol. Chem., Rapid Commun., 3, 941 (1982).CrossRefGoogle Scholar
  12. (12).
    D. Engel and R.C. Schulz, Eur. Polym. J., 19, 967 (1983).CrossRefGoogle Scholar
  13. (13).
    W.W. Kaeding and G.C. Barite in New Monomers and Polymers, B.M. Culbertson and C.U. Pittman, Eds., Plenum, New York, 1984, p. 223.CrossRefGoogle Scholar
  14. (14).
    R.P. Quirk and W.-C. Chen, Makromol. Chem., 183, 2071 (1982).CrossRefGoogle Scholar
  15. (15).
    H. Gilman and F.K. Cartledge, J. Organomet. Chem., 2, 447 (1964)CrossRefGoogle Scholar
  16. (16).
    R.P. Quirk and W.-C. Chen, J. Polym. Sci. Polym. Chem. Ed., 22, 2993 (1984).ADSCrossRefGoogle Scholar
  17. (17).
    A.J. Martin, Determination of Organic Peroxide in Organic Analysis, J. Mitchell, Ed., Interscience, New York, 1960, Vol. IV, pp. 1–64.Google Scholar
  18. (18).
    P.A. Small, J. Appl. Chem., 3, 77 (1953).Google Scholar
  19. (19).
    A. Ahmad and M. Yaseen, Polym. Eng. Sci., 19, 858 (1979).CrossRefGoogle Scholar
  20. (20).
    S.L. Aggarwal, Polymer, 17, 938 (1976).CrossRefGoogle Scholar
  21. (21).
    D.J. Meier, J. Polym. Sci. Part C, 26, 81 (1969).CrossRefGoogle Scholar
  22. (22).
    D.J. Meier in Block and Graft Copolymers, J.J. Burke and V. Weiss, Eds., Syracuse University Press, Syracuse, New York, 1973, Ch. 6, p. 105.Google Scholar
  23. (23).
    D.J. Meier, Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem., 15(1) 171 (1974).Google Scholar
  24. (24).
    E. Helfand, Macromolecules, 8, 552 (1975).ADSCrossRefGoogle Scholar
  25. (25).
    E. Helfand and Z.R. Wasserman, Macromolecules, 9, 879 (1976).ADSCrossRefGoogle Scholar
  26. (26).
    E. Helfand, Accounts Chem. Res., 8, 295 (1975).ADSCrossRefGoogle Scholar
  27. (27).
    M. Morton in Encyclopedia of Polymer Science and Technology, Wiley, New York, 1971, Vol. 15, p. 508.Google Scholar
  28. (28).
    S. Krause, J. Polym. Sci. Polym. Lett. Ed., 7, 249 (1969).Google Scholar
  29. (29).
    S. Krause, Macromolecules, 3, 84 (1970).ADSCrossRefGoogle Scholar
  30. (30).
    D.J. Meier, Block Copolymers: Science and Technology, MMI Symposium Series, Harwood Academic, 1983.Google Scholar
  31. (31).
    K. Solo, Polymer Compatibility and Incompatibility, Principles and Practice, MMI Symposium Series, Harwood Academic, 1982.Google Scholar
  32. (32).
    S.L. Aggarwal, R.A. Livigni, L.F. Marker and T.J. Dudek in Block and Graft Copolymers, J.J. Burke and V. Weiss, Eds., Syracuse University Press, Syracuse, New York, 1973, Ch. 9, p. 157.Google Scholar
  33. (33).
    R. Seguela and J. Prud’homme, Macromolecules, 11, 1007 (1978).ADSCrossRefGoogle Scholar
  34. (34).
    A.E. Platt and H. Keskkula in Encyclopedia of Polymer Science and Technology, Wiley-Interscience, New York, 1970, Vol. 13, p. 236.Google Scholar
  35. (35).
    “Typical Property Guide, Kraton D and G,” Brochure #SC 68–85, Shell Development Company, Houston, Texas, 1985.Google Scholar
  36. (36).
    L.J. Fetters, B.H. Meyer and D. McIntyre, J. Appl. Polym. Sci., 16, 2079 (1972).CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1986

Authors and Affiliations

  • Roderic P. Quirk
    • 1
  • Michael T. Sarkis
    • 1
  • Dale J. Meier
    • 2
  1. 1.Institute of Polymer ScienceThe University of AkronAkronUSA
  2. 2.Michigan Molecular InstituteMidlandUSA

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