[en] Synthesis of PMMA−PBD−PMMA (MBM) triblock copolymers with a 1,3-diisopropenylbenzene- (DIB-) based initiator is studied. Diethyl ether, tert-butyl methyl ether, N,N,N‘,N‘-tetramethylethylenediamine (TMEDA) and THF were found to be efficient polar additives for obtaining PMMA−PBD−PMMA triblock copolymers, but these triblock copolymers displayed a high 1,2-microstructure of the PBD block. A combination of the initiator seeding technique and weakly polar additives has allowed MBM triblock copolymers with high 1,4-microstructure of PBD to be obtained. These copolymers exhibited a definitely higher upper service temperature than conventional thermoplastic elastomers, i.e. SBS or SIS Kratons. The influence of chain microstructure, copolymer composition and block length on the mechanical properties has been studied. Short polystyrene blocks of ca. Mn 2000 have been incorporated in between the PBD central block and the PMMA outer sequences. A higher tensile strength was observed for these MBM-like triblock coplymers. Contamination by a diblock structure expectedly had a very depressive effect on the bulk properties, and the stress−strain behavior mainly depended on the PMMA content and secondarily on molecular weight.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Yu, Y. S.; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Difunctional initiator based on 1,3-diisopropenylbenzene. 6. Synthesis of methyl methacrylate-butadiene-methyl methacrylate triblock copolymers
Publication date :
28 July 1997
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Morton, M.; McGrath, J. E; Juliano, P. C. J. Polym. Sci., Part C, 1969, 26, 99.
Shell Chemical Co.: Kratons, Cariflex TR Belg. Pat. 671460, 1966.
Philips Petroleum Co.: Solprene Rubbers, J. R. Haws, Rubber World 1973, 27.
(a) Morton, M. Research on anionic triblock copolymers. In Thermoplastic Elastomers; Legge, N. R. Holden, G., Schroeder, H. E., Eds; Hanser: Munich, Germany, Vienna, New York, 1987.
(b) Morton, M. Anionic Polymerization: Principle and Practice; Academic Press: New York, 1983.
Schepers, H. A. J.; Roest, B. C.; Stamicarbon,N. V. Ger. Patent DE 2231993, 1973.
Goett, C.; Journe, J. Rev. Gen. Caoutch. Plast. 1976, 53, 47.
Rossi, J.; Gallot, B. Makromol. Chem. 1976, 177, 2801.
Cohen, R. E.; Bates, F. S. Gov. Rep. Announce. Index (U. S.) 1980, 80 (8), 1317; Report TR-4, Order No. AD-A0787731.
Gohen, R. E.; Bates, J. Polym. Sci., Polym. Phys. Ed. 1980, 18, 2143.
Tiyssié,Ph.; Jérôme, R.; Ouhadi, T.; Fayt, R., U.S. Patent, U.S. 4,461,874, 1984.
Teyssié, Ph.; Fayt, R.; Hautekeer, J. P.; Jacobs, C.; Jérôme, R.; Leemans, L.; Varshney, S. K. V. Macromol. Chem. Symp. 1990, 32, 61.
Helary, G.; Ladd, B.; Hogen-Esch, T. E. Polym. Prepr. 1987, 28, 318.
Long, T. E.; Broeke, A. D.; Bradley, D. J.; McGrath, J. E. J. Polym. Sei., Polym. Chem. 1989, 27, 4001.
Ladd, B. J.; Hogen-Each, T. E. Polym. Prepr. 1989, 30, 261.
Sutherland, R. J. Eur. Pat. Appl. EP 459, 588, 1991.
DePorter, C. D.; Ferrence, G. M.; McGrath, J. E. Polym. Prepr. 1993, 34, 574.
Fetter, L. J.; Morton, M. Macromolecules 1969, 2, 435.
Lutz, P.; Franta, E; Rempp, P. C. R. Hebd. Seances Acad. Sci., Ser. C 1976, 283, 123.
Foss, R. P.; Jacobson, H. W.; Sharkey, W. H. Macromolecules 1977, 10, 287.
Tung, L. H.; Lo, G. Y.-S.; Beyer, D. E. Mocromolecules 1978, 11, 616.
Long, T. E.; Allen, R. D.; McGrath, J. E. Recent advances in mechanistic and synthetic aspects of polymerization: Fontanille, M., Guyot, A., Eds.; Reidel Publ.: Dordrecht, The Netherlands, 1987; p 79.
Yu, Y. S.; Dubois, Ph.; Teyssié, Ph.; Jérôme, R. 5. Effect of polar additives and initiator seeding on the synthesis of poly-(styrene-b-butadiene-b-styrene) copolymers. Macromolecules, submitted for publication.
Allen, R. D.; Long, T. E.; McGrath, J. E. Polym. Bull., 1986, 15, 127.
Gilman, H.; Cartledge, F. K. J. Organomet. Chem. 1964, 2, 447.
Unpublished results.
Young, R. N.; Quirk, R. P., Fetters, L. J. Anionic Polymerization of Non-polar Monomers Involving Lithium. Adv. Polym. Sci. 1984, 56.
Kraus, G.; Rollmann, W. J. Polym. Sci., Polym. Phlym. Ed. 1976, 14, 1133.
Matsauo, M; Veno, T.; Hormio, H.; Churjyio, S.; Asi, H. Polymer 1989, 9, 425.