Macromolecules, 40 (8), 2798 -2805, 2007. 10.1021/ma062393d S0024-9297(06)02393-X
Web Release Date: March 21, 2007

Copyright © 2007 American Chemical Society

Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl-Substituted Polyhedral Oligomeric Silsesquioxanes

Daniel B. Drazkowski, Andre Lee,* and Timothy S. Haddad

Department of Chemical Engineering & Materials Science, Michigan State University, East Lansing, Michigan 48824, and ERC, Inc., AFRL/PRSM, Edwards AFB, California 93524

Received October 17, 2006

Revised Manuscript Received February 14, 2007

Abstract:

Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different initial morphologies were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules. The POSS octamers, R'R7Si8O12, were designed to contain a single silane functional group, R', which was used to graft onto the dangling 1,2-butadienes in the polybutadiene block and seven identical organic groups, R = isobutyl (iBu). Morphology and phase transitions of these iBu-POSS-modified SBS were investigated using small-angle X-ray scattering and rheological methods. It was observed that when iBu-POSS was grafted to the butadiene segment, the long-range and local order of the morphology were preserved, and the d-spacing showed a small, systematic increase with increasing POSS content. These observations suggest that grafted iBu-POSS were well-distributed within the butadiene domains and did not interact with the styrene domains; effectively, grafting of iBu-POSS to butadiene did not affect the segregation between butadiene and styrene domains. However, addition of iBu-POSS reduces the overall polystyrene volume. Consequently, from a morphology standpoint, this modification effectively shifts the phase diagram to lower styrene content. This was supported with SAXS and transition temperatures measurements made from the different host morphologies.


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