Chemical substituent effects on morphological transitions in styrene-butadiene-styrene triblock copolymer grafted with polyhedral oligomeric silsesquioxanes

Daniel B. Drazkowski, Andre Lee, Timothy S. Haddad, David J. Cookson

Research output: Contribution to journalArticle

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Abstract

A series of hybrid organic/inorganic triblock copolymers of polystyrene-butadiene-polystyrene (SBS) grafted with polyhedral oligomeric silsesquioxane (POSS) molecules with different chemical constituents were synthesized by a hydrosilation method. Four POSS macromers, R′R 7Si 8O 12, were designed to contain a single silane functional group, R', which was used to graft onto the dangling 1,2-butadienes in the polybutadiene soft block and seven identical organic groups, R. Small-angle X-ray scattering and Theological techniques were used to study the effect of sterically similar, yet electronically different, organic R groups, cyclopentyl (Cp), cyclohexyl (Cy), cyclohexenyl (Cye), and phenyl (Ph), on the morphology of SBS triblock copolymer and the order-disorder transition behavior. It was observed that POSS with phenyl moiety, when grafted to the polybutadiene (PB) phase, appears to show favorable interaction with the polystyrene (PS) phase; effectively, the Ph-POSS is plasticizing the SBS due to an effect whereby the Ph-POSS is at least partially solvated by the PS phase. This causes a significant decrease in the overall lamellae d spacing and the order-disorder transition temperature, T ODT, with increasing amounts of Ph-POSS attachment. As we change the POSS moiety to that of Cye, Cy, and Cp, the interaction between POSS-PS weakens, and the d spacing and T ODT become less dependent on the amounts of POSS attachment. At the highest POSS loadings investigated (20 wt %), there is a change to a perforated layer morphology, resulting in an increase of T ODT relative to the 10 wt % POSS-grafted copolymers for Cp, Cy, and Cye POSS moieties.

LanguageEnglish (US)
Pages1854-1863
Number of pages10
JournalMacromolecules
Volume39
Issue number5
DOIs
StatePublished - Mar 7 2006

Profile

Polystyrenes
Butadiene
Block copolymers
Styrene
Order disorder transitions
Polybutadienes
Butadienes
Silanes
X ray scattering
Grafts
Functional groups
Superconducting transition temperature
Copolymers
styrene-butadiene-styrene triblock copolymer
Molecules
polybutadiene

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Chemical substituent effects on morphological transitions in styrene-butadiene-styrene triblock copolymer grafted with polyhedral oligomeric silsesquioxanes. / Drazkowski, Daniel B.; Lee, Andre; Haddad, Timothy S.; Cookson, David J.

In: Macromolecules, Vol. 39, No. 5, 07.03.2006, p. 1854-1863.

Research output: Contribution to journalArticle

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abstract = "A series of hybrid organic/inorganic triblock copolymers of polystyrene-butadiene-polystyrene (SBS) grafted with polyhedral oligomeric silsesquioxane (POSS) molecules with different chemical constituents were synthesized by a hydrosilation method. Four POSS macromers, R′R 7Si 8O 12, were designed to contain a single silane functional group, R', which was used to graft onto the dangling 1,2-butadienes in the polybutadiene soft block and seven identical organic groups, R. Small-angle X-ray scattering and Theological techniques were used to study the effect of sterically similar, yet electronically different, organic R groups, cyclopentyl (Cp), cyclohexyl (Cy), cyclohexenyl (Cye), and phenyl (Ph), on the morphology of SBS triblock copolymer and the order-disorder transition behavior. It was observed that POSS with phenyl moiety, when grafted to the polybutadiene (PB) phase, appears to show favorable interaction with the polystyrene (PS) phase; effectively, the Ph-POSS is plasticizing the SBS due to an effect whereby the Ph-POSS is at least partially solvated by the PS phase. This causes a significant decrease in the overall lamellae d spacing and the order-disorder transition temperature, T ODT, with increasing amounts of Ph-POSS attachment. As we change the POSS moiety to that of Cye, Cy, and Cp, the interaction between POSS-PS weakens, and the d spacing and T ODT become less dependent on the amounts of POSS attachment. At the highest POSS loadings investigated (20 wt {\%}), there is a change to a perforated layer morphology, resulting in an increase of T ODT relative to the 10 wt {\%} POSS-grafted copolymers for Cp, Cy, and Cye POSS moieties.",
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AB - A series of hybrid organic/inorganic triblock copolymers of polystyrene-butadiene-polystyrene (SBS) grafted with polyhedral oligomeric silsesquioxane (POSS) molecules with different chemical constituents were synthesized by a hydrosilation method. Four POSS macromers, R′R 7Si 8O 12, were designed to contain a single silane functional group, R', which was used to graft onto the dangling 1,2-butadienes in the polybutadiene soft block and seven identical organic groups, R. Small-angle X-ray scattering and Theological techniques were used to study the effect of sterically similar, yet electronically different, organic R groups, cyclopentyl (Cp), cyclohexyl (Cy), cyclohexenyl (Cye), and phenyl (Ph), on the morphology of SBS triblock copolymer and the order-disorder transition behavior. It was observed that POSS with phenyl moiety, when grafted to the polybutadiene (PB) phase, appears to show favorable interaction with the polystyrene (PS) phase; effectively, the Ph-POSS is plasticizing the SBS due to an effect whereby the Ph-POSS is at least partially solvated by the PS phase. This causes a significant decrease in the overall lamellae d spacing and the order-disorder transition temperature, T ODT, with increasing amounts of Ph-POSS attachment. As we change the POSS moiety to that of Cye, Cy, and Cp, the interaction between POSS-PS weakens, and the d spacing and T ODT become less dependent on the amounts of POSS attachment. At the highest POSS loadings investigated (20 wt %), there is a change to a perforated layer morphology, resulting in an increase of T ODT relative to the 10 wt % POSS-grafted copolymers for Cp, Cy, and Cye POSS moieties.

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