Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes

Douglas A Loy, Joseph P. Carpenter, Sharon A. Myers, Roger A. Assink, James H. Small, John Greaves, Kenneth J. Shea

Research output: Chapter in Book/Report/Conference proceedingConference contribution

5 Citations (Scopus)

Abstract

Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane 1 and 1,4-bis(triethoxysilyl)butane 2 were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed with the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to preserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.

Original languageEnglish (US)
Title of host publicationMaterials Research Society Symposium - Proceedings
PublisherMaterials Research Society
Pages33-41
Number of pages9
Volume435
StatePublished - 1996
Externally publishedYes
EventProceedings of the 1996 MRS Spring Symposium - San Francisco, CA, USA
Duration: Apr 8 1996Apr 12 1996

Other

OtherProceedings of the 1996 MRS Spring Symposium
CitySan Francisco, CA, USA
Period4/8/964/12/96

Fingerprint

Alkanes
Condensation reactions
Paraffins
Monomers
Polymerization
Dimers
Sol-gels
Gels
Siloxanes
Propane
Cyclization
Butane
Carbohydrates
Propylene
Condensation

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials

Cite this

Loy, D. A., Carpenter, J. P., Myers, S. A., Assink, R. A., Small, J. H., Greaves, J., & Shea, K. J. (1996). Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. In Materials Research Society Symposium - Proceedings (Vol. 435, pp. 33-41). Materials Research Society.

Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. / Loy, Douglas A; Carpenter, Joseph P.; Myers, Sharon A.; Assink, Roger A.; Small, James H.; Greaves, John; Shea, Kenneth J.

Materials Research Society Symposium - Proceedings. Vol. 435 Materials Research Society, 1996. p. 33-41.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Loy, DA, Carpenter, JP, Myers, SA, Assink, RA, Small, JH, Greaves, J & Shea, KJ 1996, Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. in Materials Research Society Symposium - Proceedings. vol. 435, Materials Research Society, pp. 33-41, Proceedings of the 1996 MRS Spring Symposium, San Francisco, CA, USA, 4/8/96.
Loy DA, Carpenter JP, Myers SA, Assink RA, Small JH, Greaves J et al. Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. In Materials Research Society Symposium - Proceedings. Vol. 435. Materials Research Society. 1996. p. 33-41
Loy, Douglas A ; Carpenter, Joseph P. ; Myers, Sharon A. ; Assink, Roger A. ; Small, James H. ; Greaves, John ; Shea, Kenneth J. / Intramolecular condensation reactions of α,ω-bis(triethoxysilyl)alkanes. Formation of cyclic disilsesquioxanes. Materials Research Society Symposium - Proceedings. Vol. 435 Materials Research Society, 1996. pp. 33-41
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abstract = "Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane 1 and 1,4-bis(triethoxysilyl)butane 2 were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed with the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to preserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.",
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AU - Greaves, John

AU - Shea, Kenneth J.

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AB - Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane 1 and 1,4-bis(triethoxysilyl)butane 2 were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed with the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to preserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.

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