Research in Energetic Compounds.
Abstract
Studies of the synthesis and polymerization of energetic oxetanes were continued. The polymerization of 3-azidooxetane, catalyzed by boron trifluoride etherate gave diols with molecular weights of 3,000 to 3,600. A gumstock was prepared with TDI. An efficient reagent for reducing 3-azidooxetane was found to be triphenylphosphine, providing a high yield of 3-aminooxetane. The reaction of 3-nitrooxetane with tetranitromethane provided an improved yield of 3,3-dinitrooxetane. The polymerization of 3,3-dinitrooxetane with phosphorus pentafluoride gave a polymer with a melting point of 200 deg C. Copolymers of 3,3-dinitrooxetane with 3-fluoro-3-nitrooxetane were obtained with melting points as low as 137 deg C. Process development studies of 30-azidooxetane were carried out. The addition of acetic acid to epichlorohydrin was simplified by minimizing the amounts of acetic acid and ferric chloride catalyst and eliminating the use of solvent. The adduct, without work-up was treated with ethyl vinyl ether. Treatment of the product with aqueous base, followed by removal of the acetal protecting group with methanol gave 3-hydroxyoxetane. P-Toluenesulfonyl chloride and aqueous base gave oxetyl tosylate in 23% overall yield from epichlorohydrin. A safe procedure for reacting the tosylate with sodium azide was developed using polyethylene glycol as the reaction solvent and methylene chloride as the trapping solvent.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1980
- Accession Number
- ADA111502
Entities
People
- Kurt Baum
- Phillip T. Berkowitz
- Thomas G. Archibald
- Vytantas Grakauskas