Abstract: This invention relates to novel neopentyl difluoroamino compounds which are useful as plasticizers and oxidizers in energetic formulations, such as propellants, explosives, and gasifiers. These neopentyl difluoroamino compounds can be prepared either: (1) by the direct fluorination of amine derivatives containing energetic pendant groups; or (2) by first preparing NF.sub.2 -derivatives and then substituting these derivatives with energetic pendant groups. In particular, mono- and bis-(difluoroaminomethyl) oxetanes are synthesized and further reacted to yield the corresponding dinitrate esters. It has been discovered that these NF.sub.2 -dinitrate esters are very useful as energetic plasticizers in high-energy formulations.

Abstract: This invention relates to novel multifunctional oxetanes, i.e., compounds having multiple oxetane groups, which are useful as initiators in the preparation of star polymers and polymer cascades containing energetic groups. In addition, this invention relates to a process for the preparation of star polymers and polymer cascades, whereby novel multifunctional oxetanes act as initiators in the formation of theses polymers. The reaction of these initiators with various propagating, high-energy oxetanes, such as 3,3-bis-(azidomethyl)oxetane (BAMO) and 3-nitratomethyl-3-methyloxetane (NMMO), gives star polymers with varying molecular weights and functionalities. The star polymers and polymer cascades of the present invention are useful as binders in high-energy formulations.

Abstract: This application is directed to novel fluorinated polymers and prepolymers derived from mono-substituted oxetane monomers having fluorinated alkoxymethylene side-chains and the method of making these compositions. The mono-substituted fluorinated oxetane monomers having fluorinated alkoxymethylene side-chains are prepared in high yield by the reaction of a fluorinated alkoxides with either 3-halomethyl-3-methyloxetane premonomers or aryl sulfonate derivative of 3-hydroxymethyl-3-methyloxetane premonomers. Preparation of a mono-substituted 3-bromomethyl-3 -methyloxetane premonomer via a simple, high yield process amenable to commercial scaleup is also disclosed. The fluorinated oxetane monomers of this invention can be readily homo/co-polymerized in the presence of a Lewis acid and polyhydroxy compounds to obtain hydroxy-terminated polyether prepolymers having fluorinated alkoxymethylene side chains.

Abstract: This invention relates to a process for the preparation of mono- and bis(azidomethyl)oxetanes. These compounds are prepared by combining a mono- or bis-X-oxetane (wherein X is, for example, a tosylate, mesylate, halogen, etc.) with an aqueous solution of a metallic azide and a phase transfer catalyst. Mono- and bis(azidomethyl)oxetanes can be polymerized to form homopolymers and copolymers with load bearing polyether backbones and highly energetic pendant groups. Such homopolymers and copolymers of the present invention are useful as energetic binders in high-energy formulations, such as propellants, explosives, and gasifiers.

Abstract: 3-Azidomethyl-3-nitratomethyloxetane, a novel oxetane compound, is used as a monomer for the formation of homopolymers and copolymers with other known energetic oxetane monomers. The polyethers of the present invention can be subsequently cured to form elastomers suitable for use as energetic binders in propellant formulations or the like.

Abstract: The present invention provides an improved method of carrying out cationic polymerization of cyclic ether monomers substituted with high-energy, electron-withdrawing pendant groups (e.g., BAMO and NMMO). Such cyclic ether monomers are polymerized with an initiator precursor (i.e., an alcohol) and boron trifluoride tetrahydrofuranate (BF.sub.3 .cndot.THF). It has been discovered that when boron trifluoride tetrahydrofuranate is used as a catalyst in the cationic polymerization of cyclic ether monomers substituted with high-energy, electron-withdrawing pendant groups (e.g., BAMO and NMMO), polymers are produced that have improved functionality and low poly-dispersity. The polymers formed using the method of the present invention are useful for forming cross-linked elastomers which, in turn, are useful for forming elastomeric binders for high-energy compositions, such as propellants, explosives, gasifiers or the like.

Abstract: 3-Azidomethyl-3-nitratomethyloxetane, a novel oxetane compound, is used as a monomer for the formation of homopolymers and copolymers with other known energetic oxetane monomers. The polyethers of the present invention can be subsequently cured to form elastomers suitable for use as energetic binders in propellant formulations or the like.

Abstract: This invention relates to novel oxetanes containing neopentyl difluoroamino groups. More specifically, mono- and bis-(difluoroaminomethyl)oxetanes are synthesized. These compounds are prepared by the direct fluorination of blocked neopentyl amines. These mono- and bis-(difluoroaminomethyl)oxetanes can be polymerized to form homopolymers and copolymers with load beating polyether backbones and highly energetic pendant groups. The homopolymers and copolymers of the present invention are useful as energetic binders in high-energy formulations, such as propellants, explosives, and gasifiers.

Abstract: This invention relates to novel multifunctional oxetanes, i.e., compounds having multiple oxetane groups, which are useful as initiators in the preparation of star polymers and polymer cascades containing energetic groups. In addition, this invention relates to a process for the preparation of star polymers and polymer cascades, whereby novel multifunctional oxetanes act as initiators in the formation of theses polymers. The reaction of these initiators with various propagating, high-energy oxetanes, such as 3,3-bis-(azidomethyl)oxetane (BAMO) and 3-nitratomethyl-3-methyloxetane (NMMO), gives star polymers with varying molecular weights and functionalities. The star polymers and polymer cascades of the present invention are useful as binders in high-energy formulations.

Abstract: This invention relates to novel oxetanes containing neopentyl difluoroamino groups. More specifically, mono- and bis-(difluoroaminomethyl)oxetanes are synthesized. These compounds are prepared by the direct fluorination of blocked neopentyl amines. These mono- and bis-(difluoroaminomethyl)oxetanes can be polymerized to form homopolymers and copolymers with load bearing polyether backbones and highly energetic pendant groups. The homopolymers and copolymers of the present invention are useful as energetic binders in high-energy formulations, such as propellants, explosives, and gasifiers.

Abstract: Nitrato alkyl oxetanes are synthesized directly from the corresponding hyxy alkyl oxetanes by nitrating the hydroxy alkyl oxetane under non-acidic anhydrous conditions. A hydroxy alkyl oxetane is reacted with an anhydrous nitrate ester of a carboxylic acid at temperatures below about 10.degree. C. The product of the method, nitrato alkyl oxetane, is produced in relatively high yield without opening of the oxetane ring.

Abstract: Novel block polymers which are thermoplastic elastomers which are thermoplastic elastomers are provided for use as binders in high-energy compositions such as propellants, explosives, gasifiers or the like. The block polymers have an ABA structure wherein the A blocks are crystalline at temperatures below 60.degree. C. and the B blocks are amorphous at temperatures above -20.degree. C. Both the A and B blocks are polyethers formed from monomers of oxetanes and/or tetrahydrofuran. The block polymers melt in the range of 60.degree. C. to 120.degree. C. and have low viscosities above their melting points due to mutual miscibility of the A and B blocks.

Abstract: Internally plasticized elastomeric binders for projectile propellants are cured polyethers containing THF, CYMMO plus BMEMO, BEEMO and/or OMMO mer units. The polyethers are fluid at room temperature and are miscible with nitrate ester plasticizers. Propellant binders prepared from these polyethers are curable, have low T.sub.g 's, good mechanical properties, and I.sub.sp 's comparable to PEG-based binders.

Abstract: Nitramine oxetanes, specifically 3-methyl nitraminomethyl-3-methyl oxetane and 3,3-Bis (methyl nitraminomethyl) oxetane are synthesized. Polyethers are formed incorporating the nitramine oxetanes, which polyethers are curable with isocyanates to form elastomers suitable for use as binders in propellants or the like.

Abstract: The present invention provides a method for synthesizing a novel oxether-1 monomer by a two step reaction scheme which involves effecting a reaction between 3-methyl-3-hydroxymethyl oxetane and 1,1,1-trinitroethane to form an intermediate reaction product which in turn is reacted with methyl iodide to produce the oxether-1 monomer. The monomer is easily polymerized using conventional polymerization techniques to produce a poly(oxether-1) polyol useful as a binder component in smokeless propellants and explosives.

Abstract: Energetic copolymers having repeating mer units derived from different monomers, one or both of which have pendant energetic groups such as azido, nitro or nitrato groups. Copolymers have improved formulating characteristics compared to homopolymers of the energetic monomers; e.g., they are less crystalline or less viscous. Preferably the monomers are cyclic oxides having three to six atoms in the ring. The energetic monomers are preferably azido, nitro or nitrato derivatives of oxetane or THF. Copolymerization is preferably carried out by cationic polymerization using an adduct of the preinitiator precursor (e.g., 1,4-butane diol) and a catalyst suitable for cationic polymerization (e.g., boron trifluoride etherate) which is employed in stoichiometric proportion to the monomers and a low molecular weight, low polydispersity copolymer results. Certain novel monomers also are provided.

Abstract: Method of carrying out cationic polymerization with molecular weight control in which a preinitiator precursor, e.g. a diol and a catalyst effective for cationic polymerization (or a preformed adduct of such precursor and catalyst) are mixed with a monomer (e.g. a cyclic ether) in proportions of one mol of precursor or adduct and n mols of monomer, where n is the relatively small number of mer units desired in the polymer, causing polymerization to proceed to completion, then treating the resulting living cationic polymer as desired, e.g. quenching with water to introduce a terminal hydroxyl group, adding another monomer to produce a block polymer, reacting with an anionic polymer, etc. Also polymers so formed. Such polymers have low polydispersity and conversion and yield of the desired polymer are high.