FIELD OF THE INVENTION The present invention is directed to novel polyethers, particularly for use in binder formulations for high-energy, nitrate ester plasticized propellants. More specifically, this invention relates to the synthesis and polymerization of 3-azidomethyl-3- nitratomethyloxetane (AMNO).

BACKGROUND OF THE INVENTION High-energy solid formulations, such as propellants, explosives, and gasifiers, generally consist of paniculate solids, such as fuel material, oxidizers, or both, held together by an elastomeric binder. These formulations may also include a liquid plasticizer, such as a nitrate ester, which contributes to the elastomeric characteristics of the binder and adds additional energy to the formulation.

While the elastomeric binder matrix is an important means of dispersing and immobilizing the fuel material and oxidizer, the materials used in the binder burn with substantially lower energy than does the fuel material. The binder thus imposes a limit on the energy content available from the fuel material. One way to minimize this limitation is to use an elastomeric binder which releases as much energy as possible when burning with the fuel material. It is desirable, therefore, that the elastomeric binder have pendant groups which themselves are relatively high in energy.

Plasticizers are used in solid propellants and explosives to facilitate processing and increase flexibility and toughness, in addition to providing other benefits which vary with the nature and use of the formulation. Energetic or high-energy plasticizers are those that provide energy in addition to flexibility and toughness, and their inclusion therefore does not lessen the performance of the formulation. Considerations involved in the selection and use of plasticizers include compatibility with the other components of the formulation, including the primary energetic compounds and any binders present, the oxygen balance of the plasticizer, energy content, safety {i.e. , stability with regard to detonation) and melting point. Plasticizers with melting points in a range which causes them to crystallize readily, for example, are of limited utility, since crystallization is detrimental to the plasticizer function and can adversely affect the

mechanical properties of the propellant or explosive.

If a nitrate ester plasticizer is included in the formulation, it is desirable that the elastomeric binder be compatible with the nitrate ester plasticizer, i.e. , nitroester- miscibility is required. If the binder system is insufficiently miscible with the nitrate ester plasticizer, the plasticizer will weep or flow and settle out from the binder. Certain polymers which have sufficiently high energies and would otherwise be useful elastomers for binders cannot be used in certain binder systems because they are incompatible or immiscible with the nitrate ester plasticizer. Polyethers prepared from tetrahydrofuran (THF) are examples of such polymers. These polyethers have sufficiently high energies, high load-bearing capabilities, and low glass transition temperatures (T _g 's), but because they are immiscible with nitrate esters, they cannot be used in binder systems which utilize nitrate ester plasticizers. In addition to being high in energy, therefore, the polyethers and the elastomers formed therefrom should contain pendant groups which impart miscibility of the elastomers with nitrate ester plasticizers. Nitro, nitrato, nitroamino and cyano groups are examples of pendant groups which impart nitrate ester-miscibility to the polymer and have relatively high energies so as to contribute to the performance of the propellant.

In view of the foregoing, there exists a need for novel polyether polymers which, in addition to retaining the necessary characteristics of a binder, such as good elastomeric and strength characteristics, are sufficiently high in energy and sufficiently miscible with nitrate ester plasticizers.

SUMMARY OF THE INVENTION It has been discovered that when an oxetane ring is asymmetrically substituted at the 3-position with an azidomethyl (-CH ₂ N ₃ ) substituent and a nitratomethyl (-CH ₂ ONO ₂ ) substituent, a highly energetic oxetane compound is produced. In particular, this oxetane compound is useful as a monomer in the preparation of polyethers which may be subsequently cured to form energetic binder materials useful in energetic formulations.

It has also been discovered that, unlike the homopolymerization of many oxetane monomers which give crystalline compounds, the homopolymerization of 3- azidomethyl-3-nitratomethyloxetane gives an amorphous oil which has a unique combination of thermal stability, chemical functionality and physical properties. These qualities make the AMNO homopolymer highly useful as elastomeric binders in high- energy propellant formulations.

It has further been discovered that 3-azidomethyl-3-nitratomethyloxetane can be copolymerized with other known energetic oxetane monomers to produce amorphous materials. The presence of 3-azidomethyl-3-nitratomethyl, even in small amounts, prevents crystallinity and provides copolymers which are amorphous in character.

The novel homopolymers and copolymers of the present invention, in

addition to retaining the necessary characteristics of a binder, such as good elastomeric and mechanical strength properties, are sufficiently high in energy and sufficiently miscible with nitrate ester plasticizers to be useful as elastomeric binders in propellant formulations or the like.

Other advantages, objects, features and embodiments of the present invention will become apparent from the detailed description which follows.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS The oxetane of the present invention has the formula:

The oxetane of Formula I, 3-azidomethyl-3-nitratomethyloxetane (ANMO), is synthesized using 3-bromomethyl-3-hydroxymethyl oxetane (BMHMO) as the starting material. Reaction of 3-bromomethyl-3-hydroxymethyloxetane with sodium azide (NaN ₃ ) in acetone or dimethylformamide (DMF) gives the conesponding 3-azidomethyl-3-hydroxy- methyloxetane in essentially quantitative yield. Subsequent reaction of 3-azidomethyl-3- hydroxymethyloxetane with acetyl nitrate gives the oxetane AMNO.

The oxetane AMNO is particularly useful for polymerizing to form polyethers which may be subsequently cured to form energetic binder materials useful in energetic formulations. This oxetane monomer can be used to form either homopolymers or copolymers. When homopolymerized, the resulting polyethers have the formula:

In the above formula, x is an integer having a value selected so that the homopolymer has a molecular weight ranging from about 1,000 to about 100,000. Homopolymers of 3-

azidomethyl-3-nitratomethyloxetane having molecular weights ranging from about 4,000 to about 25,000 are preferred.

Certain copolymers in accordance with the present invention are those having the general formula:

In the above formula, R ¹ and R ² are independently selected and may be functional groups including, but not limited to, H, lower alkyl, NF ₂ , ONO ₂ , NO ₂ , N ₃ , and N(R ³ )NO ₂ , where R ³ is H or a lower alkyl. The term "independently selected" is used herein to indicate that the two R groups, R ¹ and R ² , may be identical or different. The term "alkyl" is used herein to refer to substituents that are monovalent aliphatic hydrocarbon radicals. The alkyl groups may be straight-chain or branched-chain, limited only by steric hinderance. Additionally, since alkyl groups do not add to the energetic character of the molecule, shorter alkyl groups (i.e. , 1-4 carbons) and saturated alkyl groups are prefened. The index, x, in Formula III is an integer having a value selected so that the copolymer has a molecular weight ranging from about 1,000 to about 100,000.

Within the scope of Formula III, certain copolymers are preferred, namely those in which R ¹ and R ² are independently either ONO ₂ or N ₃ ; and x is an integer having a value such that the copolymer has a molecular weight ranging from 2,000 to 50,000. Further preferred are copolymers in which R ¹ and R ² are both ONO ₂ ; and x is an integer having been selected so that the copolymer has a molecular weight ranging from about 4,000 to about 25,000. Also prefened are copolymers in which R ¹ and R ² are both N ₃ ; and x is an integer having been selected so that the copolymer has a molecular weight ranging from about 4,000 to about 25,000.

Further copolymers, in accordance with the present invention, are those formed from AMNO and at least one other oxetane monomer unit(s), in any proportion, order or arrangement. The oxetane monomer unit(s), other than AMNO, in unpolymerized form has the general formula:

In above formula, R ¹ and R ² are members independently selected from the group consisting of H, lower alkyl, NO ₂ , ONO ₂ , N ₃ , and N(R ³ )NO ₂ , where R ³ is H or a lower alkyl. Examples of oxetanes used to form copolymers with AMNO in accordance with the invention include, but are not limited to, the following:

BEMO 3 , 3-bis-(ethoxymethyl)oxetane,

BCMO 3,3-bis-(chloromethyl)oxetane,

BMMO 3,3-bis-(methoxymethyl)oxetane,

BFMO 3,3-bis-(fluoromethyl)oxetane, HMMO 3-hydroxymethyl-3-methyloxetane,

BAOMO 3 , 3-bis-(acetoxymethyl)oxetane,

BHMO 3 ,3-bis-(hydroxymethyl)oxetane,

OMMO 3-octoxymethyl-3-methyloxetane,

CMMO 3-chloromethyl-3-methyloxetane, AMMO 3-azidomethyl-3-methyloxetane,

BIMO 3,3-bis-(iodomethyl)oxetane,

IMMO 3-iodomethyl-3-methyloxetane,

PMMO 3-propynomethyl-3-methyl oxetane,

NMMO 3-nitratomethyl-3-methyloxetane, DMMO 3-difluoroaminomethyl-3-methyloxetane,

BDMO 3 ,3-bis-(difluoroaminomethyl)oxetane,

BMNAMO 3 , 3-bis-(methylnitratomethyl)oxetane,

MNAMMO 3-methylnitratomethyl-3-methyloxetane, and

BAMO 3,3-bis-(azidomethyl)oxetane. Within the scope of Formula IV, certain oxetane monomer units are preferred, namely those in which R ¹ and R ² are both ONO ₂ , i.e. , the oxetane monomer unit is 3,3-bis- (nitratomethyl)oxetane (BNMO), or those in which R ¹ and R ² are both N ₃ , i.e. , the oxetane monomer unit is 3,3-bis-(azidomethyl)oxetane (BAMO).

Certain of these copolymers are prefened, namely those copolymers comprising between about 5 to about 95 molar percent of AMNO and about 5 to about 95 molar percent of at least one other oxetane monomer unit(s). Also preferred are copolymers comprising between about 30 to about 65 molar percent of AMNO and about 35 to about 70 molar percent of at least one other oxetane monomer unit(s). Further preferred are copolymers comprising between about 10 to about 20 molar percent of AMNO and between about 80 to about 90 molar percent of at least one other oxetane

monomer unit(s). Even furthered preferred are copolymers comprising between about 10 to about 20 molar percent of AMNO and between about 80 to about 90 molar percent of either BAMO or BNMO.

Additionally, copolymers, made up of AMNO and at least one other oxetane monomer unit(s), having molecular weights ranging from about 2,000 to about 25,000 are preferred. Further preferred are copolymers, made up of AMNO and at least one other oxetane monomer unit(s), having molecular weights ranging from about 4,000 to about 12,000.

Since propellants and explosives are preferably elastomeric in character, structures, both polymeric and non-polymeric, which are amorphous in character are preferred over those that are crystalline. In the present invention, this is achieved by asymmetrically substituting the oxetane ring at the 3-position with an azidomethyl substituent and a nitratomethyl substituent. One of the primary advantages of 3- azidomethyl-3-nitratomethyloxetane is that it is an amorphous oil that has very useful thermal stability, chemical functionality and physical properties.

Copolymers are generally advantageous relative to homopolymers because the presence of an additional oxetane monomer unit(s), even in small amounts, substantially reduces stereoregularity. Homopolymers having a high degree of stereoregularity exhibit substantial chain folding, resulting in a compact structure which tends to be crystalline or highly viscous. However, unlike the homopolymerization of many oxetane monomers, the homopolymerization of 3-azidomethyl-3-nitratomethyloxetane gives a polymer which is amorphous in character and which exhibits a unique combination of thermal stability, chemical functionality and physical properties. Due to the asymmetrical substitution of this monomer, the polymer backbone contains random asymmetry which prevents crystallinity. These AMNO homopolymers are very useful in forming energetic binders for propellant formulations or the like.

Furthermore, 3-azidomethyl-3-nitratomethyloxetane can be copolymerized with other known energetic oxetane monomers. Frequently, existing high-energy oxetane monomers which have identical groups on the 3-position, such as 3,3-bis- (azidomethyl)oxetane (BAMO) or 3,3-bis-(nitratomethyl)oxetane (BNMO), give crystalline polymers which are not useful in binder applications. In order to obtain amorphous materials suitable for use as elastomeric binders, mono-energetically substituted monomers, such as 3-azidomethyl-3-methyloxetane or 3-nitratomethyl-3-methyloxetane, have been added to give copolymers which are amorphous in character, but which have diminished energy content. 3-Azidomethyl-3-nitratomethyl oxetane, however, can be used to form amorphous copolymers with monomers such as BAMO and BNMO without compromising the energy content. The presence of even small amounts (10 to 20%) of the asymmetrically substituted 3-azidomethyl-3-nitratomethyloxetane monomer will be

sufficient to produce amorphous polymers with monomers that usually give crystalline homopolymers, such as BAMO and BNMO.

Oxetane compounds can be synthesized using a variety of different methods. The methods used vary depending upon the oxetane compounds desired. 3-Bromomethyl- 3-hydroxymethyl oxetane (BMHMO), for example, is a convenient and inexpensive route for the preparation of 3,3-asymmetrically di-substituted oxetane compounds. Reaction of 2,2-bis-(bromomethyl)propane-l,3-diol (i.e. , neopentyl glycol dibromide) with base co- reactants, such as sodium ethoxide in ethanol, gives BMHMO. Additionally, BMHMO can be obtained from the reaction of neopentyl glycol dibromide with sodium hydroxide in dimethylformamide (DMF), sodium hydroxide in dimethylsulfoxide, sodium or potassium hydroxide in ethanol, and by neat reaction with fused potassium hydroxide. Once formed, BMHMO can be used as the starting point for a large number of energetic, asymmetrically di-substituted oxetanes. Oxetanes containing energetic pendant groups such as azido, nitrato, nitro, difluoroamino, nitroamino, dinitramino, cubyl and carboranyl can be synthesized using BMHMO as starting material. Table I lists examples of structures that can be synthesized using BMHMO as starting material.

Table I. Asymmetrically Di-substituted Oxetanes

The polymers of the present invention may be prepared in accordance with conventional procedures. Polyethers are formed from the oxetane monomers by cationic polymerization. This technique employs an initiator formed from an adduct of a substance such as a diol (e.g., 1,4-butanediol) and a catalyst for cationic polymerization. Such catalysts include, but are not limited to, boron trifluoride etherate, boron trifluoride, fluoroboric acid, or aluminum, phosphorous and antimony halides. The initiator reacts with one of the available oxetane monomers to form an initiating species, and polymerization proceeds by chain elongation until substantial, e.g., greater than about 95%, exhaustion of the monomers. The length of the chains is largely dependent upon the molar equivalents of monomers (m) and the initiators (n), the average chain length being approximately m/n mer units long. Generally, for use in propellant binders, polyether chains are prepared having molecular weights (weight average) of between about 2,000 and about 25,000. Distribution of mer units throughout the polymer chains and polydispersity of the chains depends on specific polymerization conditions. Polyethers in accordance with the present invention generally have polydispersities between about 1.5 and about 2.5. The molar ratio of mer units in the formed polyether generally reflects the molar ratios of the available monomers, but may also depend upon the relative reactivities of the monomers in the polymerization reaction. The polymers of the present invention are hydroxy-terminated, and thus they are curable with isocyanates through chain extension and cross-linkable to form elastomers. Polymeric chains which terminate at both ends with primary alcohol groups have a particular advantage since such groups are more reactive toward isocyanate groups during curing than the corresponding secondary and tertiary hydroxyl end groups. Elastomers are formed from the polyethers of the present invention by curing with isocyanates having a functionality of at least two, e.g., toluene diisocyanate. To promote chain elongation, at least one equivalent of an isocyanate is required. Preferably, cross-linking is also promoted by using an isocyanate of higher functionality or by adding a separate cross- linking agent, such as trimethylolethane or trimethylolpropane. The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes, and are intended neither to limit or define the invention in any manner.

EXAMPLE I This example illustrates the preparation and properties of 3-azidomethyl-3- nitratomethyloxetane.

A. Preparation of 3-Bromomethyl-3-hydroxymethyloxetane Sodium ethoxide in ethanol (21 %, 185.74 g, 0.573 mol) was added over a period of 10 min to a solution of 2,2-bis-(bromomethyl)propane-l,3-diol (150 g, 0.573 mol) in 650 mL of ethanol. This solution was refluxed for 2 h, stirred at ambient temperature for 16 h, filtered and then evaporated to give an oil containing solids. The resulting residue was dissolved in 200 mL of methylene chloride, filtered and evaporated to give 98 g of crude oxetane. An analytical sample was purified by distillation at 113°C and 3-mm pressure. 52.95 g, representing a 52% yield, of 3-bromomethyl-3- hydroxymethyl oxetane were obtained. NMR: *H NMR 3.75 (s, 2 H), 3.88 (d, J = 4.9 Hz, 2 H), 4.45 (s, 4 H); ¹³ C NMR 36.336 (t, J = 152.78 Hz), 45.0935 (s), 63.995 (t, J = 143.3 Hz), 77.216 (t, J = 152.78 Hz).

B. Preparation of 3-Azidomethyl-3-hydroxymethyloxetane

A mixture of sodium azide (9.5 g, 0.14 mol), 3-bromomethyl-3- hydroxymethyloxetane (24.0 g, 0.14 mol), 20 mL of acetone and 20 mL of water was refluxed for 12 h. The acetone was evaporated and the resulting residue was extracted with two portion of 40 mL of ethyl acetate. The combined organic extracts were dried over magnesium sulfate (MgSO ₄ ). The solvent was removed by evaporation. 18.0 g, representing a 94% yield, of 3-azidomethyl-3-hydroxymethyloxetane were obtained as an oil. This oil was found to be essentially pure by gas-liquid chromatography (GLC) analysis. NMR: 'H NMR 3.70 (s, 2 H), 3.84 (d, J = 4.9 Hz, 2 H), 4.44 (s, 4 H); ¹³ C NMR 44.283, 53,852, 64,073, 76.227.

C. Preparation of 3-Azidomethyl-3-nitratomethyloxetane

Nitric acid (100%, 2.65 g, 42 mmol) was added dropwise to acetic anhydride (4.73 g, 45 mmol), and the solution was stirred for 10 min and cooled to 0°C. A solution of 3-azidomethyl-3-hydroxymethyloxetane (5.0 g, 35 mmol) in 13 mL of methylene chloride was added over a period of 10 min, and then the solution was stirred for 30 min. The reaction mixture was washed with 10% aqueous sodium hydroxide, filtered and evaporated to 4.5 g, representing a 68% yield, of 3-azidomethyl-3- nitratomethyloxetane as a slightly yellow oil. Differential scanning calorimetry (DSC) showed an onset of decomposition at 206.4°C, and a maximum at 221.4°C; Heat Flow: 279 Joules/g; NMR: Η NMR 3.75 (s, 2 H), 4.43 (d, J = 6.9 Hz, 2 H), 4.46 (d, J = 6.9 Hz, 2 H), 4.69 (s, 2 H); ¹³ C NMR 41.875, 53.947, 72.864, 75.583.

EXAMPLE II This example illustrates the preparation and properties of the homopolymer poly(3-azidomethyl-3-nitratomethyloxetane).

A. Preparation of Poly( ^" 3-azidomethyl-3-nitratomethyloxetane) A solution of butane- 1,4-diol (24 mg, 0.266 mmol) and boron trifluoride etherate (77.9 mg, 0.548 mmol) in methylene chloride (1.26 g) was stirred at ambient temperature for 15 min under nitrogen in a dry polymerization flask. The solution was cooled to 8°C and then a solution of 3-azidomethyl-3-nitratomethyloxetane (1.00 g, 5.32 mmol) in methylene chloride (1.32 g) was added over a period of 10 min. The resulting solution was stirred for 1 h at 10°C at which time Η NMR analysis of an aliquot indicated that the reaction was 53% complete. The solution was warmed to ambient temperature, stirred 16 h, and quenched with O.l mL of water. 20 mL of methanol were added and the organic layer was decanted from the polymer that had precipitated as an oil. The oil was washed with methanol and dried for 24 h in vacuo (2 mm) to give 0.75 g, representing a 75% yield, of poly(3-azidomethyl-3-nitratomethyloxetane), as an amorphous oil.

Differential scanning calorimetry showed an onset of decomposition at 175 °C, and a maximum at 215 °C; Heat Flow: 440 Joules/g; Gel Permeation Chromatography (GPC): Number Average Molecular Weight (Mn) 4,368, and Weight Average Molecular Weight (Mw) 6,320; Polydispersity (Disp.): 1.47; NMR: 'H NMR 3.39-3.45 (m, 6 Hz), 4.45 (s, 2 Hz).

The foregoing is offered primarily for purposes of illustration. It will be readily apparent to those skilled in the art that the operating conditions, materials, procedural steps and other parameters of the systems described herein may be furthered modified or substituted in various ways without departing from the spirit and scope of the invention.