US3104262A - Alkyl ether of linear methylene nitramines - Google Patents

Description

United States Patent 3,104,262 ALKYL ETHER 0F LINEAR METHYLENE NITRAMINES William A. Gey and Robert W. Van Dolah, China Lake, Califl, assignors to the United States of America as represented by the Secretary of the Navy No Drawing. Filed Jan. 27, 1953, Ser. No. 333,623

1 Claim. (Cl. 260-584) (Granted under Title 35, US. Code (1952), sec. 266) The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

The invention relates to new chemical compounds, more particularly, it relates to ethers of linear methylene nitramines of the structure wherein R is selected from the group consisting of hydrogen, alkyl or alkoxy, R is alkoxy and x is an integer.

An objective in the production of high explosives is an explosive which is relatively insensitive to detonation by mechanical shock and highly sensitive to detonation by explosive shock. A number of explosives which have high explosive efiiciency are unsuitable for military or commercial use because their sensitivity to mechanical shock makes handling of them extremely hazardous. iAn expedient which has been used .to overcome this difiiculty in a number of explosive compositions is the incorporation therein of an additive which reduces the sensitivity of the explosive to mechanical shock. For example, parafiin hydrocarbons have been added to such explosives as tetranitromethane; nitro aromatic hydrocarbons have been added to blasting gelatine; and celulose acetate has been added to nitroglycerin for the above purpose. A difliculty attendant to the incorporation of additives in explosive compositions is the fact that ordinarily certain desirable qualities such as brisance, density and others are sacrificed. Accordingly, this procedure ordinarily results in a compromise between various properties of the explosive.

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The additives of this invention which meet the above objects comprise alkyl ethers prepared from NSX(1- nitroxy 2,4,6-trinitro 2,4,6 triazaheptane), ATX(1,7- di nitroxy 2,4,6 trinitro 2,4,6 triazaheptane), lnitroxy 2,4,6 trinitro 2,4,6 triazadecane and 1,9 dinitroxy 2,4,6,8 tetranitro 2,4,6,8 tetrazanonane. The ethers found most suitable are those having from four to eight atoms in the alkyl chain. The compounds are prepared by heating an excess of the appropriate alcohol with NSX, ATX, 1-nitroxy-2,4,6-trinitro-2,4,6-triazadecane, l,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-terazanoname, or other appropriate linear methylene nitramine.

The following specific examples will serve to illustrate the preparation of the compounds of the invention:

Example 1 The butyl ether from NSX was prepared by adding 5 grams of NSX to 20 cc. of n-butyl alcohol and stirring the mixture at 95 C. until solution was effected. The solution was poured into an equal volume of benzene, cooled at 0 C. for 48 hours and filtered. The product was recrystallized from methanol.

The compound has the following structural formula:

The above procedure was repeated to produce the amyl, hexyl and heptyl ethers from NSX by reacting the appropriate alcohol with NSX with the exception that the mixtures producing these three ethers were heated one hour, one and three-fourths hours and three hours respectively. The yields of butyl, amyl and heptyl ethers were 5 grams (97%), 4.4 grams (82%), 5.5 grams (97%) and 5.5 grams (94%), respectively.

Example 2 The di-n-octyl ether from ATX was prepared by heating 25 grams of n-octyl alcohol at 85 C. for 2 hours with 5 grams of ATX to give complete solution. The solution was filtered while hot, cooled, refiltered at room temperature and further purified. The compound formed has the following formula:

Petroleum Waxes have been used in the past as additives to such high explosives as RDXJ Although these additives reduce the sensitivity of the explosive to mechanical shock, they also produce a final composition which is excessively sticky. This latter characteristic makes processing difficult. In addition, their incorporation in the explosive results in a lowering of its overall density, thus resulting in a less compact explosive with resultant loss of explosive power.

It is, therefore, an object of this invention to provide additives for explosives which reduce the sensitivity of the explosive to mechanical shock without adversely affecting other desirable explosive properties.

It is another object of this invention to provide additives for explosives which produce a product which is not tacky or sticky.

It is still another object of this invention to provide additives for explosives which produce a product of increased density.

It is a further object of this invention to provide additives for explosives which produce a final product having good storage stability.

The above procedure was repeated to produce di-nbutyl, di-n-amyl, di-iso-amyl, di-n-hexyl and di-n-hepty1 ethers from ATX by reacting the appropriate alcohol with ATX.

Example 3 Example 4 The di-n-hexyl ether from 1,9-dinitroxy-2,4,6,8-tetra nitro-2,4,6,S-tetrazanonane was prepared as follows:

15 cc. of 1,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-tetrazanonane were mixed with 4 grams of n-hexyl alcohol and the mixture stirred at 120 C. until complete solution and for 20 minutes thereafter. The mixture was cooled at 0 C. for one hour, filtered and the ether recovered by recrystallization for methanol. 3.9 grams of the ether were obtained, amounting to an 89% yield.

The compound has the following structural formula:

ETHERS FROM 1-NITROXY-2,4,6-TRINITRO-2,4,6-TRIAZA- DECANE methyl. 92-93 ETHERS FROM 1,9-DINI'IROXY-2,4,6,8-TEIRANITRO-2,4,6,8- TETRAZANONANE As disclosed in the co-pending application of William A. Gey, entitled Explosive Compositions, Serial IIlI IHI'II II-II 1EIIITOQIII1TOZIIINHZIIINOQIII HHHHHH H-(IJ-CI(IJCCIJCIIOCNfi3-N(f-N? -0-( J- ('J-( :c l- 1-H H H H H H H H H H H H 1'1 1'1 1'1 III H I! Example 5 No. 333,622, filed in the US. Patent Ofiice January 27, 1953, which has matured into Patent No. 2,982,639, Examples 1 t0 4 Show h genfil'al methods of P P issued May 2, 1961, the addition of the above ethers to a the compounds o the invention, the speclfic p p such high explosives as RDX results in an explosive of i165 0f thfisfi belng glvel'l as follows! improved density and therefore higher explosive power.

In addition, the presence of these ethers renders the ex- ETHERS FROM NSX plosive less sensitive to mechanical shock. For example, Percent Percent M If such a composition is disclosed in the above application nitrogen nmogen it having a ballistic mortar value 138.1% that of TNT, a 3 5 3- (d gg s density of 1.661 grams per cc., a heat of explosion of 1230 calories per gram and an impact sensitivity close bum 2709 27.77 101402 to that of composition A. Further, the addition of the amyll l g g present compounds to explosives does not render them 1'1 hgpijyl 23.86 23.96 88.5-89 0 g igz z g ig gg they can be readlly processed The ether of the formula ETHERS FROM A'IX N02 H N02 H NO, H

I l l di-n-butyL .3 HCH2NC--NCNC-O C4118 (li-n-amyl 20 .50 22 .25 82-83 l (li-iso-amyl 83.5-85 H H H gfgfigifg' gig; References Cited in the file of this patent di-n-0ctyl 16- 17-50 80-82 2,381,408 Senkies Aug. 7, 1945 2,678,927 Wright et a1. May 18, 1954 45 OTHER REFERENCES Chute et a1.: Canadian Journal of Research, Vol. 27B, pages 503-19 (1949).