2,698,228 United States Patent Office Patented Dec. 28, 1954 1. 2 (a) Nitroxyalkyl nitramines having the general struc 2,698,228 tural formula: FLASHLESS PROPELLANT R2 John F. Kincaid, Jefferson Township, Alegheny County, 5 NOO-R-N-NO2 where R1 is an alkylene group and R2 is a nitroxyalkyl and Russell C. McGill, Baldwin Township, Aliegheny group or an alkyl group; asCounty, represented Pa., assignors by the Secretary to the United of the States Navy of America (b) Polynitrate esters of polymethylolicycloalkanones of the general formula: No Drawing. Application December 30, 1944, 0 Seria No. 570,808 C(CH2ONO2) 5 Claims. (CE. 52-13) C(CH2ONO2); The present invention relates to propellants and more 5 where n is a small whole number; and particularly to new and improved essentially flashless (c) Polynitrate esters of polymethylolicycloalkanols of propellants suitable for large caliber guns and cannon. the general formula: It has long been recognized that during military and naval operations carried out at night, an essentially flash C (CHONO) less propellant should be used in order to obviate brilliant 20 (CEI), CHONO2 muzzle flash that might reveal the friendly gun position or momentarily blind command and fire control personnel b(CHONo. in the vicinity of the weapon. Within recent years, British where n is a small whole number. experimenters have made great strides in solving this As illustrative examples of the foregoing types of non problem by incorporating a substantial proportion (about 25 volatile explosive nitric esters, the following specific com 55%) of nitroguanidine in a double base or “Cordite” pounds may be mentioned purely by way of illustra type of powder. The resulting composition (referred to tion; bis(2-nitroxyethyl) nitramine (hereinafter called generally as "Cordite-N') is essentially flashless when "DNA”), tetramethylolicyclopentanone tetranitrate fired in large caliber cannon and has a force approxi (hereinafter called "Fivonite”), tetramethylolicyclopen mately equivalent to that of Pyro powder. 30 tanol pentanitrate (hereinafter called "Fivolite"), tetra Nevertheless, like other double base powders of the methylolicyclohexanone tetranitrate (hereinafter called prior art, Cordite-N, while far superior from the view "Sixonite'), and tetramethylolicyclohexanol pentanitrate point of flash, suffers from the disadvantage that it con (hereinafter called "Sixolite"). tains a volatile high potential plasticizer, namely nitro glycerine. Under conditions of high temperature storage, I. PREPARATION OF THE NON-VOLATILE this volatile component tends to vaporize with the result PLASTCZERS that the ballistic properties of the powder may undergo The preparation of DINA, as described and claimed in a significant change during storage. In addition, under the copending applications of Wright and Chute, Serial the conditions prevailing in air conditioned and ventilated Nos. 570,813, now Patent No. 2,461,582 and 570,814, powder magazines on modern naval vessels, the nitro 40 now Patent No. 2,462,052, and Blomquist and Fiedorek, glycerine in double base powders exhibits a demonstrable Serial No. 570,804, now Patent No. 2,678,946, all filed of tendency to distill, thereby creating a potential hazard even date herewith, may be accomplished by the dehy due to the possible condensation of a highly sensitive ex dration of the bis(nitroxyalkyl)amine nitrate obtained by plosive at various points in the magazine and ventilating nitrolysis of the appropriate dialkanolamine; for example: system. For these reasons, Cordite-N, while far superior HNO3 to Pyro in respect to flash, does not represent the ideal (a) (HOCH2CH2)2NH -) solution to the flash problem. (b) The principal object of the present invention is to pro (NOOCH2CH2)2NEI.HNO3 mulu-3 vide a new and improved essentially flashless gun powder. (chloride Another object is the provision of a gun or cannon catalyst) powder having the desirable flashless characteristics of 50 Cordite-N without the disadvantages associated with a (NOOCH2CH2)2N-NO -- EO double base powder that contains a volatile high explosive Certain homologues of DINA of the type: pier for the nitrocellulose component of the pro pellant. (Noort–H)n-No. A further object is to provide a commercially feasible 55 R. R. method of preparing an essentially flashless non-hygro scopic propellant that does not materially alter in ballistic where one R is an alkyl group and the other hydrogen properties when stored at high temperatures. may be prepared in a similar manner from higher homo Other objects and advantages will be apparent as the logues of diethanolamine, as described and claimed in invention is hereinafter more particularly described. 60 Blomquist and Fiedorek application, Ser. No. 570,805, In accordance with the present invention, it has been now Patent No. 2,481,283, also filed of even date here found that the foregoing objects may be accomplished by with. Certain analogues of DINA of the type: substituting certain relatively non-volatile explosive nitric esters for the nitroglycerine heretofore employed as a where R is an alkyl group, obtained in a similar manner nitrocellulose plasticizer in a Cordite-N type of cannon from the appropriate secondary alkanolalkylamine, are powder. More particularly, the improved propellant of described and claimed in another copending application of the present invention consists of a modified double base Blomquist and Fiedorek, Ser. No. 570,804, also filed of type of powder comprising: even date herewith. (1) Nitrocellulose, 70 The plasticizers of the class represented by Fivonite, (2). An essentially non-volatile thermally stable explo Fivolite, Sixonite and Sixclite are prepared as described in E. nitric ester capable of plasticizing the nitrocellulose, the literature (Ger. Pat. 509,118; Br. Pat. 345,859; U. S. a . 1962,065; compare Davis, The Chemistry of Powder and (3) A sufficient proportion of nitroguanidine to render Explosives, John Wiley and Sons, 1943, vol. II, page 285). the finished propellant essentially flashless when fired in a large caliber gun or cannon. 75 II. PREPARATION OF THE PROSPELLANT The nitrocellulose plasticizers employed in accordance In preparing the improved propellant of the present in with the present invention may for example consist of vention, any suitable procedure heretofore used for the the essentially non-volatile members of the following illus preparation of double base powders such as Cordite-N trative classes of compounds that are capable of plas may be used, with the exception that one or more of the ticizing nitrocellulose, namely: 80 above identified relatively non-volatile nitrocellulose plas 2,698,228 3 4 ticizers are substituted for the nitroglycerine employed in to the proper length, tied in bundles and dried in an elec the prior art propellants. Thus the powders of the present tric oven for one day at 30° C. and fourteen days at 45 C. invention may be made in conventional "solvent-extru Other experimental compositions have been prepared sion' equipment without material alteration of the proce successfully using pyrocotton and various mixtures of dural steps heretofore employed in the production of guncotton and pyrocotton. Different solvent proportions double base powders containing a substantial proportion (between 50%-50% and 80%-20% acetone-alcohol) of nitroguanidine. have also been found satisfactory. Experiments have The amount of non-volatile plasticizer required for the also been made with shorter mixing cycle and different present propellants will depend in part on the nature of water jacket temperatures. For most preparations a spa the particular plasticizer and other components selected O ghetti process has also been found advantageous to re and in part upon the characteristics desired in the finished move clumps of uncolloided nitrocellulose and poorly powder. In general, however, satisfactory powders may mixed material as well as contributing to the mechanical be made using approximately the following proportions work done on the colloid. of ingredients: Per cent 5 EXAMPLE II-PREPARATION OF PROPELLANT CONTAINING Nitrocellulose ---------------------------- 15 to 35 FIVONITE AS AN NG SUBSTITUTE Non-volatile explosive plasticizer------------ 15 to 35 The following description will serve as an example of Nitroguanidine --------------------------- 70 to 30 the use of Fivonite as a nitroglycerine substitute. The composition was chosen again so that the finished powder In order more clearly to disclose the nature of the pres 20 would have approximately the same thermochemistry and ent invention, several specific examples will be described flash properties as British Cordite-N. in detail below. It should be clearly understood, however, The composition of a typical propellant made with that the examples are purely illustrative of the fundamen Fivonite was as follows: tal principles involved and are in no sense intended either Per cent to delineate the breadth or scope of the invention or to 25 Nitrocellulose (13.4% N)--------------------- 23.0 limit or restrict the ambit of the appended claims. Nitroguanidine ------------------------------ 55.0 EXAMPLE. I.-PREPARATION OF A PROPELLANT CONTAINING Fivonite ----------------------------------- 19.0 DINA AS AN NG SUBSTITUTE Centralite #1-------------------------------- 3.0 As an example of the use of DINA as a nitroglycerine The Fivonite may be prepared in ordinary laboratory substitute in nitroguanidine propellants, there is described 30 equipment by the procedure described in