FR2706890A1 - 1,3-Diisocyanato-2,2-bis(azidomethyl)propane and its intermediates and application to the vulcanisation of a system containing energising (energy-providing) urethanes - Google Patents

Abstract

1,3-Diisocyanato-2,2-bis(azidomethyl)propane and its intermediates and application to the vulcanisation of a system containing energising urethanes. To produce a vulcanised propellant, a binder, a urethane plasticiser, an oxidant and a fuel are mixed with 1,3-diisocyanato-2,2-bis(azidomethyl)propane and vulcanisation is carried out. The vulcanisation agent is obtained by a process containing six reaction stages. Application to the production of intermediates and of vulcanisation agents for solid propellants for rocket (engine)s and gas generators.

Description

The present invention relates generally to solid propellants and

  gas generators, as well as a method for causing hardening maturation, or vulcanization, of associated energy systems forming urethane or urethane type. The present invention also relates, more specifically, to an azide diisocyanate, a vulcanizing agent which can specifically

  apply to the vulcanization of such energy systems

  urethane trainers. The invention also relates to the intermediate compounds and to a process for the preparation of

  these intermediates and this vulcanizing agent.

  To make solid propellants, which

  takes propellants for (engines) rockets and for gener-

  gas, a poly-

  mother, such as glycidyl azide polymer (GAP) as a binder to hold the fuel together, the oxidant and other compounds making up the propellant or the gas generator. An energy binder of the GAP type is described in US Pat. No. 4,268,450 (Frankel et al.) Which can be

refer.

  Gas generators, such as propellants for hunting or war projectiles, can incorporate binders formed by nitrocellulose plasticized with GAP, as described in US Pat. No. 4,288,262 (Flanagan and

  al.), which may be referred to.

  Addition of vulcanizing or hardening agents

  Such prepolymer systems cause crosslinking between the functional groups of the prepolymer, such as GAP prepolymer primed with glycerol, which gives a polymer. The physical properties of the polymer vary depending on the degree of crosslinking. This degree can be varied by acting on the quantity and type of vulcanizing agent that is added. In general, we

  wishes to achieve -the hardening of vulcanization of the prepo-

  lymers to such an extent that the resulting polymer has

  the physical properties of an elastomer.

  Examples of agents known for curing or vulcanization maturation are represented by di-

  isophorone isocyanate, 3-nitra-za-pentane l-, 5-diisocyanate, and the trimer biuret of hexamethylene diisocyanate ("N-100"), which is a polyfunctional isocyanate produced at industrial scale by Mobay Chemical Company. It is usually desired to suspend other compounds in the composition of the polymeric binder. For example, a solid rocket or rocket propellant composition could include such a polymer into which a plasticizer, an oxidant and a fuel have been incorporated. Examples of suitable fuels could

  be represented by light metals and light metal hydrides. Examples of suitable oxidants for-

  could be represented by perchlorates and nitrates. To briefly summarize the invention, one could

  indicate that it proposes an agent to carry out the maturation-

  hardening or vulcanization of energy systems

  urethane-like products, a method for producing such a vulcanizing agent for energy systems, and a method for using said vulcanizing agent to effect the vulcanization hardening of systems

energetic urethanes.

  An object of the present invention therefore consists in

  provide a method for causing vulcan curing

  role of urethane polymer systems

energetic.

  Another object of the present invention consists in providing a new hardening vulcanizing agent, of the azide diisocyanate type, and a new process for its preparation. The invention also relates to intermediaries

for obtaining this agent.

  Other objects and corresponding advantages emerge

  will be evident from the following description of

  the invention. The aims of the present invention are achieved by carrying out the synthesis of a new vulcanizing energy agent, of the azide diisocyanate type, which is the

  2,2-bis 1,3-diisoeyanate (azidomethylY-propane (DIBAMP).

  The synthesis of the energetic azide diisocyanate, DIBAMP, is carried out according to the present invention in a

  sequence of reactions comprising six steps.

  The starting material is 3,3-bis (cyanomethyl) oxetane (1). Treatment of the starting material (1) with aqueous hydrobromic acid gives 3-bromo-2,2-bis (cyanomethyl) -l-propanol (2), which is then reacted

  with pyridine and with p-toluenesul chloride

  fonyl to transform it into 3-bromo-2,2-bis (cyanomethyl) l-propyl (3) tosylate. Then the reaction of tosylate

  (3) with sodium azide in the presence of dimethylsul-

  foxide produces 2,2-bis (azidomethyl) -1,3-dieyanopropane

  (4). This is followed by the hydrolysis of 1,3-

  dicyanopropane (4), by heating to reflux of a solution of dicyanopropane (4) and potassium hydroxide, which gives 3.3bis (azidomethyl) -glutaric acid (5) which is converted into reacting with zinc chloride and phosphorus pentachloride in the presence of benzene, to 3,3-bis (azidomethyl) glutaryl chloride (6). We

  obtains the new vulcanizing agent, diisocyanate-

  (1,3) of 2,2-bis (azidomethyl) -propane, by reacting glutaryl chloride with a mineral azide in the presence of ethylene dichloride to form a di (acylazide)

  intermediate, which we submit to decomposition and trans-

  position to obtain the desired disocyanate.

  The properties of DIBAMP are summarized in Table I below. TABLE I Name: 2,2-bis (azidomethyl) -propane 1,3-diisocyanate Structure: CH2N3

1

OCNCH2CCH2NCO

  CH2N3 Raw formula: C 7H8N802 Appearance: yellow mobile liquid Equivalent weight: 125 (theoretical value: 118) Purity: 94.4% Boiling point: 70 C under 0.01 mm Sensitivity to impact:> to 22, 6 Nm (more than 200 inch-pounds) Sensitivity to friction:> 3.53 J (> 36 kg / cm) AH: + 381 kJ / mole (+ 91 kCal / mole; estimated value) Elementary CHN analysis: Calculated 35.59 3.39 47.46 Found 35.06 3.37 46, 84 A more detailed explanation is given below.

the synthesis of DIBAMP.

  3-bromo-2,2-bis (cyanomethyl) -1-propanol - (2) In a suitable reactor, equipped with an agitator,

  9.6 g (0.07 mole) of 3.3-bis (cyanomethyl) were placed -

  oxetane and 50 ml of water. To this mixture, 14.6 g of 47% hydrobromic acid (0.09 mol) were added dropwise over 15 min. The reaction mixture was subjected to overnight

  stirring at room temperature, then 4 hours of heating

  fage at reflux. The organic phase was separated, dried and concentrated to give 13.1 g (85%)

of a solid white.

  Elementary analysis: calculated for C7H9BrN20:

C, 38.73; H, 4.18; N, 12.91

  found: C, 38.76; H, 4.47; N, 12.59.

  3-bromo-2,2-bis (cyanomethyl) -l-propyl tosylate

(3)

  To a mixture of 12.8 g (0.059 mole) of 3-bromo-2,2-bis (cyanomethyl) l-propanol and 29.5 g of pyridine, in

  a suitable container, a solution of 12.4 g (0.06 mole) of p-toluenesulfonyl chloride (chlorine) was added at a temperature between about 0 and about 5 ° C.

  tosyl rure) in 15 ml of chloroform as solvent. We

  subjected the reaction mixture to temperature

  ambient temperature for about a week, then it was poured into 500 ml of water to stop the reaction. The organic layer has been separated; it was washed with water, with dilute hydrochloric acid and with water; dehydrated over anhydrous and concentrated magnesium sulfate to give 17.9 g (81.7%) of a white solid, the point of which

fusion is 86.8 C.

  Elementary analysis: calculated for C14H 15BrSO3:

C, 45.29; H, 4.07; N, 7.55

  found: C, 45.24; H, 4.42; N, 7.09.

  2,2-bis (azidomethyl) -1,3-dicyanopropane (4) A 17.9 g mixture was heated to 65 C

  (0.048 mole) of 3-bromo-2,2 bis tosylate (cyanomethyl) -

  1-propyl and 50 ml of dimethyl sulfoxide, and 9.4 g (0.145 mole) of sodium azide was added thereto. The mixture was then heated to a temperature between 95

  and 98oC for 22 h, then poured into 800 ml of water.

  The aqueous phase was extracted with 3 x 25 ml of chloro-

  form, and washed with water to remove dimethyl sulfoxide. After dehydrating the solution on

  anhydrous magnesium sulfate, this solution was concentrated

  tion, which gave 6.4 g (65.3%) of a white solid, of which

  the melting point is 68.5 -69.5 C.

  Elementary analysis: calculated for C7H8N8

C, 41.51; H, 3.95; N, 54.88

  found C, 41.21; H, 4.37; N, 54.70 3,3-bis (azidomethyl) -glutaric acid (5) A solution of reflux was heated for 24 h

  29.6 g (0.15 mole) of 2,2-bis (azidomethyl) -1,3-dicyanopro-

  pane, 150 ml of water and 57.3 g (0.87 mole) of 85% potassium hydroxide; the solution was cooled and acidified with concentrated hydrochloric acid. The solid product was collected, washed with water and dried to give 23.7 g (67.5%) of product; Fusion point

123 -124 C.

  Elementary analysis: calculated for C 7H10 N604:

C, 34.71; H, 4.16; N, 34.70

  found C, 34.41; H, 4.67; N, 35.16.

  3,3-bis (azidomethyl) glutaryl chloride (6) To a mixture of 8.9 g (0.037 mole) of 3,3-bis (azidomethyl) glutaric acid, 15 ml of anhydrous benzene and 0.07 g of zinc chloride, 15.4 g (0.074 mole) of phosphorus pentachloride was added in portions over 1 hour while

  stirring to maintain the temperature of the reaction mixture-

  nel at a value between about 10 and about

   C. The reaction mixture was subjected to overnight agitation.

  room temperature, then filtered, and

  concentrated, which gave 10.3 g (100%) of a yellow solid.

  Elemental analysis: calculated for C7H8C12N602;

  C, 30.11; H, 2.87; CI, 25.45; N, 30.11

  found C, 30.59; H, 3.10; Cl, 24.48; N, 29.71.

  2,2-bis (azidomethyl) -propane 1,3-diisocyanate

(DIAMP)

  A solution of 9.3 g (0.14 mole) of sodium azide in 37 ml of water was cooled in an ice bath, and a solution of 5.0 g was added dropwise (0.018 mole) of 3,3-bis (azidomethyl) glutaryl chloride and 25 ml of ethylene dichloride. This reaction mixture was stirred for 10 min, then the second solution above was added. The organic phase was separated and dried over anhydrous magnesium sulfate. We have

  slowly heated the solution to 50 C, which caused the decomposition, with release of nitrogen, of the intermediate diazide. Finally, the solution was heated to reflux to complete the decomposition, and concentrated, to give 3.8 g (90%) of a yellow liquid.

  Elementary analysis: calculated for C7H8N802:

C, 35.59; H, 3.39; N, 47.46

  found C, 35.06; H, 3.37; N, 46.84.

  As previously stated, when used in

  energy urethane systems, the vulcani-

  sation of the present invention will influence the duration of

  pot life, i.e. the time available for the manu-

  retention of this agent between the mixing operation and the start of vulcanization until complete setting, which

  depends on the specific materials used, the temperature

  the size of the other components, such as fuel, etc. The mixing of the urethane generator system is normally carried out by operating at ambient temperature or at the higher temperature necessary to give a viscosity sufficiently low to allow thorough mixing. Depending on factors such as the time that one wishes to allocate to the vulcanization, the temperature of the vulcanization of the hardening can be varied.

  of the system. However, the temperature is typically maintained

  vulcanization rature between the vicinity of the temperature

  room temperature and 60 C (140 F), a preferred range is

  between 43.3 C and 54.4 C (between 110 and 130 F).

  The method according to the present invention for producing an energy urethane system, this system comprising at least one binder, a plasticizer, an oxidant and a fuel, comprises: (a) mixing a binder, a plasticizer , an oxidant and a fuel; (b) the introduction of a vulcanizing agent of

  azide diisocyanate type, 2,2-bis- 1,3-diisocy-.nate

  (azidomethyl) -propane; and (c) the vulcanization of this energy urethane system. In short, it can be said that a new azide diisocyanate has been developed as a vulcanizing agent, a

  process for its preparation and that of intermediates, and the use of this product in a vulcanization process.

  It goes without saying that the above description is presented for illustration only and is in no way limitative and

  that it is possible, within the framework of the above teachings, to make various modifications coming within the scope and the spirit of the invention.

Claims (30)

  1. Product which is 2,2-bis- 1,3-diisocyanate (azidomethyl) -propane.   2. Application of 2,2-bis 1,3-diisocyanate (azido-   methyl) -propane as an agent for the vulcanization of   energetic binders of urethane type.   3. Method for maturing and vulcanizing an urethane-forming energy system, this system comprising   a binder, a plasticizing urethane, an oxidant and a   bustible, process characterized in that it comprises:   (a) mixing a binder, a plastic urethane   tifier, an oxidant and a fuel;   (b) the introduction of 2,2-bis- 1,3-diisocyanate -   (azidomethyl) -propane as vulcanizing agent, and   (c) the vulcanization of said form energy system urethane mater.   4. Process for preparing 2,2-bis (azidomethyl) propane 1,3-diisocyanate, process characterized in that it   includes the operations of: (a) mixing and reacting the 3,3-bis (cyano-   methyl) oxetane with hydrobromic acid, to pro-   dilute 3-bromo-2,2-bis (cyanomethyl) -1-propanol; (b) combine and react 3-bromo-2,2-bis (cyanomethyl) -l-propanol, pyridine and p-toluene sulfonyl chloride, which makes it possible to obtain 3-bromo- tosylate 2,2-bis (cyanomethyl) -1-propyl;   (c) prepare a mixture of 3-bromo-2,2- tosylate   bis (cyanomethyl) -l-propyl and dimethyl sulfoxide, which incorporates sodium azide to cause   reaction to produce 2,2-bis (azidomethyl) -1,3- dicyanopropane;   (d) refluxing a solution of 2,2-bis (azi-   domethyl) -1.3 dicyanopropane and potassium hydroxide and produce 3,3-bis (azidomethyl) -glutaric acid; (e) preparing a reaction mixture of 3,3-bis (azidomethyl) glutaric acid, benzene, zinc chloride   and phosphorus pentachloride and to react this   diaper to prepare 3,3-bis (azidomethyl) chloride   glutaryl; and (f) combine 3,3-bis (azidomethyl) glutaryl chloride and ethylene dichloride, introduce this   seems in a sodium azide solution and carry out a reaction between these products to obtain the 2,2-bis (azidomethyl) propane 1,3-diisacyanate. 5. Method according to claim 4, characterized in that the hydrobromic acid used in step (a) is hydrobromic acid at 47%, and the reaction mixture was subjected to stirring overnight. at room temperature and then heated to reflux for 4 h. 6. Method according to claim 4, characterized in that, in step (b), chloride of   p-toluene sulfonyl in chloroform.   7. Method according to claim 4, characterized in that, in step (c), it was heated between 95 C and 98 C   for 22 h the reaction mixture formed of 3- tosylate   bromo-2,2-bis (cyanomethyl) -l-propyl, dimethylsulfoxide and sodium azide, then the mixture was poured into some water.   8. Method according to claim 4, characterized in that, in step (d), the solution of 2,2-bis (azidomethyl) -1,3-dicyanopropane and   of potassium hydroxide, cooled and then acidified   dified using a mineral acid.   9. Method according to claim 8, characterized in that the mineral acid is concentrated hydrochloric acid.   10. As a product, 3-bromo-2,2-bis (cyano- methyl) -1 propanol.   11. Process for producing 3-bromo-2,2-bis (cyano-   methyl) -l-propanol, characterized in that the 3, 3-bis (cyanomethyl) oxetane is mixed and reacted with acid hydrobromic.   12. Method according to claim 11, characterized in that the hydrobromic acid is hydrobromic acid ll aqueous at 47%, and in that the reaction mixture is subjected to a night of stirring at room temperature, then it is heated at reflux for 4 h.   13. As a product, tosylate, or p-toluene sulfo-   nate, of 3-bromo-2,2-bis (cyanomethyl) -1-propyl. 14. Process for producing 3-bromo-2,2-bis (cyanomethyl) -1lpropyl p-toluene sulfonate, characterized in that a mixture of 3bromo-2,2-bis (cyanomethyl) is combined and reacted - 1-propanol, pyridine and chloride p-toluene sulfonyl.   15. Method according to claim 14, characterized in that p-toluene sulfonyl chloride is used in a solvent.   16. The method of claim 14, characterized in that the reaction mixture was subjected to one week of stirring at room temperature then it was poured into water, and then a separation was carried out. of   the organic layer and a concentration thereof.   17. Method according to claim 15, characterized   in that the solvent is chloroform.   18. As product, 2,2-bis (azidomethyl) -1,3- dicyanopropane.   19. Process for producing 2,2-bis (azidomethyl) -   1,3-dicyanopropane, characterized in that a   mixture of 3-bromo- p-toluene sulfonate (or tosylate)   2,2-bis (cyanomethyl) -1-propyl and dimethylsulfoxide,   to which sodium azide is added for the reaction.   20. The method of claim 19, characterized in that it heats between 95 C and 98 C for 22 h the   reaction mixture formed from p-toluene sulfonate (or tosy-   late) of 3-bromo-2,2-bis (cyanomethyl) -1-propyl, of dimen-   thylsulfoxide and sodium azide, then pour the mix in water.   21. The method of claim 20, characterized in that, after pouring into water, the aqueous phase is subjected to an extraction with chloroform and it is   wash with water to remove dimethyl sulfoxide.   22. As product, 3,3-bis (azidomethyl) acid - glutaric.   23. Process for producing 3,3-bis (azido-   methyl) -glutaric, characterized in that it comprises the heating at reflux of a solution of 2,2-bis (azido-   methyl) -1,3-dicyanopropane and potassium hydroxide.   24. Method according to claim 23, characterized   in that the solution of 2,2-bis (azidomethyl) was submitted -   1,3-dicyanopropane and potassium hydroxide after 24 hours of heating at reflux, then it was cooled and then acidified with a mineral acid.   25. The method of claim 24, characterized in that the mineral acid is concentrated hydrochloric acid.   26. As a product, 3,3-bis chloride (azido-   methyl) -glutaryl. 27. Process for producing 3,3-bis (azidomethyl) glutaryl chloride, characterized in that it comprises the preparation of a reaction mixture comprising 3,3-bis (azidomethyl) glutaric acid, benzene, zinc chloride and phosphorus pentachloride, and reacting this mixture to produce 3,3bis chloride (azidomethyl) glutaryl.   28. The method of claim 27, characterized   in that the reaction mixture has been cooled to   maintain a reaction temperature within an hour between 10 C and 20 C.   29. Process for producing 2,2- 1,3-diisocyanate   bis (azidomethyl) -propane, characterized in that it comprises   the combination of 3,3-bis (azidomethyl) gluta- chloride   ryle and ethylene chloride, the introduction of this en-   seems in a sodium azide solution and the realization   tion of a reaction between these components to form 2,2-bis (azidomethyl) -1.3 propane diisocyanate, a compound obtained by passing through a non-isolated intermediate of the di (acyl azide) type. 30. The method of claim 29, characterized in that causes the decomposition of the di (acylazide)   intermediate by slowly heating up to 50 C the solu- reaction.