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Ferrocene derivatives

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US3755311A
US3755311A US3755311DA US3755311A US 3755311 A US3755311 A US 3755311A US 3755311D A US3755311D A US 3755311DA US 3755311 A US3755311 A US 3755311A
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Prior art keywords
burning
rate
ferrocene
ferrocenylmethylene
propellant
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Galler R Zimmer
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US Secretary of Navy
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US Secretary of Navy
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00Metallocenes
    • C07F17/02Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46Two or more oxygen, sulfur or nitrogen atoms
    • C07D239/60Three or more oxygen or sulfur atoms
    • C07D239/62Barbituric acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D263/00Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings

Abstract

ARE DISCLOSED WHEREIN R is O, NR'' and S and each R'' is hydrogen, lower alkyl, phenyl, cyano and nitro.

Compounds useful as burning rate catalysts for solid propellants characterized by low volatility and having the formula

Description

Unite States Zimmer-Galler tet 1 [451 Aug. 28, 1973 FERROCENE DERIVATIVES [75] Inventor: Roswitha Zimmer-Galler,

Washington, DC.

[73] Assignee: The United States of America as represented by the Secretary of the Navy, Washington, DC.

[22] Filed: Sept. 19, 1967 [21] Appl. No.: 670,018

OTHER PUBLICATIONS Levina et al., Russian Chem. Reviews, (English Translation), Vol. 29, PP- 446 to 452 (1960).

Primary ExaminerLeland A. Sebastian Attorney-R. S. Sciascia and J. A. Cooke S 7 ABSTRACT Compounds useful as burning rate catalysts for solid propellants characterized by low volatility and having the formula are disclosed wherein R is 0, NR and S and each R is hydrogen, lower alkyl, phenyl, cyano and nitro.

4 Claims, 1 Drawing Figure PATENTEDnucza ms 3. 755.; 31 l BURNING RATE VS. PRESSURE OF POLYESTER RDX- PROPELLANT- O 0 Burbiturylferrocenylmefhene A No modifier 0.05 I I I INVENTOR Roswifha Zimmer -GaHer FERROCENE DERIVATIVES BACKGROUND OF THE INVENTION This invention relates generally to a novel burning rate catalyst and more particularly to a novel burning rate catalyst characterized by very low volatility and which is especially useful for controlling the burning rate of high energy composite type propellants.

Solid propellant compositions are generally classed as being either composite, if they consist of a mixture of a solid oxidant in a matrix of a resinous or elastomeric fuel-binder composition, or homogeneous, if they contain in a single molecule all the required fuel and oxygen necessary for combustion.

The type of propellant composition useful for a given application often is directly dependent upon the burning characteristics required by the particular application. For example, to drive the turbo-pump feed system of the fuel injector of a reaction motor, it is desirable to use a high gas producing propellant characterized by slow burning and low flame temperature; a composition often referred to as a gas generating propellant or simply gas generator. For such applications, it would be desirable to use nitramine oxidant containing composite propellants because of their generally good burning properties, high energetics and high density which permits higher energy release per unit volume. However, due to their exceptionally low burning rates at the operating temperatures and pressures normally required, the nitramines have not been successfully adapted for gas generator applications.

Burning of a solid propellant is a localized phenomena in that it occurs only on the exposed surface of the propellant grain. The burning surface regresses by burning parallel layers in a direction perpendicular to the surface in accordance with Saint-Roberts or Veilles Law;

where r is the burning rate; 11", b" and n are constants and P is pressure. The constant n is referred to as the burning rate exponent.

It has long been known that the Veille Law constants can be adjusted favorably by adding certain additives, known as burning rate catalysts, to the composition. These additives tend to accelerate the exothermic reactions at the burning surface thereby acting to increase the burning rate of the composition.

Previously, however, no catalyst has been found which is entirely satisfactory for increasing burning rates of nitramine containing composite propellants. Ferrocene compounds, for example, although long known to be effective burning rate catalysts for many compositions, have not been wholly acceptable for composite propellants because of their undesirably high volatility at moderate storage temperatures. Because of this high volatility, compositions catalyzed by ferrocene compounds possess a continually changing burning characteristic as a function of storage time due to vaporization of the ferrocene compounds from the compositions.

It would be desirable, therefore, to provide a burning rate catalyst which is essentially non-volatile at normal storage temperatures and which may be used to control the burning rate of composite propellants, such as nitramine containing composite propellants.

SUMMARY OF THE INVENTION It is therefore an object of this invention to provide a relatively non-volatile burning rate catalyst which will accelerate the burning rate of composite propellants without deleteriously affecting their storage stability. It is also an object of this invention to provide a burning rate catalyst which is efiective in accelerating the burning rate of nitramine oxidants such as RDX and HMX.

Finally it is an object of this invention to provide a method for producing a novel non-volatile ferrocene burning rate catalyst useful for accelerating the burning rate of composite type propellants.

These and other objects are achieved herein by providing the novel burning rate catalysts of the formula:

wherein R is selected from the group consisting of 0, NR and S, each R being selected from the group consisting of hydrogen, lower alkyl, phenyl, cyano, and nitro.

BRIEF DESCRIPTION OF THE DRAWING One of the many advantages of the foregoing burning rate catalyst can best be appreciated by reference to a drawing.

The solitary FIGURE is a graph illustrating the change in burning rate as a function of pressure for a polyester RDX type nitramine containing propellant.

DESCRIPTION OF THE PREFERRED EMBODIMENTS invention include S-ferrocenylmethylene-Z- phenylimino-4,6-dihydroxy pyrimidine 5 ferrocenylmethylene thiobarbituric acid, 5

ferrocenylmethylene-Z-methyliminc-4,6-dihydroxy pyrimidine, 5-ferrocenylmethylene-2-ethylimino-4,6- dihydroxy pyrimidine, S-ferrocenylmethylene-Z- cyanoimino-4,6-dihydroxy pyrimidine, 5- ferrocenylmethylene-Z-nitroimino-4,6-dihydroxy pyrimidine and S-ferrocenylmethylene barbituric acid.

Because of the very low volatility (Table II) of these compounds, they will not vaporize readily from the composition and hence may be stored almost indefinitely without significantly affecting the burning characteristics of the propellant as a function of storage time; a problem characteristic of the prior art ferrocene burning rate catalysts. While the ferrocene compound of this invention are useful catalysts for a wide variety of propellant compositions, they are particularly useful for accelerating the burning rate of composite type propellants. The drawing is a graph of the log of the burning rate of a polyester-RDX composite propellant as a function of the log of the operating pressure. The slope of the burning rate-pressure curve is the burning rate exponent n. In the system illustrated, the burning rate exponent of the unmodified propellant (curve 2) is 0.72 whereas that containing 1 percent S-ferrocenylmethylene barbituric acid (curve 1) is 0.61. As will be noted, the immediate ferrocene catalyst has a greater effect on the burning rate at lower operating pressures of about 500 psi, than at the higher operating pressures of about 1000 psi. Pressure was determined by burning the propellant in a suitable inert atmosphere in a pressurized bomb and burning rate was determined by microwave detection means whereby microwaves are reflected from the burning surface to a detecting device and the standing wave front so created is measured as a function of time.

Essentially similar results are obtainable with the other ferrocene compounds disclosed herein and with other oxidants other than the nitramines. For example, desirable burning acceleration can be obtained with ammonium perchlorate or ammonium nitrate containing propellants.

The particular binder selected for the composite propellant is not critical to the functioning of these catalysts and a wide variety may be used in the compositions with similar results. For example, operable binders include, asphalt, the phenolic resins, hydrocarbons TABLE I 71% RDX, 25% polyglycoladlpate Modifier T CQ) unmodified 190C 1% ferrocene 167C 1% S-ferrocenylmethylene barbituric acid 176C Having generally described the invention, the following examples are provided herein for purposes of illustration only and are not intended to be binding in any manner.

EXAMPLE A solution of 3 g (0.024 mole) of barbituric acid in 100 ml water was added to 4.3 g (0.02 mole) of ferrocene-aldehyde in 100 ml ethyl alcohol. The reaction resulted in the precipitation of a blue-violet colored product which after filtration was washed with water and ether. By recrystallization from ethyl alcohol blue needles were obtained which decomposed 294C. (Determined by Differential Thermal Analysis).

C 11 N Fe Anal. calcd for The yield wag 6.15pm).

The following compounds can also be prepared in essentially the same manner except using the corresponding active methylene containing compound dissolved in a suitable alcohol. Preferably the reactants are used in approximately equi-molar amounts. Among those reactants which may be reacted with ferrocene aldehyde include: Z-phenylmalonyl guanidine, thio-barbituric acid, 2-methyl-malony1 guanidine, 2-ethylmalonyl guanidine, 2-cyanomalonyl guanidine and 2-nitromalonyl guanidine. Condensation of these reactants with ferrocene aldehyde provides respectively; 5- ferrocenylmethylene-2-phenylimino-4,6-dihydroxy pyrimidine, S-ferrocenylmethylene thiobarbituric acid, 5-ferrocenylmethylene-2-methylimino-4,6-dihydroxy pyrimidine, 5-ferrocenylmethylene2-ethylimino-4,6- dihydroxy pyrimidine, S-ferrocenylmethylene-Z- cyanoimino-4,6-dihydroxy pyrimidine, and 5- ferrocenylmethylene-2-nitroimino-4,6-dihydroxy pyrimidine.

Table 11 describes the vapor pressure of barbiturylferrocenylmethene as compared with the prior art burning rate catalyst; ferrocene.

TABLE II Vapor Presures of Ferrocene Temperature Pressure Q mm Hg 50.0 0.09 63.1 0.27 70.8 0.40 80.5 0.70 92.0 1.47 97.0 2.13

Vapor Pressures of 5ferrocenylmethylene barbituric acid Temperature Pressure "C m Hg 40.0 0.016 55.0 0.025 70.0 0.034 85.0 0.043 98.5 0.055

As will be noted from the foregoing Table, the vapor pressure of 5-ferrocenylmethylene barbituric acid at normal storage temperatures is significantly lower than that of ferrocene. This difference in volatility reduces the tendency of the catalyst to vaporize from its propellant compostion thereby reducing the tendency for the burning characteristics of the propellant to change with storage time. Having described the invention, it will be apparent to those skilled in the art that many modifications and changes can be without departing from the scope and spirit thereof.

I What is claimed as new and desired to be secured by Letters Patent of the United States is:

1. A compound represented by the general formula:

wherein R is selected from the group consisting of 0, 3. The compound of claim 1 of the formula NR and S, each R being selected from the group consisting of hydrogen, lower alkyl, phenyl, cyano and ni- 2. The compound of claim 1 of the formula 5 c l Nli 0 ,"-Cu: cayw g N6 k e 7"CI'I=C c=rw T Fe wherein R is selected from the group consisting of hydrogen, lower alkyl, phenyl, cyano and nitro.

wherein R"is selected from the group consisting 0H) 4, Th c ound of claim 1 which is 5- and S- ferrocenylmethylene barbituric acid.

Claims (3)

  1. 2. The compound of claim 1 of the formula
  2. 3. The compound of claim 1 of the formula
  3. 4. The compound of claim 1 which is 5-ferrocenylmethylene barbituric acid.
US3755311A 1967-09-19 1967-09-19 Ferrocene derivatives Expired - Lifetime US3755311A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5218166A (en) * 1991-09-20 1993-06-08 Mei Corporation Modified nitrocellulose based propellant composition
US5602361A (en) * 1994-03-18 1997-02-11 Oea, Inc. Hybrid inflator
US5616883A (en) * 1994-03-18 1997-04-01 Oea, Inc. Hybrid inflator and related propellants
US5630618A (en) * 1994-03-18 1997-05-20 Oea, Inc. Hybrid inflator with a valve
US5695216A (en) * 1993-09-28 1997-12-09 Bofors Explosives Ab Airbag device and propellant for airbags
US5711546A (en) * 1994-03-18 1998-01-27 Oea, Inc. Hybrid inflator with coaxial chamber
US5821448A (en) * 1994-03-18 1998-10-13 Oea, Inc. Compact hybrid inflator
US6039819A (en) * 1982-03-04 2000-03-21 Atlantic Research Corporation Solid propellant containing ferrocenyl phosphine derivatives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271402A (en) * 1966-09-06 Carbon-z-thiobarbituric acids
US3324125A (en) * 1965-02-23 1967-06-06 Takeda Chemical Industries Ltd Barbituric acid derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271402A (en) * 1966-09-06 Carbon-z-thiobarbituric acids
US3324125A (en) * 1965-02-23 1967-06-06 Takeda Chemical Industries Ltd Barbituric acid derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Levina et al., Russian Chem. Reviews, (English Translation), Vol. 29, pp. 446 to 452 (1960). *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6039819A (en) * 1982-03-04 2000-03-21 Atlantic Research Corporation Solid propellant containing ferrocenyl phosphine derivatives
US5218166A (en) * 1991-09-20 1993-06-08 Mei Corporation Modified nitrocellulose based propellant composition
US5695216A (en) * 1993-09-28 1997-12-09 Bofors Explosives Ab Airbag device and propellant for airbags
US5602361A (en) * 1994-03-18 1997-02-11 Oea, Inc. Hybrid inflator
US5623116A (en) * 1994-03-18 1997-04-22 Oea, Inc. Hybrid inflator and related propellants
US5627337A (en) * 1994-03-18 1997-05-06 Oea, Inc. Hybrid inflator and related propellants
US5675102A (en) * 1994-03-18 1997-10-07 Oea, Inc. Method of assembling a hybrid inflator and related propellants
US5679915A (en) * 1994-03-18 1997-10-21 Oea, Inc. Method of assembling a hybrid inflator
US5616883A (en) * 1994-03-18 1997-04-01 Oea, Inc. Hybrid inflator and related propellants
US5711546A (en) * 1994-03-18 1998-01-27 Oea, Inc. Hybrid inflator with coaxial chamber
US5821448A (en) * 1994-03-18 1998-10-13 Oea, Inc. Compact hybrid inflator
US5630618A (en) * 1994-03-18 1997-05-20 Oea, Inc. Hybrid inflator with a valve

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